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\ F E R R A N T IDesigned for industrial ~ s e , this. . .. - .immediate readings of viscosityP O R T A B L E V I S C O M E T E Rcoaxlal cylinder viscornete: giveswhen the cylindersare immersedl o w , medium a n d h i s hin liquids and serni-iiquids.Three models are avai!able forviscosities.FERRANTI hrst rnto the h t U P 3FERRANTI LTD. MOSTON. MANCHESTER 10Tcl: FAllsworth 2071London Office: MILLBANK TOWER - MILLBANK - S.W.I. VlCtoria 661 IF I242BOOKSSCIENTIFIC & TECHNICALLARGIE STOCK OF BOOKS on the Biological, Physical,Chemical and Medical Sciences supplied from stock, or obtained to order.FOREIGN DEPARTMENT. Books not in stock obtained toorder with the least possible delay.LENDIN6 LISRARYSCIENTIFIC AND TECHNICALAnnual Subscription from L2 5s.Prospectus post free on application.Bi-monthly list of New Books and New Editions added to the Librarysent post free to any address regularly.THE LIBRARY CATALOGUE, revised to December, 1963.PartI, the index of Authors and Titles is available. Part 11, the indexof Subjects is in the Press and will be published in late 1965. Thecomplete catalogue (2 parts), to Library Subscribers, LI. 10s.; tonon-subscribers, L2. 15s. net; postages 4s. 3d.H. K. LEWIS & CO. LTD. 136, Gower Street, WCi. EUSton 4282d S K THE CHEMICAL SUPPLY CO LFDfor details of the chemicals they are manuficturingEster Solyents Alkyl & Aryl Ester PlasticisersFormaldehyde & HexamineSpecial Plastic Gra&sCadmium Colours Aromatic ChemicalsMolybdic Products Copper FungicidesFull technical details and sampleswill be sent on requestTHE CHEMICAL SUPPLY CO LTD7 IDOL LANE, EASTCHEAP, LONDON EC3Tel: Mansion House 6854Grams: Kemsupply, Phone London1Acid resisting, alkali resisting, heatresisting, mechanically strong,Pfaudler glassed-steel equipment isthe perfect answer to the corrosionmenace in chemical plant.The Pfaudler range, which includesstorage, processing and reactionvessels for high and low pressures,condensers, receivers, evaporatingpans, transport tanks, pipes andvalves, has the following importantadvantages :Highly resistant to most acids aridalkalis.Can be used at temperatiires lip to450°F for some applications.Product does not adhere to linitrg-undesirable build-up of poij.mPrizcdproducts eliminated.No catalytic effects.0 Ease of cleaning ensures consloritpiwity of producr and low maintritaiicecosts.Flexibility of applicatioir-proccs.~\tsand chemicals can be charigtd atshort notice.HENRY BALFOUR& CO.LTD.A member of Pfaudler Permutit I n cLeven, Fife. Telephone : Leven 1371.Artillery House, Artillery RowLondon, S.W.l. Telephone: ABBey 741 1...11Fe DARTON & COe LTD.Established I834WATFORD, ENGLANDDistant Recording ThermographMERCURIAL BAROMETERSMANOMETERS HYGROMETERSBAROGRAPHS HYGROGRAPHSTHERMOGRAPHSAvailable through your Laboratory SupplierMAKERS OFpH TEST BOOKS andINDICATOR PAPERSSClENCE AND INDUSTRYDetails and prices from :iModern Aspects of €lectrochemistry-3edited by J.0’ M. Bockris, D.Sc., Ph.D., D.I.C., F.R.I.C.and B. E. Conway, D.Sc., Ph.D., D.I.C., F.R.I.C.464 pages i llustrated 95s.Physico=Chemical Calculations in Scienceand Industryby H. Fromherz, B.Sc., Ph.D. Translated by G. H. Kinner, B.Sc.373 pages illustrated 87s. 6d.Stereochemistry: the static principlesby J. Grundy, B.Sc., A.R.I.C.237 pages i I lustrated 35s.Chemotherapy of Tuberculosisedited by V. C. Barry, D.Sc.289 pages illustrated 79s. 6d.INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRYI67 pages70 pagesOrganic Photochemistryi I lustrated 40s.The Reactivity of Solidsillustrated 20s.Organo-Phosphorus Compounds198 pages illustrated 45s.The Chemistry of Natural Products-3198 pages i I lustrated 60s.Dissociation Constants of OrganicBases in Aqueous SolutionCompiled by D. D. Perrin522 pages E788 Kingsway, London, W.C.2BUTTERWORTHSIE. A. Mwl-HughesSHORT COURSE OF PHYSICBL 1 CHEMISTRYIntended for students of chemistry at universities and techkalcolleges, this boob; gives a compacz treatmem of physical chemistry,in as many of its aspects and applications as can be contained in ashort volume. The author writes on a firm basis of accurate data(much of the experimental information is contributed at first hand)and covers the modern theoretical. approaches-the kinetic theory,thermodynamics, statistical mechanics.Pubhkution: Spring 1966 Probable price: 45s netAnnual Reports on theProgress of ChemistryBack Numbers (less certain volumes now out of print)are available-Volumes (1904) to LX (1963)AlsoCollective Index of Volumes I to XLVIInquiries are invited by:TEECHEMICAL SO€"YBurlington Hause . London, W.

ISSN:0365-6217    

DOI:10.1039/AR96461FP001

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

ANNUAL REPORTSON THEPROGRESS OF CHEMISTRYGENERAL AND PHYSICAL CHEMISTRY1. INTRODUCTIONBy P. G. Ashmore(Department of Chemistry, A!!anclzester University Faculty of Technology)THIS Section of the Annual Reports follows the pattern of previous yearsby reviewing progress in five active fields. We describe the principaladvances announced during the past year or, if the topic has not beencovered in recent Annual Reports, over a longer period.The electronic spectra of diatomic molecules were discussed by Barrowand Merer in the Reports for 1962, but work on polyatomic molecules hasnot been reported since 1960 when Mills discussed the determination of thestructure of small polyatomic molecules. There has been no lack of workon electronic spectra, however, and this year Walsh has confined his reportto small polyatomic molecules, though included in the Organic Section ofthis Report are accounts of investigations on the electronic structure ofmolecules of various sizes.Electron spin resonance was reported in 1962, but such an active fieldof investigation deserves at least a biennial report.The problem of energy transfer between molecules in various energystates, and between atoms, radicals, and molecules, lies a t the heart of thedetailed molecular interpretation of reaction rates.Callear’s article coversrecent work on the exchange of energy between molecules and atoms orother molecules, and it is hoped in a later report to deal with energy ex-changes involving radicals.The great output of papers on solutions of electrolytes was noted lastyear by two articles, but the topic of electrode processes has not beencovered since Randles’s report in 1959.Thus Parsons’s report, dealing withthe electrode double layer and elect.rode reactions, covers the work of severalyears.Murtirner’s report on thermochemistry concentrates mainly on the periodDecember, 1963, to December, 1064, with some reference to important topicswhich have developed since the last report on this topic by Skinner in 1960.Thescope of the subjects has grown, and it seems appropriate to aim to coverthem in reports spread over a few years. Accordingly, this year’s reportby Bond concentrates on catalysis by metals, without attempting to coverthe more physical aspects of studies of chemisorption on metals.Adsorption and catalysis were last reported by Kemball in 19562.ELECTRONIC SPECTRA QF POLYATONIC MOLECULESBy A. ID. Walsh(Chemistry Department, University of St. Andrews, Queen's College, Dundee)THE last occasion on which a review of work on the electronic spectra ofpolyatomic molecules appeared in AnnuaZ Reports was in the Volume for1960. The present Report will, therefore, deal, not with 1964 alone, but withthe four-year period from the end of 1960 to the end of 1964. As a con-sequence, some limitation of the breadth of the Report is necessary; thatadopted is to deal only with gaseous spectra and hence only with com-paratively small molecules.Reviews that have appeared elsewhere during the four-year periodinclude those in ref.1-4.We shall use Walsh's well-known orbital " correlation diagrams " 5 , 6as a basis for discussion of spectra.AH, Molecules.-(a) Five electrons: BH,. On the assumption that thepresence of one electron in the (al--nU) orbital represented on the relevanfcorrelation diagram by a curve that descends steeply from right to leftis sufficient to cause bending (as in the first excited state of PH, or in theground state of NO,; see below), the BH, free radical should be bent in itsground state and should have a low-energy first electronic transition. Onthe other hand, the first excited state should be linear. The absorptiontransition should, therefore, (a) be represented as- - - (q?)2(Gi)2(nu)', 21L f- * (a1)2(b#(aJ*, *A1,( b ) be allowed, ( c ) arouse a progression in the upper-state bending vibration,and, therefore, ( d ) occupy an extensive region of the spectrum.Bauer, Herzberg, and Johns7 briefly report that a spectrum due toBH, has been observed in the red and the nestr-infrared region.That aspectrum should be observed at such long wavelengths automatically meansthat the ground state must be bent. One awaits with interest a detailedanalysis of the spectrum.AlH, should possess a similar spectrum.(b) Six ekctrons: CH,, SiH,. From the relevant correlation diagram,the ground state of CH, is expected to be either singlet and bent (lA1),or triplet and linear (3C,). Experimentally, the existence of these twostates lying close in energy has been confirmed and the triplet linear formhas been shown, in fact, to lie the lower.81 P.G. WWson, J . MoE. Spectroscopy, 1961, 6, 1.2 D. A. Ramsay, Ann. Rev. Phys. Chenz., 1961, 12, 255.D. A. Ramsay, " Dekermination of Organic Structures by Physical Methods ",4 G. Herzberg, 12th Spiers Memorial Lecture, Discuss. Farday Soc., 1963, 35, 7.Academic Press, Inc., New York, 1962, Vol. 11, p. 245.A. D. Walsh, J . Chem. Soc., 1953, 2260, 226G, 2288, 2396, 2301, 2306.A. D. Walsh, Photoelectric Spectromet. Group Bull., 1961, No. 13, p. 348.7 S. H. Bauer, G. Herzberg, and J. W. C. Johns, J . Mol. Spectroscopy, 1964,13,256.8 G. Herzberg, Bakerian Lecture of the Royal Society, Proc. Roy. Soc., 1961,A , 262, 291WALSH: ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 9The singlet bent form, as expected, Is associated with a strong absorptionin the visible and the near-infrared region. This absorption has beenanalysed in detail by Herzberg and Johns9 who have pointed out its possibleimportance in the spectra of comets and the major planets.It is clearfrom the analysis that the major change in geometry caused by the electronictransition is it large increase in apex angle to a linear or nearly linear upperstatme. Preliminary arguments 8 yield the value 103" for the apex angle int'he lower state. The analysis as a whole fits very well the detailed pre-dictions from the correlation diagram. A second (weaker) absorptionsystem of singlet CH, is reported 8,9 to occur around 3400 A; Herzbergsuggests that it 2-electron jump may be responsible, but definite interpretationmust await further work.The known absorption spectrum of the triplet linear form of CH_ 1' ies, asexpected, wholly in the vacuum-ultraviolet. The spectrum starts witha band group a t 1415 A, followed by another a t 1306 A and then two more.I*The strongest features in each group fit the Rydberg series formula:R(fi - 0.12)2; = 3-6 Y (ern.-') = 83851 -and hence they yield the first ionization potential of linear CH, as 10-396 ev.loThis value does not agrze with earlier values (e.g., 11.82 & 0.5 ev 11) obt,ainedby electron-impact experiments, but the fit of the four band groups in theRydberg formula given above is so good that there can be little doubt ofthe correctness of the spectroscopic value.* The main band of the 1415 8group is proved t o be a CcC transition.Since the ground state is 3C+,, theupper state (for the transition to be allowed) must, therefore, be 3C-u. Ofthe various possible Rydberg orbitals, only ( d n g ) yields a 3Z-u upper state.The 1415 band is thus uniquely fixed as the n = 3 member of a Rydbergseries of parallel transitions to . . . (7~,~)(3dn,), 3C-u upper states. Thereshould, however, be other allowed Rydberg series. Transitions of anelectron from the (nu) orbital to p Rydberg orbitals should be forbidden, buttransitions t o (nsa,) Rydberg orbitals should be allowed. The first of these,i.e., the perpendicular transition to the . . . (nu)(3sa,), 3rZ, state, should liefar to long wavelengths of 1415 &&-perhaps, from correlation with thespectrum of the united atom (oxygen),12 around 2000 8.Presumably, thefailure of the expected long-wavelength Rydberg transition t o appear isdue to the attainment of insufficient concentration of CH,. It may bea G. Hcrzberg and J. 137. C . Johns, Jit6rn. Roy. SOC. Likge, 1962, 7, 117.lo G. Herzberg, Cunad. J. Phys., 1961, 39, 1511.l1 E. W. C . Clarke and C . A. XcDowell, Proc. CJzem. SOC., 1960, 69.l2 A. D. Walsh, unpublished work.* If the CH,+ ion is linear, the Rydberg series converges to the lowest 21T, stateof the ion. In such a state, a Renner-Teller splitting is expected and, if this splittingwere large enough, i t could lead to the result that one componeiit of the z l T u state,has a potential minimum in a bent configuration, while the other (higher) componentremains with a minimum in the linear coilfiguration.If this happened, the limit ofthe observed Rydberg transitions (which have no accompanying vibrational structureand must, therefore, proceed to the linear component of CH,+) would not representthe lowest ionization potential. HerzberglO marshals arguments against the possi-bility that the lowest state of CI&+ is bent as a result of the Renner-Teller effect.though it should be remembered that the recent discovery that the lowest state ofBH, (which is isoelectronic with CH,+) is bent weakens some of these arguments10 GENERAL AND PHYSICAL CHEMISTRYthat the fist Rydberg transition will turn out to be represented, as in thespectrum of H,O, by a continuum that requires a somewhat higher appear-ance pressure than do the later Rydberg transitions.If water were a veryscarce commodity and only low concentrations of it could be attained, itsspectrum would appear not to start until 1240 8, whereas, in fact, the firstRydberg absorption is known to peak at 1655A. There should also beallowed perpendicular Rydberg transitioiis to (do,) and (dd,) orbitals.Assuming (as is probable for 3d orbitals and even more probable for 4dorbitals) only small splittings of the d atomic orbital into a,, n,, and 6,molecular orbitals, there should be two I1 -4 transitions near 1415 8 andanother two near to 1306 8. Herzberg suggests that these transitions arerepresented by line-like features on the short-wavelength side of the mainbands in each observed band groups. For the 1415 A group, these featureslie at 1410 and 1397 A.If Herzberg’s suggestions are correct, the implica-tion is that a (dn,) orbital is more tightly bound than the corresponding(do,) or (dd,) orbital. Coulson and Stamper,l3 in a theoretical paper, couldreach no firm conclusion as to where the (do,) orbital lay in relation to theother two, but calculated the (dn,) orbital to be less tightly bound than the(dd,)-which is the opposite of Herzberg’s implication. On simple groundsof penetration, one might have expected the (do,) orbital to be more tightlybound than the (dn,) orbital, and the latter to be more tightly bound than(dd,), because the o, n, and 6 orbitals have, respectively, 0, 1, and 2 nodalplanes containing the H-C-H axis.Coulson and Stamper’s order dis-agrees with this; Herzberg’s order half agrees and half disagrees with it.Further work is clearly necessary.Attempts to find a spectrum of SiH, have so far been only partiallysuccessful.~4 No spectrum of the expected triplet linear form has been found.However, a new absorption system found after the flash photolysis of phenyl-silane is very similar to the bands of singlet, bent CH, and may representthe corresponding transition of SiH,.(c) Seven electrons: NH,, PH,. Dressler and Ramsay l5 analysed ingreat detail the visible absorption bands of NH,. It is remarkable that theground-state apex angle was found to be 103’20’ & 30’, which is virtually thesame as that reported later for the ( C G ~ ) ~ ( ~ , ) ~ ( C C ~ ) ~ , lAl state of CH, (see above)and closely similar to that of the ground state of H,O (104’27‘).Accordingto the AH, correlation diagram, the apex angle in the ground state of H,O+and in the lowest singlet state of H,02+ should be virtually the same as inthe ground state of H,O. Since H,O+ is isoelectronic with NH,, andH,02+ is isoelectronic with CH,, the implication seems to be that the AH,correlation diagram is, not only qualitatively, but also quantitatively muchthe same whether A is C, N, or 0.According to the analysis by Dressler and Ramsay, the upper state ofthe NH, absorption transition is linear. On the other hand, for the corres-ponding transition of PH,16 there is evidence3 (obtained by comparisonl3 C.A. Coulson arid J. G. Stamper, MoZ. Php., 1963, 6, 609.l4 G. Herzberg, ICSU Rev., 1962, 4, 179.l5 K. Dressler and D. A. Ramsay, Phil. Trans., A , 1959, 251, 553.l6 D. A. Ramsay, Nature, 1956, 178, 374WALSH: ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 11of the spectrum of gaseous PH, with that of PH, trapped in solids at 4 . 2 " ~ )that the upper state is non-linear. Supporting evidence for this comes froma particularly interesting theoretical paper by Dix0n.l' Dixon investigatesthe problem of what happens to the vibrational energy level pattern whena bent triatomic molecule has sufficient vibrational energy to overcome thepotential barrier to linearity. Using a harmonic potential modified by anexponential hump [a exp (-pq2)], he shows that, for a wide range of theparameters a and 18, a plot of the vibrational spacing for K = 0 levels againstthe vibrational energy shows a sharp change in slope at an energy corres-ponding to the potential maximum a t the linear configuration.The ex-perimental data for PH, yield just such a plot with a sharp change in slopeat m. 24,000 cm.-l above the ground state. This suggests rather stronglytha.t the first excited state of PH, is bent and that, if the first observedPH, band (at 18,000 cm.-l) is the OOOt000 band, the height of the potentialhump in this state is ca. 6000 cm.-l. Dixon goes on from this to show thatthe apex angle in the excited state is probably close to 120".The similarity of the first excited state (2AJ of NH, and the upper state(lBJ of the singlet CH, absorption in being linear or nearly linear is notperhaps surprising in view of the near-equality of the apex angles in theground state of NH, and in the lA, state of CH,; but a problem that requiresclarification is '' why should the ground state of BH, and the first excitedstate of PH, be bent and thus differ in shape from the 2A1 state of NH2a.nd the lB1 state of CH, ? " All these four states have a single electron inthe (al-nu) orbital whose occupation is particularly connected with bending.NO, is not a strictly comparable molecule, but it too, in its ground state,has a single electron in an (al-nu) orbital, which is evidently sufficient tomake the molecule bent.A problem similar to that posed above ariseswith the shapes of AH, molecular states (see below).Factors involvedprobably include the magnitude of the p s promotion energy in the variousA atoms and the influence of d orbitals when A is not in the first row of thePeriodic Table.(d) Eight eEectrons: H,O, H,S. The only region of the absorptionspectrum of H,O which shows sharp rotational structure is that below1240 8, where strong bands occur associated wit,h Rydberg Series leadingt'o the well-established first ionization potential. Johns has photographedunder high resolution the 1240 8 bands of both H,O and D,O. His workestablishes, from the rotational structure, that the 1240 A band representsa transition polarized parallel to the axis of greatest moment of inertia.Since the ground state has the configuration(ul)z(~~)2(~~)2(~l)2, %,the upper state must have B, symmetry and, therefore, the orbital towhich an electron is transferred must have a, symmetry.Various con-siderations leave no doubt that the upper orbita,l is in fact (3pa,). Thedegeneracy of the atomic (3p) orbital must be split in the lowered symmetry17R. N. Dixon, Tra.ns. Paraday SOC., 1964, 60, 1363.la J. W. C. Johns, Canad. J . Phys., 1963, 41, 20912 GENERAL AND PHYSICAL CHEMISTRYof the H20 molecule. Transitions to the (3p4 and (3pb,) components areallowed; that to the (3pb2) component is forbidden. By elimination, itbecomes clear that a separate electronic transiOion occurring close to the12408 band but at somewhat shorter wavelengths (at 1219A) is that tothe (3pb1) upper orbital.I n other words, the 3p degeneracy is measurablysplit and the (3pa1) is mare tightly bound than the ( 3 ~ 4 ) orbital. Thisagrees with the order (3pb2 < 3paI < 3 9 , ) calculated by La Paglia.lgThe degeneracy of the atomic (3d) orbital should also be split, yieldingfour allowed transitions. Johns suggests that under the resolution hithertoused the d-degeneracy has not been measurably split, all four allowedtransitions being represented by a, band a t 1115 8. However, the d-degeneracy is measurably split in other small molecules (see, e.g., CH, above)and, while the 1115 A band undoubtedly represents one of the allowedtransitions to d upper orbitals, (i) a band at 1128 8 thought by Johns torepresent transition t o the (4s) orbital may in reality represent another ofthe d transitions, and (ii) the remaining two allowed d transitions, togetherwith the (4s) transition, may underlie certain vibronic bands accompanyingthe 1240 and 1219 A electronic transitions.20 Clearly, extension of thehigh-resolution work to the very difficult region lying a t wavelengthsshorter than 1240 A is most desirable.The rotational constants obtained from the analysis of the 1240 A bandsshow that the changes brought about, by the transition, in the apex angleand 0-H bond length are small (ca.2" and ca. 0.05 8, respectively). Thiswas to be expected for Rydberg excitation of an electron from the (b,)ground-state orbital and provides experimental evidence for the statementmade above that the apex angles in the ground states of H20+ and H20should be about the same.Absorption and photoionization cross-sections of H20 in the region1110-850 and of H,S in the region 2100-1060 8 have been measured byWatanabe and Jursa,21 using photoelectric methods.The work with H,Oextends the earlier data of Watanabe and Zelikoff 22 for the region 1850-It iswell known that a group of bands occurring around 4050 8, a t first believedt o be due to the CH, molecule, is in fact due to the 12-electron C, molecule.Douglas23 analysed the main band (at 4050 A) and showed that the C,molecule is linear and symmetrical in both the upper and the lower electronicstate; but he was unable to decide whether the electronic transition is1 I l c 1C or 1Cc lI'I.Gausset, Herzberg, Lagerqvisf, and Rosen 24 have nowobtained high-resolution spectra of the group of bands in absorption afterthe flash photolysis of diazomethane. Reinvestigation of the 000-000(main) band shows the electronic transition to be lI'IUc 'C+, and not lE+u +lI'Ig.1100 8.Non-hydride Triatomic Molecules.-(a) Less than sixteen electrons.S. R.. La Paglia, J. Mol. Spectroscopy, 1963, 10, 240.20 S. Bell, Thesis, TJniversity of St. Andrews, 1963.21K. Watanabe and A. S . Jursa, J . Chem. Phys., 1964, 41, 1650.22 I<. Watanabe and M. Zelikoff, J. Opt. SOC. Amer., 1953, 43, 753.23 A. E. Douglas, Astrophys. J . , 1951, 114, 466.24 L. Gausset, G. Herzberg, A. Lagerqvist, and B. Rosen, Discuss. Furuduy SOC.,1963, 35, 113WALSH: ELECTRONIC SPECTRA O F POLY-QTOMIC MOLECULES 13It may be noted that, from the correlation dia'gram for AB, non-hydridemolecules, the ground state of C, is expected to beand the two lowest-energy allowed transitions from the ground state areexpected to beandFrom the analysis of bands other than the O O O t O 0 0 , Gausset et al.havearrived at the interesting conclusion that the bending frequency of theground state is most unusually low, viz., m. 70 cm.-l; this provides one reasonfor the complexity of the absorption spectrum, since even at room tempera-ture the population of the vi' # O levels will be considerable. The easewith which ground state C, can be bent relative to, say, C 0 2 can be under-stood to some extent from the correlation diagram.Z5 On that diagram,of the two curves leading to the nu orbital that is occupied in the groundstate of C,, one rises and one falls from left to right; whereas both curvesleading to the n, orbital (occupied in the ground state of CO,, but not in theground state of C,) fall from left to right.Four electrons in the q, orbitalshould therefore have a much bigger effect in tending to increase the re-sistance to bending of the linear molecule than four electrons in the zuorbital.Herzberg and Travis 26 have photographed under high resolution a,complicated group of bands appearing in absorption around 3290 A in theflash photolysis of diazomethane. Rotational analysis of the strongest(OOO+-OOO) band shows that the spectrum arises from either a 317uc3X-g ora 31T,+ ,C+, transition of the linear symmetric 14-electron molecule NCN.The first of these possibilities is undoubtedly correct because of the expecta-tion that the ground state of NCN should have the configuration* * (29N)2(2sN)2((os)2(au)2(nu)4(~~)~(n~)~, 3=s;and that the two lowest-lying allowed transitions should be.. . ( 2 s N ) 2 ( 2 9 N ) 2 ( G g ) 2 ( a u ) 2 ( n u ) 3 ( ~ g ) 3 , 8 ~ - ~ + 3 ~ - ~and . . . (29N)2(29N)2(ag)2(au)(n~)4(Tdg)3, 3 ~ 1 3 + c - ~ .From what has been said above concerning C,, one would expect the bendingfrequency to be appreciably less in the ground state of NCN than in t'heground state of CO, (667 cm.-l), though considerably greater than in theground state of C,.A somewhat uncertain value of ca. 370 cm.-l for thebending frequency of the ground state of NCN accords with this expectation.McGrath and Morrow 27 have reported a complex absorption systemobtained by the reaction of 0 atoms with cyanogen and by the flash photo-lysis of fulminic acid (HCNO). This system they attribute to the freefulminate radical, CNO. While the methods of producing the spectrumsupport its attribution to CNO, the position of the system (3330-3250 8). . . (29)2(~8)2(a,)2(o,)2(~~)4, is+,. . . (29) 2( 29) Z ( Gg) 2( au) 2( nu) 3( Zg), 1C+u+1C+g. . . (29)2(29)2(as)2(au)(~u)4(~g), 1r1~+lx+~.25 A. D. Walsh, Discuss. Paraday SOC., 1963, 35, 370.2 * G. Herzberg and D. N. Travis, C a d . J . Phys., 1964, 42, 1658.2 7 W.D. McGreth and T. Morrow, Nature, 1964, 203, 61914 GENERAL AND PHYSICAL CHEMISTRYis so close to the 3290 A system of NCN that one wonders whether theMcGrath and Morrow system might be attributed not to CNO but to NCN;however, the detailed band measurements reported do not seem to agreewith those for NCN.A fifteen-electron BAB molecule should have a linear ground state withthe configurationand the first two excited states should both be linear and have the con-figurations. . . ( ~ ~ ) ~ ( ( s ~ ) ~ ( 0 ~ ) ~ ( a e ~ ) ~ ( 7 c ~ ) ~ ( n g ) ~ , 2J&;andTransition from the ground state is allowed to each of these excited states.Johns 28 has observed the so-called '' boron flame bands " or " boric acidfluctuation bands " in absorption during the flash photolysis of mixtures ofboron trichloride and oxygen.The absorption bands lie in the region6800-3800 A. In emission the bands are responsible for the green coloura-tion of flames containing boron.* Detailed analysis by Johns shows: (i)that the bands are due, not to the B203 molecule as used to be supposed, butto the linear symmetric 15-electron molecule BO,; (ii) that transitions toboth the above excited states (confirmed to be linear) are involved; and(iii) that the B-0 distance changes from 1.265 A in the 211g state to 1.302and 1.273 8, respectively, in the 217u and the ,C+, state. Because the B-0distance changes much more in the 217uc than in the 2Efu+- Z I T g transi-tion, the former transition results in much more extensive vibrationalstructure.Increases in B-0 distance were to be expected, because the(ng) orbital is B-0 non-bonding, whereas the (uu) and the (nu) orbitals arebonding. Evidently, the (a,) is much more weakly bonding than the(nu) orbital. The bending frequency in the ground state is found to be464 cm.-l, a value which is, as expected from our discussion above, inter-mediate to the value of v2 in the ground state of CO, and the probable valueof v2 in the ground state of NCN. Details of the spectrum confirm thecorrectness of the correlation diagram in placing the (b2-n,) orbital curveabove the (a,-n,) orbital curve. The OOO-+OOO band lies at a higher energyin the 2X+u+-2rl[g transition than in the 211u+-211g transition. In this andmany other respects the BO, spectrum is similar to the spectrum of theisoelectronic molecule CO,+ where also the two transitions have been found.On the other hand, the spectrum of the NCO molecule (which is also a15-electron molecule) indicates that the state corresponding to 217u liesat higher energy than the state corresponding to 2Z+u.30s 3l There is much9 8 J.W. C. Johns, Canad. J. Php., 1961, 39, 1738.29 C. W. Matthews and K. K. Innes, J. Mol. Spectroscopy, 1964, 13, 93.30 R. N. Dixon, Phil. Trans., 1060, A , 252, 165.s1 R. N. Dixon, Canad. J. Phys., 1960, 38, 10.* The bands are also produced29 by discharges through EF, vapour, presumablyby reaction involving the SiO, of the glass discharge tubeWALSH : ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 15scope for theoretical work on the similarities and differences of the spectraof the many 15-electron molecules (BO,, CO,+, NCO, CS,+, N,O+, NCS, N3,OCS+) now known.The analysis of the BO, spectrum has led 32 to certain improvements inthe analysis of the spectrum of COz+.(b) Sixteen electrons: COZY CS,.The so-called '' carbon monoxide flamebands" have long been a puzzle to assign in detail, though it has beengenerally accepted that they are due to emission from a bent, electronicallyexcited state of CO,. The bands have now been photographed under highresolution,33,34 and a big step forward has been made towards definiteassignments. If we assume a transition from a bent excited state of CO,to the linear ground state, in general the bands will proceed to high vibra-tional levels of the ground state. It is well known that the pattern of thesevibrational levels is complicated by Fermi resonance.Dixon 34 thereforeset about the major task of calculating this pattern for levels of high vibra-tional quantum numbers; and he succeeded in showing that all the strongbands between 3100 and 3900 8, and most of the weak bands, can beexplained with the aid of his calculated ground-state energy-level patternif it assumed that all the transitions arise from the various rotational levelsof one upper-state level of species B,. According to Dixon, the upper state(i) has an energy of about 46,700 cm.-l above the lowest level of the groundstate, (ii) has an equilibrium apex angle of 123" & 3", and (iii) is probablythe singlet species lB,.The bent and B, nature of the upper state are inaccord with the theoretical expectation that the first excited state of CO,should be bent and have B, symmetry.The near-ultraviolet absorption spectrum of CS, consists of two distinctregions of absorption, one extending from 3800 to 2900 and a muchstronger one extending from 2300 to 1850 8 (the 2100 A bands). The f%stof these may itself be divided into a weak absorption region from 3800 to3300 A (the " R " region) and a stronger region from 3300 to 2900 8.Kleman 35 has reported a high-resolution study of the R region. It turnsout that even the limited R region involves at least two electronic transitions.The lowest excited state is shown to be bent with an apex angle of 135.8".The OOOt000 band probably lies at 3818 A.The species of the excitedstate is puzzling. On the one hand, there is a pronounced magnetic-rotation36 and Zeeman37 effect on some of the bands-which seems toindicate that the upper state is triplet. On the other hand, Kleman findsno evidence of a triplet structure in the bands of the R region and hisanalysis accords well with the upper state's being lB,. Thus, at present, theZeeman effect and the fine structure of the bands give conflicting indica-tions as to the multiplicity of the lowest excited state. More detailedstudies of the Zeeman effect and further studies of the other electronictransitions involved in the 3800-2900 A region are needed.32 J. W. C. Johns, Canad.J . Phys., 1964, 42, 1004.33 J. H. Callomon and A. C. Gilby, J . Ghem. SOC., 1963, 1471.34 R. N. Dixon, Discuss. Faraday SOC., 1963, 35, 105.3 5 I3. Kleman, Canad. J. Phys., 1963, 41, 2034.36 P. Kusch, J . Mol. Spectroscopy, 1963, 11, 385.37 A. E. Douglas, Canad. J . Phys., 1958, 38, 14i16 GENERAL AND PHYSICAL CHEMISTRYDouglas and Zanon 38 have studied the 2100 A bands of CS, under highresolution. Although some features of the system are not understood,strong evidence has been obtained that the upper state is bent and has thespecies lBz, an apex angle of 153" and a C-S bond length of 1-66 A com-pared with 1.55 A in the ground state. 153" is an unusually large value forthe apex angle of a bent triatomic molecule, but is in accord with the pre-diction by Walsh that the upper state would be found to be slightly bent.The lB, species and the appreciably increased C-S bond length also accordwith Walsh's predictions: he assigned the 2100 A bands to transition tothe 'B, state which correlates with the linear species lZ+u and is the secondlB, state: .. . (aa)(b#(bl), 1Bz f- . . . (ng)4, lE+g.(c) Seventeen ekctroles: NO,. Ritchie, Walsh, and Warsop 39 havephotographed under high resolution the 2491 A electronic transition ofNO, a d carried out a rotational analysis of the OW+- 000 band. A previousanalysis was known to be incorrect since it led to, e.g., a value of the apexangle in the ground state of l54", whereas yecent microwave studies haveshown conclusively that the correct value is 134'15'.The new analysisis consistent with the upper state belonging to the C2,, point group and having2B, electronic symmetry with an N-0 length of 1.314 A and an ON0 angleof 121'2'. The N-0 length is considerably greater than the ground-statevalue of 1,197 A, and the ON0 angle is somewhat less than the ground-state value.The vacuum-ultraviolet absorption spectrum of NO, includes a verylarge number of narrow bands lying between 1650 and 1350 A. Ritchieand Walsh 40 have shown that these bands arise from a transition in whichthe shape of the rnoleeule changes from bent to linear. The transition isRydberg in type and it is not surprising, therefore, that the upper stateresembles the ground state of the NO,+ ion in being linear. The upperstate has 2Cfu symmetry, and the Rydberg orbital to which the excitedelectron is transferred is (pa) in type.The N-0 length in the upper stateis decreased from its ground-state value, showing the somewhat anti-bonding nature of the (ul-nu) orbital from which the excited electronoriginates.The infrared and visible electronic transitions of NO, still largely defysatisfactory analysis. Bands stretch all the way from ccx. 9000 b to a broadmaximum at cu. 4000 A and beyond. Probably two electronic transitionsare involved. From studies of the absorption spectmm of NO, producedand trapped in y-irradiated single crystals of NaNO, at room temperature,Atherton, Dixon, and Kirby41 find the polarization of the light absorbedaround 4000 to be parallel to the line joining the oxygen nuclei. Thisimplies that the upper state is 2B2 and suggests assignment of the electronictransition to .. . (b2)(a1)2, 2B, f- . . . (b2)2(a,), 2A,.38A. E. Douglas and I. Zanon, Canad. J . Phys., 1964, 42, 627.3 9 R. K. Ritchie, A. D. Wnlsh, and P. A. Warsop, Proc. Roy. XOC., 1962, A , 266,257.40 R. K. Ritchie and A. D. Walsh, Proc. Roy. SOC., 1962, A , 267, 395.4 1 N. M. Atherton, R. N. Dixon, and G. H. Kirby, Trans. Faraday Soc., 1964,60, 1688WALSH: ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 17The absorption observed begins at about 5250 A and rises steadily to a broadmaximum at 4000 A; the conclusion of Atherton et. al., therefore, presumablyrelates to the second transition of NO,, absorption due to the first transitionbeing too weak to be observed under the conditions used.Unfortunately,the conclusion of Atherton et. al. is in direct conflict with work by Douglasand H~ber.~2 The latter authors have found a long progression of red-degraded bands of gaseous NO, in the region 4600-3700 A. Rotationalanalysis shows that these bands are the K = 1 to K = 0 sub-bands of theelectronic transition ZBl+ 2A,, i.e., that the transition concerned is polarizednot parallel, but perpendicularly, to the 0-0 line.(d) Eighteen electrons .- SO,. Merer 43 has made a partial rotational analysisof some bands of the lowest-energy absorption system of SO, occurringaround 3800 A. His conclusion is that the bands, which are perpendicular,represent transition to a 3B1 upper electronic state in which the OSO angleis 126'5' compared with 119"Z' in the ground state.From the correlationdiagram, B, is expected to be the symmetry of the first excited state, and theapex angle is expected to increase somewhat in the transition. The tripletnature of the upper state of the 3800 A bands is in accord with the know-ledge37 that the system shows a pronounced Zeeman effect. One mighthave thought that the second, stronger, absorption system (whose maximumintensihy occurs at 2900 A and which displays no Zeeman effect) wouldrepresent transition to the corresponding lB1 upper state. However, the2900 A system has a much more extensive vibrational structure and, there-fore, apparently has an upper-state geometry very different from that ofthe 3800 A system.Further, according to Merer,44 the only band of the2900 system with sharp K-structure is parallel and therefore has a lB,upper state.Dubois and Rosen 459 46 have studied the vibrational structure of theabsorption system lying between 2400 and 2000 A. At leash two electronictransitions occur in this range. One of these is particularly analysed andshown to have its origin around 2367 8. The occurrence and intensity ofbands involving the v 3 antisymmetric stretching vibration are taken tomean that the upper state has unequal bond lengths (see below). The3800 and the 2900 A system are also claimed to involve the excitation ofGolomb, Watanabe, and Marmo 49 have measured, by a photomultipliertechnique, absorption coefficients of SO, in the region 2100-1050 A; andWarneck, Marmo, and Sullivan5* have extended their work to cover therange 3150-1849 A.The latter authors report an absorption coiitinuunibeginning at 2280 A; the data of the former authors suggest a second con-tinuum beginning a t 1680 A. The range 2280-1680 A corresponds to an3r3,47, 4842 A. E. Douglas and K. P. Huber, unpublished work.43 A. J . Merer, Discuss. Faraday SOC., 1963, 35, 127.O 4 A. J. Merer, Discuss. Faraday Soc., 1963, 35, 230.4 5 I. Dubois, Bull. SOC. Roy. Sci. LiLge, 1963, 32, 777.4(i I. Dubois and B. Rosen, Discuss. Furday SOC., 1963, 35, 121.47 R. K. Russell, B. L. Landrum, and E. E. Vezey, ASTIA doc., 1956, AD 81060.48 J. B. Coon, Bull. Amer. Phys. Soc., 1957, 2, 100.O 9 D.Golomb, K. Watanabe, and F. F. Marmo, J. Chem. Phys., 1962, 36, 958.P. Warneck, F. F. Marmo, and J. 0. Sullivan, J. Chem. Phys., 1964, 40, 113218 GENERAL AND PHYSICAL CHEMISTRYenergy difference of 45 kcal./mole, which is the excitation energy of thelD state of atomic oxygen above its ground state. Warneck et al. thereforesuggest thatSO, + hv+ SO + O(3P)andSO, + hv ---+ SO + O(l0)are responsible, respectively, for the 2280 and the 1680 A continua. Animplication is that 125 kcal./mole (corresponding to 2280 8) representsan upper limit for the energy required to dissociate SO, to ground-stateSO and 0.(e) Nineteen electrons: ClO,, NF,. To say that a triatomic moleculehas unequal bond lengths is equivalent to saying that there are two minimain the potential as a function of the antisymmetrical vibrational co-ordinate.We have referred above to the possibility that this state of affairs exists inseveral excited states of the SO, molecule.Coon, Cesani, and Loyd5lhave discussed the evidence that the upper state of the near-ultraviolettransition of C10, has a double-minimum potential. Others (Coulson,52Walsh,= and Ritehie, Walsh, and Warsop55) have joined thediscussion.Humphries, Walsh, and Warsop 56 have reported three band systems(at 1829, 1628, and 1568 8) of ClO, in the vacuum-ultraviolet region. Thegeometries and vibrational frequencies of the upper states are discussed.Each system represents a Rydberg transition. The 1829 and the 1628 8system are associated with the first ionization potential of the molecule ;the 1568 system m y be associated with the second ionization potential.However, the latter association implies the existence of an intravalency-shell transition of C10, around 10,000 8; and, in spite of a search, Coon 57finds no such transition.Johnson and Colburn 5* reported absorption by the NF, radical, formedby the thermal decomposition of tetrafluorohydrazine ; but the dispersionused was such that they were able to say little more than that the absorptionhad a maximum a t 2600 8 with a half-width of 200 A.Goodfriend andW O O ~ S , ~ ~ and independently Kuznetsova, Kuzyakov, and Tatevskii,60 havefollowed up the work of Johnson and Colburn by studying the 2600absorption under higher dispersion, The absorption is then seen to consistof a series of diffuse bands, of which the Russian authors (using heatedNF,) report some 14 or 16, and Goodfriend and Woods (using room tempera-ture) report at least 8.Because of the diffuseness, measurement of these5 1 J. B. Coon, F. A. Cesani, and C. M. Loyd, Disct~s. Faraday SOC., 1963, 35, 11 8.52 C. A. Coulson, Discuss. Faraday Soc., 1963, 35, 224.53 J. C. D. Brand, Discuss. Faraday SOC., 1963, 35, 224.64 A. D. Walsh, Discuss. Faraday SOC., 1963, 35, 224.55 R. K. Ritchie, A. D. Walsh, and P. A. Warsop, " Spectroscopy ", Institute of66 C. M. Huaphries, A. D. Walsh, and P. A. Warsop, Disczcss. Furadccy SOC., 1963,57 J. B. Coon, personal communication.6 8 F. A. Johnson and C. B. Colburn, J . Amer.Chem. SOC., 1961, 83, 3043.59 P. L. Goodfriend and H. P. Woods, J . Mol. Spectroscopy, 1964, 13, 63.60 L. A. Kuznetsova, Yu. Ya. Kuzyakov, and V. M. Tatevskii, Optics and Spectro-Petroleum, London, 1962, p. 289.35, 137, 230.scopy, 1964, 16, 295WALSH: ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 19bands is difficult, but the band separations in the two sets of work agreebetter than the band measurements themselves. The Russian authorsgive 390 cm.-l for the average separation, Goodfriend and Woods giveca. 380 cm.-l. The smallness makes it very probable that 380 or 390 cm.-lrepresents the bending frequency in the upper state; and one notes that theelectronic transition greatly reduces the frequency from its surprisinglyhigh value The transition is mostprobably eitherorThe second of these is the transition identified as responsible for the near-ultraviolet (3600 8) absorption system of the isoelectronic molecule C10,;but the observed long progression in Y,' fits better with assignment of theNF, transition as the first of the above alternatives.The 2A1-+2B1 transi-tion should be associated wit,h a considerable increase in FNF angle fromits ground state value 6, of ca. 104" and is the analogue of the transitionresponsible for the infrared and visible bands of NH,. Whereas, however,the NH, transition leads to a linear upper state, the ,Al state of NF, maystill be bent, since (i) the bent nature of the ground state of NO, indicatesthat in non-hydride AB, molecules one electron in the (al-zu) orbital issufficient to cause bending, and (ii) the (bl-nu) orbital curve rises from leftto right on the correlation diagra.m for AB, but is horizontal on the correla-tion diagram for AH,.Interest in the XeF, moIecule hasextended to its spectrum. It is known that, in accord with the correlationdiagram, the molecule is linear in its ground state.Wilson, Jortner, andRice 63 have studied the spectrum of the gas as far as 1100 8. A weaktransition of maximum intensity around 2300 A has been found, withE,,,. - 100 1. mole-1 cm.-l, followed by five sharp, much stronger bandsat 1580,1425,1335,1215, and 1145 8, each with E ~ ~ ~ . - 10,000 l.mole-lcm.-l.The assignment of the various transitions has been discussed by Wilsonet u Z . , ~ ~ by C o ~ l s o n , ~ ~ and by Isra61i65 Coulson takes the ground-stateconfiguration to beThe three lowest-energy singlet-singlet intravalency shell transitions arethen .. . (0~)2(ng)4(nU)3(0u)ly 1ITgt'C+g. . . ( 1 ) . . . (ag)2(~g)3(nu)4(0u)ly 1rIuclX+g. . (2)and . . . (ag)'(ns)4(nu)4(au)ly 1C+utlC+g (3)with, according to Coulson, the second and third lying close. The firsttransition is forbidden; the second and third are allowed. Coulson follows61 F. A. Johnson and C. B. Colburn, Inorg. Chem., 1962, 1, 431.62 M. D. Harmony, R. 5. Myers, L. J. Schoen, D. R. Lide, and D. E. Mmn, J.6a E. 0. Wilson, J. Jortner, and S. A. Rice, J . Amer. Chern. Soc., 1963, 85, 813.64 C. A. Coulson, J. Chem. SOC., 1964, 1442.6 5 Y. J. Israeli. Bull. SOC. chim.France, 1964, 648.of 730 cm.-l in the ground state.(a2)2(b2)2(.1)(b1)2Y 2 A l f- (a2)2(b2)2(a1)2(bl)Y %* (a2>(b2)2(%)2(h>2Y 2-42 f- * . - (a2)2(b2)2(a1)2(bl), 2B,.(f) Twenty-two eZectrons: XeF,.(2sF) 2(2aF) 2( 5sXe) 2(0u) 2 ( n ~ ) 4(0g) 2(zg) 4(nu) 4(0u)0y 'X'g-Chem. Phys., 1961, 35, 112920 GENERAL AND PHYSICAL CEEMISTRYWilson et aZ. in assigning the very strong 1580 A transition to (3). He thenassigns (2) to the weak 2300 L% transition which, since 2300 and 1580 L% areseparated by about 2.5 ev, is hardly consistent with his own expectationthat (2) and (3) should lie close together. Further, it is not altogetherobvious that (3) should be so much stronger than (2). The 2300 A transitionhas indeed of a magnitude often associated with symmetry-forbiddenelectronic transitions made allowed by vibrational interaction.Thissupports the assignment, by Wilson et al., of the 2300 A absorption as (I).(see ref. 66). However, the transition is supposed to be made allowed byexcitation of the bending (nu) vibration ; whereas according to the correlationdiagram the transition should Be of linearchear type and so should notmarkedly arouse the bending vibration. Further, the assignments byWilson et at?. do not make it clear what has happened to the transition (2).As regards transition (3), one would expect it to lead to dissociation, andyet bofh Coalson and Wilson et al. assign it to the sharp band at 1580 A.Wilson et aZ. suppose the remaining four strong, sharp bands to be Rydbergin type.The high emax. values, and the sharpness, of these bands stronglysupport such an assignment but afford little experimental support forsupposing that the 1580 A transition is quite different (intravalency shell)in type. Wilson et al. suppose the 1425 and the 1215 A bands belong toone Rydberg series, which they write asY (cm.-l) = 92,000 - R / ( n + 0.2)2;and the 1335 and 1145 A bands belong to a second Rydberg series, written asY (cm.-l) = 98,000 - R / ( n + 0.2)e.The first ionization potential is therefore supposed to be 11.5 ev, as comparedwith 12.12 ev for the free xenon atom. The two-membered nature of eachseries must, however, make extrapolation to the ionization limits very un-certain. The existence of two series is ascribed to spin-orbit coupling conse-quent upon the presence of the heavy xenon atom This is to imply that thefist ionization removes an electron from st n, rather than a c, orbital, afeature which is in accord with Coulson's formulation (above) of the ground-state configuration.On the other hand, it is by no means certain that theorbital energy order is as Coulson formulates it, and not as would be ex-pected from the AB, correlation diagram, vix.:Israeli65 has also given a tentative analysis of the XeFz spectrum. Hedoes not assign the 2300 A system, but supposes all the strong, sharp bandsto be intravalency shell in type, Chree of them representing electronicallyforbidden transitions. This seems improbable. More work is requiredbefore assignments of the XeF, transitions can be aceepted with confidence.HAB Molecules.-(a) Eleven electrons: HCO.The earlier work ofHerzberg and Ramsay on the 7500-4500 A absorption system of HCO hasbeen extended and revised by Johns, Priddle, and Ramsay.67 In agreementwith expectations from the HAB correlation diagram, the transition in-( 2 8 ~ ) '( 2 8 ~ ) ~ ( o g ) 2( bu) (nu) '( ng ) '(nu) '( ug) 2(ou) '*66E. S . Pysh, J. Jortner, and s. A. Rice, J . Chem. PhYs., 1964, 40, 2018.6' J. W. C. Johns, S . H. Priddle, and I). A. Ramsay, Discuss. Fu~aduy Soc., 1963,35, 90WALSH: ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 21volves a bent ground state (CHO angle = 119'30') and a linear upper state.In disagreement with the correlation diagram, the electronic transition wasearlier thought to be %++ 2A".The later work now leaves no doubt thatthe transition is in fact 2 I I c 2A' in accord with the correlation diagram. Thereassignment leads to an understanding of many details of the spectrumin terms of large vibronic splittings (cf. ref. 15) due to the effects of electronic-vibrational interaction (the so-called " Renner effect ").The so-called " hydrocarbon flame bands " (4100-2200 A) have usuallybeen supposed to be due to HCO as emitter. That they are due to anemitter containing H is oertain because of the existence of an isotope effect.Vaidya,6* using considerably improved sources, has been able to extendthe system and carry out a vibrational analysis of the isotopic bands.The origin of the transition is found to lie at 2522.5 8.A ground-statefundamental frequency of 1895 cm.-l (reduced to 1857 cm.-l in the deuterium-substituted emitter) is found. This value is not quite the same as that(1820 cm.-l) found by Johns et al. for the HCO ground state C=O stretchingfrequency (cf. ref. 69).The original work of Dalby 70on the visible absorption bands of the twelve-electron molecules HNO andDNO has been extended to much greater absorption intensities by Bancroft,Hollas, and Ram~ay.7~ Seven new bands of HNO and six new bands ofDNO have been found and analysed, leading to improved eqwlibrium valuesfor the geometrical parameters of the excited state. The ground state ofthe molecule is bent, with an apex angle 7 O of 108.6". The absorptionspectrum is due to the expected lowest-energy singlet-singlet transition(lA"c lA') and involves, also as expected, an increase in apex angle.Dalby'svalue of 116.3" for the apex angle in the excited state has been revisedslightly to 114'25' & 2'. Clement and Ramsay '2 have obtained twelvebands of HNO and 18 bands of DNO in emission (during the reaction of Hor D with NO) and have made a particular study, continued in the absorp-tion work of Bancroft et al., of predissociation in the molecule. An upperlimit of 48.6 kcal./mole for D(H-NO) is found.They are, therefore,expected, and found, each to possess a very low-lying electronic absorp-tion system (in the region 6000-4100 A). A detailed fine-structure analysisof the bands in these absorption systems has been carried out by Herzbergand Verma.73 Hence the geometrical structure of the molecules in both theupper and the lower states has been established.For the lower state, prob-ably the ground state, it is found that, for HSiC1,while, for HSiBr,(b) Twelve electrons: HNO, HSiCl, HSiBr.HSiCl and HSiBr are also 12-electron molecules.rJSi-H) = 1.56 A, ro(Si-Cl) = 2-064 A, H&C1 = 102.8;r,,(Si-H) = 1.56 A (assumed), ro(Si-Br) = 2-231 A, HgiBr = 102.9'.6 8 W. M. Vaidya, Proc. Roy. SOC., 1964, A , 279, 572.'OF. W. Dalby, Canad. J . Phys., 1958, 36, 1336.Z'J. L. Bancroft, J. M. Hollas, and D. A. Ramsay, Canad. J . Phys., 1962, 40, 323.r 2 M. J. Y. Clement and D. A. Ramsay, Canad. J . Phys., 1961, 39, 205.73 G. Herzberg and R. D. Verma, Canad.J . Phys., 1964, 42, 395.D. E. Milligan and M. E. Jacox, J . Chem. Phys., 1964, 41, 303222 GENERAL AND PHYSICAL CHEMISTRYThe two molecules thus have virtually the same apex angle. For the upperstate of HSiClro(Si-H) = 1.50 A, ro(Si-Cl) = 2-047 A, %Sic1 = 116.1”;while for the upper state of HSiBrro(Si-H) = 1-60 A (assumed), yo(Si-Br) = 2.208 A, H6h3r = 116.6’.As expected from the HAB correlation diagram,5 the apex angle increasesin the electronic transition. The changes in bond lengths are, as expected,small, although it should be noted that r,(Si-Hal) changes in the oppositedirection from that expected [and found for r,(N-0) in HNO 707 7 7 . Certaindetails of the band structures can be accounted for if it is assumed thatthe transitions are triplet+ singlet (Le., probably ,A”+ lA’) rather thansingleft- singlet ; but no triplet splitting has been resolved.The absorption spectrum of the 13-electron molecule HO, still defiesdiscovery and identification.AH, and AB, Molecules.-The absorption spectrum of NH, has receivedmuch attention.At least five electronic transitions can be recognized 74 tolong wavelengths of 1200 8. The first, third, and fourth of these haveorigins at 2168, 1434, and 1330 8, respectively. The origin of the secondwas originally thought to lie at 1665 8, but was later 75 shown to lie at1689 A. The fifth is of unknown origin but is responsible for bands in theneighbourhood of 1268 8. Each transition is represented by a long pro-gression in the upper-state out-of-plane vibration.The first four transitionsare each proved,74 by a vibrational analysis, to have planar upper states.All the transitions are Rydberg in type,* and the ground state of the NH,+ion is deduced as planar. Douglas and Hollas 75 have studied the secondof the five transitions in absorption at high resolution; and, by a rotationalanalysis of six of the bands, independently shown the upper state to beplanar. The upper state of the first electronic transition has l A i r sym-metry 74 76 and results from excitation of an electron from a non-bondingorbital to an s Rydberg orbital.74 The upper state of the second transitionhas E” symmetry 75 and results from excitation of an electron to a p Rydbergorbital;74, 75 Zeeman studies 76 confirm the degeneracy of the upper state.Theoretical calculations 77 are in agreement with the first two electronictransitions’ having the upper-state symmetries cited, though the calculatedpositions of the transitions are less satisfactory.Douglas 76 discusses thepredissociation observed in the various excited states.Walsh and Warsop,’* and Humphries, Walsh, and war so^,^^ comparethe spectra of PH,, PD,, ASH,, AsD,, and SbH, with those of NH, and74 A. D. Walsh and P. A. Warsop, Trans. Faraday SOC., 1961, 57, 345.75A. E. Douglas and J. M. Hollas, Canad. J . Phys., 1961, 39, 479.76 A. E. Douglas, Discuss. Faraday SOC., 1963, 35, 158.77 S . BratoB and M. Allavena, J . Chem. Phys., 1962, 37, 2138.78 A. D. Walsh and P. A. Warsop, Adv. Mol. Spectroscopy, 1962, 582.7D C.M. Humphries, A. D. Walsh, and P. A. Warsop, Discuss. Faraday Soc.,1963, 35, 148.* Correlation of the possible molecular orbitals with the atomic orbitals of the fusedatom (Ne) shows that every transition of the NH, molecule (like those of the H,Omolecule) can be described as RydbergWALSH: ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 23ND,. Unlike the NH, case, the first electronic transitions of PH,, ASH,,and SbH, are all represented by continuous absorption (certain bandspreviously reported in the absorption spectrum of PH, around 2300 A arealmost certainly due to impurities *O, 8l). The other electronic transitions,however, are represented by long progressions in the vz‘ frequency, as withNH,. It is clear, therefore, that a considerable change in HA€€ angleaccompanies each discrete electronic transition.It does not necessarilyfollow that the upper states are planar as with NH,. The progressionsobserved are all regular, which is compatible with the upper states beingeither (i) planar, or (ii) pyramidal with such a low barrier to inversion thatall the vibronic transitions observed are to vibrational levels well above thetop of the inversion barrier, or (iii) pyramidal with such a formidable barrierto inversion that all the transitions observed are to vibrational levels wellbelow the top of the inversion barrier. Walsh and Warsop 78 and Humphrieset a2.79 call attention to the remarkable fact that whereas the spacing of theobserved progressions of NH, and ND, is w;’, the spacing of the observedprogressions of the other hydrides and deuterides is -v2”/2.The contrastis used as an argument that these other hydrides and deuterides may haveupper states (and positive-ion ground states) described by (ii) rather than(i) (cf. ref. 82).Humphries et al.V9 also describe and discuss the spectra of PF, andPCL,. Here it appears that the upper states (and the ground states of thePF,+ and the PCl,+ ion) are to be described as (iii). Halmann,S3 using aquartz spectrograph purged with nitrogen and studying the region 220-1850 A, has given A,,,. positions for the first electronic transitions of PH,and PCl, which do not agree with those obtained with vacuum spectrographs.No spectra have yet been reported for BH, or SiH,.The spectrum ofCH, has been referred t o in a previous Annual Reprt.84Miscellaneous Molecules.-Work on the near-ultraviolet absorptionspectrum of HCHO has been reviewed by Ramsay.3 It is well lmown thatthe absorption leads to pyramidal upper states (,A2 and lA2) showing thephenomenon of inversion. Parkin, Poole, and Raynes 85 have discussedcertain perturbations observed in the singlet-singlet system and ascribedthem to vibration-rotation interactions between the member levels of aninversion doublet, of a kind described by Lide.86 The origin band of thesinglet-singlet system is forbidden both electronically and vibronically asan electric-dipole transition, but nevertheless appears weakly. Callomonand Innes *’ have reviewed the explanations that have been advanced forthe appearance of the band and concluded that the band appears as a resultof a magnetic-dipole transition.Jeunehomme and Duncan 88 have measured80 L. Mayor, A. D. Walsh, and P. A. Warsop, J . Mol. Spectroscopy, 1963, 10, 320.81 D. P. Stevenson, G. M. Coppinger, and J. W. Forbes, J. Amer. Chem. SOC.,82 J. L. Duncan, Discuss. Faraday SOC., 1963, 35, 231.83 M. Halmann, J. Chem. SOC., 1963, 2853.84 I. M. Mills, Ann. Reports, 1960, 57, 42.8 5 J. E. Parkin, H. G. Poole, and W. T. Raynes, Proc. Chena. SOC., 1962, 248.86 D. R. Lide, J . Mol. Spectroscopy, 1962, 8, 142.1961, 83, 4350.J. 13. Callomon and K. K. Innes, J. MoZ. Spectroscopy, 1963, 10, 166.M. Jeunehomme and A. B. F. Duncan, J. Chsm. PAp., 1964, 41, 169224 GENERAL AND PHYSICAL CHEMISTRYthe decay time of the fluorescence from the lA, state; they conclude thatthe f number of the singlet-singlet system is probably more than an orderof magnitude higher than previously reported and is calculated as cu.0.013.La Paglia and Duncan 89 have found the phosgene (carbonyl chloride)molecule to possess, in addition to its near ultraviolet band system, severalseparate electronic transitions in the vacuum-ultraviolet region and havetentatively interpreted these. Brand, Callomon, Moule, and Tyrrell90have examined the absorption of thiophosgene (thiocarbonyl chloride) inthe region 6000-4000 A under high resolution. Two electronic systems arepresent in the region, corresponding to transitions to 3A, and lA, states,just as with formaldehyde.The origin of the singlet system is close to5340 A. Of particular interest is the strong evidence presented that thelA, state is pyramidal as in formaldehyde and, indeed, has an almostidentical inversion barrier height.Brand, Callomon, and WatsonYg1~ 92 and Brand and Willia111son,~3 havestudied the absorption, in propynal and propenal, respectively, whichcorresponds to the lA,+-lA, transition of formaldehyde. In the upperstates of these conjugated molecules, the barrier to planarity vanishes ornearly vanishes, so that the upper states are like the ground states in beingplanar. Studies of the vibrations aroused by the electronic excitationmake it clear that the excitation is not localized in the CHO group-whichis presumably the reason why, unlike formaldehyde, the upper states arenot markedly non-planar.Rotational and remarkably complete vibrationalanalyses have been carried out. The analogue of the aA2c1A, system offormaldehyde has its origin a t m. 4143 A in propynal and at ca. 4122 A inpropenal; the analogue of the lA2c1A1 system of formaldehyde has itsorigin at 3821 A in propynal and at m. 3865 in propenal. Muirhead 94has studied the near-ultraviolet spectrum of tetrolaldehyde (but-2-pal),CH ,*CXWHO.When excited by light in the far-ultraviolet region or in an electrodelessdischarge, formic acid emits an extensive band spectrum. The probabilityis that the actual emitter is the radical HCO,. Peacock, Rias-Ur-Rahman,Sleeman, and Tuckley 95 report self-consistent-field molecular-orbitalcalculations on the states of this radical and, with these as a basis, attemptan interpretation of the observed spectrum.The spectrum of formic acid itself (and of acetic acid and ethyl acetate)in absorption has been studied by Nagakura, Kaya, and Tsubomura.96A new transition of monomeric formic acid (cf.the earlier work of Price8 9 s . R. La Paglia and A. B. F. Duncan, J . Chem. Phys., 1961, 34, 125.90 J. C. D. Brand, J. N. Callomon, D. C. Moule, and J. Tyrrell, Proc. Chem. SOC.,91 J. C. D. Brand, J. H. Callomon, and J. K. G. Watson, Canad. J. Phys., 1961,9 2 J. C. D. Brand, J. H. Callomon, and J. K. G. Watson, Discuss. Paraday SOC.,93 J. C, D. Brand and D. G. W-illiamson, Discuss. Parada?/ SOC., 1963, 35, 184.9 4 J.S. Muirhead, University of California (Lawrence Radiation Laboratory,9 5 T. E. Peacock, Rias-Ur-Rahman, D. H. Sleeman, and E. S. G. Tuckley, Discuss.96 S. Nagakura, K. Kaya, and H. Tsubomura, J. MoZ. Spectroscopy, 1964, 13, 1.1963, 337.39, 1508.1963, 35, 175.Berkeley), Ph.D. Thesis, 1964.Faruday Xoc., 1963, 35, 144WALSH: ELECTRONIC SPECTRA O F POLYATOMIC MOLECULES 25and Evans 97 which, swprisingly, is not referred to by Nagakura et al.)has been found at 1590 A with E ~ ~ ~ . = 2400. The nature of the newtransition is discussed.As a result of the initial experiments of Dixon and Norman,g flow tech-niques are now widely used to study thermal free-radical reactions. Fulldetails of the reactions between *OH radicals and aliphatic alcohols 10 andacidsll in aqueous solution have now been given.Acetic acid yields theradical CH,-CO,H and a smaller concentration of methyl radicals. Thecx-proton splitting in substituted methyl radicals *CH,X decreases along theseries X = H, alkyl, CO,H, C1, RCO, OH, and alkoxy. Attack on chloro-and dichloro-acetic acid yields the *CHCl.CO,H and -CCI,CO,H radicalswhich exhibit rare examples of chlorine hyperfine structure.In equally elegant experiments, Fischer 12 has studied the reactionsbetween *OH and many important monomers, detecting free radicals formedin the early stages of polymerisation. Acrylonitrile, for example, yieldsthe initial radical HO.CH,CH(CN)* which gives a well-resolved spectrum.Fischer has succeeded in solving finally the mystery of the spectrum ob-served in irradiated poly(methy1 methacrylate).This spectrum, which hasoften been interpreted in terms of a superposition of two different spectra,.o*is in fact due to a single radical of type (1). The electron spin resonance(e.s.r.) spectrum of aqueous solutions containing *OH radicals and metha-crylic acid shows 16 lines, analysable in terms of a methyl splitting of 22.46gauss and two non-equivalent protons with splittings 13.75 and 11.04 gaussseverally. The spectrum exhibits a pattern of nine groups and it is quiteclear that, in the solid phase, a " 5 + 4 " line pattern exhibiting line-widthalternation would be expected ; Symons7s earlier interpretation l3 is thuscorrect.Waters and his collaborators have continued their studies of transient8 R.W. Fessenden, J . Phys. Chem., 1964, 68, 1508.13 W. T. Dixon and R. 0. C. Norman, Proc. Chem. SOC., 1963, 97.lo W. T. Dixon and R. 0. C. Norman, J . Chem. SOC., 1963, 3119.l1 W. T. Dixon, R. 0. C. Norman, and A. L. Buley, J . Chem. SOC., 1964, 3626.l2 H. Fischer, 2. Naturforsch., 1964, 19a, 866; H. Fischer, Polymer Letters, 1964,l3 M. C. R. Symons, J . C h m . SOC., 1963, 1186.2, 529CARRINGTON : ELECTRON SPIN RESONANCE 29radicals, using flow systems. Following their detection of the phenoxy-radical 14 and various related species 15 formed by oxidation of phenols withceric sulphate in aqueous sulphuric acid, they have now shown1s thatnitrobenzene derivatives can be reduced and studied in aqueous alkalinesolution by using sodium dithionite.Oxidation of resorcinol in acid oralkaline solution17 results in the previously unobserved radical (2) withsplitting constants (in gauss) as shown. Carrington and Smith l8 have madea similar study of the radical formed by oxidation of pyrogallol. Onvarying the pH they observed radicals possessing 2,1, and 0 protons attschedto the oxygen atoms. Apparently intramolecular hydrogen bonding pre-vents rapid proton-exchange with the solvent.Oxidation of hydrazine with ceric sulphate 19 yields the interesting radical,*N2H,+, with nitrogen and proton couplings of 11.5 and 11.0 gauss, respec-tively, whilst oxidation of oximes with ceric ammonium nitrate in methanol 2ogives rise to iminoxy-radicals (e.g., Me,C=N-O*) which have abnormallylarge nitrogen splittings.There is continued interest in monocyclicradicals and radical ions.The benzene anion splitting has been found toincrease slightly on lowering of the temperature.21 The cyclopentadienylradical 21 has an overall width (Le., separation between extreme lines) (Q)of 30.0 gauss, whilst *C,H, 22 and *C,H,- 23 have Q values of 27.4 and 25.7gauss, respectively. The reasons for these differences are not properlyunderstood and, until they are, comparisons of detailed spin-density calcu-lations and hyperhe splittings for more complex radicals are of uncertainvalue.The deuterobenzene anion has a non-uniform spin distribution, thepara-proton splitting being somewhat smaller than the remaining proton~plittings.~~ In contrast, the deuterocyclo-octatetraene anion has a uni-form spin distribution and this difference may be understood in terms ofthe Jahn-Teller effe~t.2~ The o-xylene anion has been reinvestigated byBolton,26 who finds that the earlier interpretation by Tuttle 27 is incorrect:the proton splittings are, in fact, in good agreement with molecular-orbitaltheory. Hulme and Symons28 have shown that the hexamethylbenzenecation, formed by ultraviolet irradiation of the parent molecule in concen-trated sulphuric acid, is moderately stable, and shows a splitting of 6-45gauss from eighteen equivalent protons.(ii) Xtuble free radical-ions.l4 T.J. Stone and W. A. Waters, Proc. Chem. SOC., 1962, 253.l6 T. J. Stone and W.A. Waters, J. Chem. Soc., 1964, 213.lSP. L. Kolker and W. A. Waters, J . Chem. SOC., 1964, 1136.l7 T. J. Stone and W. A. Waters, J. Chem. SOC., 1964, 4302.A. Carrington and I. C. P. Smith, MoE. Phy$., 1964, 8, 101.l o J. Q. Adam and J. R. Thomas, J . Chem. Phys., 1963, 39, 1904.2o J. R. Thomas, J. Amer. Chem. SOC., 1964, 86, 1446.21 R. W. Fessenden and S. Ogawa, J . Amer. Chem. Xoc., 1964, 86, 3591.2 2 A. Carrington and I. C. P. Smith, MoE. Phys., 1963, 7 , 99.23 T. J. Katz and H. L. Strauss, J . Chem. Phys., 1960, 32, 1873.24 R. G. Lawler, J. R. Bolton, G. K. Fraenkel, and T. H. Brown, J. A m . C h .25 A. Camhgton, H. C. Longuet-Higgins, and P. F. Todd, MoE. Phys., 1964, 8, 45.26 J. R. Bolton, J. Chem. Phys., 1964, 41, 2455.27 T. R. Tuttle, J .Amer. Chem. SOC., 1962, 84, 2839.28 R. Hulme and M. C. R. Symons, Proc. Chem. Soc., 1963, 241.Soc., 1964, 86, 52030 GENERAL AND PHYSICAL CHEMISTRYStrauss, Katz, and Fraenkel 29 have now described their studies of thecyclo-octatetraene anion in greater detail. From a study of the line broaden-ing due t o electron-transfer, they deduce that the compression energy ofcyclo-octatetraene itself is 21 kcal./mole. Carrington and Todd 30 havestudied a number of alkylcyclo-octatetraene anions; the degeneracy of thenon-bonding molecular orbitals is removed by the substituent, and theresults are in accord with molecular-orbital predictions for a planar eight-membered ring.The discussion about the interpretation of isotropic nitrogen splittingsin aromatic radicals continues, the point at issue being whether 14N splittingsdepend upon the spin density on adjacent carbon atoms or not.It wasoriginally asserted 31 that the spectra of several azine radical-anions couldbe adequately interpreted by assuming that the nitrogen splitting is propor-tional to the n-electron spin density on the nitrogen. This view has beenquestioned on the grounds that the theory developed for 13C splittings shouldalso apply to 14N. In principle this is true, but if one were to apply thetheory, modified only to take account of the much smaller nuclear g factorfor I4N, one would predict that the effect of n-electron densities on boththe nitrogen and the adjacent carbon atom would be to produce very smallhyperfine splittings.The real difference between the two cases is, therefore,to be found in the direct effect of n-electron density on the atom in question,which is much more important for 14N than for 13C. Very careful studiesby Stone and Maki 32 and by Barton and Fraenkel 33 have confirmed thatthe proportionality constant &zN relating the 14N splitting to the spin densityon an adjacent carbon atom is very small (-2-5 gauss); even its sign isuncertain.Cyanobenzene anions have been produced by both electrolytic 34 andchemical the results obtained by different methods being ingood agreement with each other. The perturbation of the ring system by thecyanide groups is substantial, but the results may nevertheless be reasonablyinterpreted in terms of the molecular orbitals of benzene itself. Othernitrogen-containing aromatic anions to be studied include cycl0[3,2,7]azine,3~1,4-dicyanotetrazine ,3 7 and 7,7,8,8- tetra c yano quinodimet hane .38The pairing theorem for alternant hydrocarbons has received furtherverification through the observation that the 13C coupling constants in theanthacene positive and negative ion are nearly identical.39 Larger aromaticring systems have also been studied.The anions of dibenzocyclo-octa-H. L. Strauss, T. J. Katz, and C. K. Fraenkel, J . Amer. Chem. SOC., 1963, 85,2360.ao A. Carrington and P. F. Todd, MoZ. Phys., 1964, 7, 533.a1 A. Carrington and J. S. Veiga, MoZ. Phys., 1962, 5, 21.aaE. W. Stone and A. H. Maki, J . Chem. Phys., 1963, 39, 1634.33 B.L. Barton and G. K. Fraenkel, J . Chem. Phys., 1964, 41, 1455.B4 P. H. Rieger, I. Bernal, W. H. Reinmuth, and G. K. Fraenkel, J . Anaer. Chem.a6A. Carrington and P. F. Todd, MoZ. Phys., 1963, 6, 161.36 N. M. Atherton, F. Gerson, and J. N. Murrell, Mo2. Phys., 1963, 6, 265.37 A. Carrington, P. F. Todd, and J. S . Veiga, MoZ. Phys., 1963, 6, 101.8 8 P. H. Fischer and C. A. McDowelI, J . Amer. Chem. SOC., 1963, 85, 2694.39 J. R. Bolton and G. K. Fraenkel, J . Chem. Phys., 1964, 40, 3307.SOC., 1963, 85,. 683CARRINGTON : ELECTRON SPIN RESONANCE 31tetraene, tetra~henylene,~~ and hexa-m-phenylene 4 1 show well-resolvedhyperfine patterns ; the spin distribution can be calculated by consideringthe way in which the lowest antibonding molecular orbitals of the componentn-electron subsystems react on each other, The anion and cation oflob, 1 Oc-dihydro- trans- 1 Ob , 1 Oc-dimethylpyrene (3) show pro ton couplingsin good agreement with molecular-orbital calculations for the peripheral14-membered n-electron system.42 The cation and anion of 1,3,6,8-tetra-azapyrene have very similar splitting constants.43 We also draw attentionto studies of aromatic thio-radicalsp4 the anions of benzaldehyde and othercompounds which show isomerism or conformational semiquinonephosphates which often show phosphorus hyperfhe splittingst6 variousalloxan and isoalloxazine semiq~inones,~7 and some aromatic hydrocarbontriani0ns.~8Levy and Myers 49 have described the first study of a simple olefin anion.Butadiene can be reduced electrolytically in liquid ammonia and gives awell-resolved spectrum with a 2.791 gauss splitting from the protons atpositions 2 and 3 and a 7.617 gauss splitting from the methylene protons.These coupling constants are in good agreement with Hiickel molecular-orbital calculations. Liquid ammonia appears to be an excellent solventfor free radical-anions.50A most unexpected result is the observation by Bowers and Greene 51that cyclopropane can be persuaded to accept an electron, giving a spectrumin which six equivalent protons produce a 2.33 gauss splitting.Further studies of intramolecular electron-transfer have been reported.The anion of the cyclobutane derivative (4) shows equal hyperfine splitting40 A.Carrington, H. C. Longuet-Higgins, and P.F. Todd, Mol. Phys., 1964, 8, 845.41 P. H. H. Fischer, K. H. Hawser, and H. A. Staab, 2. Naturforsch., 1964, 19a,42 F. Gerson, E. Heilbronner, and V. Boekelheide, Helv. Chim. Acta, 1964,47, 1123.44 E. A. C. Lucken, J . Chem. SOC., 1964, 4240; H. J. Shine, C. F. Dais, and R. J.Small, J . Org. Chem., 1964, 29, 21; E. A. C. Lucken, Theor. Chim. Acta, 1963, 1, 397.45 E. W. Stone and A. H. Maki, J. Chem. Phys., 1963, 38, 1999; G. A. Russelland E. T. Strom, J . Arner. Chem. SOC., 1964,86,744; N. Steinberger and G. K. Frmnkel,J . Chern. Phys., 1964, 40, 723.47 C. Lagercrantz and M. Yhland, Acta Chem. S c a d . , 1963, 17, 1677; A. V. Guzzoand G. Tollin, Arch. Biochem. Biophys., 1963, 103, 231.48 P. Brassem, R. E. Jesse, and G. J.Hoijtink, Mol. Phys., 1964,7, 587; K. Mobiusand M. Plrtto, 2. Naturforsch., 1964, 19a, 1240.r s D . H. Levy and R. J. Myers, J . Chem. Phys., 1964, 41, 1062.A. Maximadshy and F. Dorr, 2. Naturforsch., 1964, 19b, 359; E. Brunner andF. Dorr, Ber. Bunsen Geaellschaft Phys. Chem., 1964, 68, 468.61K. W. Bowers and F. D. Greene, J . Amer. Chem. Soc., 1963, 85;, 2331.816.F. Gerson, Helv. Chirn. Ada, 1964, 47, 1484.B. T. Allen and A. Bond, J . Phys. Chem., 1964, 88, 243932 GENERAL AND PHYSICAL CHEBIISTRYfrom the four nitrogen atoms,52 indicating that the electron-transfer rateis very fast; this is interpreted in terms of direct 1,3-n-interaction, ratherthan hyperconjugation. Harriman and Maki 53 have studied electron-transfer in some di-(p-nitrophenyl) anions (5).When X = CH,.CH,, the transfer rate is slow and the spectrum characteristicof localisation of the electron on one ring is observed.The 4,4'-dinitro-biphenyl anion itself exhibits fast transfer, but with X = 0 or S it is apparentthat the rate of transfer and the h y p e h e couplings (in Mc./sec.) are ofcomparable magnitude. In these cases the role of the solvent is important.Cowell, Urry, and WeissmanM have studied mono- and di-anions of bis-2,2'-biphenylylene, in which the two ring systems are non-coplanar : thehyperfine structure in the monoanion indicates rapid electron-transferbetween the ring systems; the dianion possesses a low-lying triplet state,which may even be the ground state, and the spin-spin interaction, measuredin a rigid medium, suggests that there is one odd electron localised on eachbiphenylene fragment.In contrast, the dianion of bis-(2,2'-biphenylylene)-silane is diamagnetic ;b5 in the monoanion the odd electron is again delocalisedover both ring systems. These results suggest conjugation of the two non-coplanar ring systems through use of the silicon d orbitals.The initial observations byAdam and Weissman 56 that the spectra of aromatic anions frequently showadditional hyperfine splitting from the counter-ion (usually an alkali-metalcation) has stimulated intense study of ion-association effects in e.8.r. spectra.Perhaps the most interesting and novel recent observations are those of de(iii) Ion-association and solvent effects.Boer and Mackor 57ation between thewho have studied the solvent-dependence of the associ-pyracene anion (6) and various alkali-metal cations.Reduction of pyracene with potassium in dimethoxyethane at -70" yieldsa spectrum which may be unambiguously interpreted in terms of the un-associated anion.The ring-proton splitting is 1-58 gauss and the methylenecoupling is 6.58 gauss. Reduction with sodium in tetrahydromethylfuran69 M. T. Jones, R. A. LaLancette, and R. E. Benson, J . Chem. Phys., 1964,41,401.ba J. E. Harrimm and A. H. Maki, J . Chem. Phys., 1963, 39, 778.6aR. D. Cowell, G. Urry, and S. I. Weissmctn, J . Chem. Phys., 1963, 38, 2028.66 R. D. Cowell, G. Urry, and S. I. Weissman, J . Amer. Chem. SOC., 1963, 85, 822.6 6 F. C. Adam and S. I. Weissmaa, J .Amer. Chem. SOC., 1958, 80, 1518.a7E. de Boer and E. L. Mslckor, J . Amr. Chena. SOC., 1964, 86, 1513CARRINGTON : ELEC'I!RON SPIN RESONANCE 33at -83" yields a quite different spectrum due to the pyracene- Na+ ionpair. A splitting of -0.17 gauss from the 23Na nucleus is observed; further-more, the methylene protons are no longer equivalent but produce twoquintet splittings, of 6-93 and 6.37 gauss severally. Presumably the cationis adjacent to the methylene groups at one end of the molecule. Pinally,reduction with potassium in tetrahydrofuran at -30" yields a spectrum inwhich the nine groups of lines arising from the dominant methylene splittingexhibit marked alternation of line width; there is, in addition, a smallsplitting from the 39K nucleus.The line-width effect indicates that themethylene coupling is undergoing a time-dependent modulation, due tocation-transfer between the pairs of methylene groups at opposite endsof the molecule. That the rate process is, indeed, intramolecular is provedbeyond question by the fact that the potassium hyperhe splitting is notaffected, showing that the spin orientation of the potassium nucleus is pre-served during the transfer process. De Boer and Mackor show that thepotassium splitting can be removed by the addition of alkali halide, owingto rapid cation-exchange. Similar effects have been observed for the pyrazineanion by Atherton and G0ggins.~8Nitrobenzene anions show interesting effects due to ion pairing, as wasfirst pointed out by Ward.59 He showed that the m-dinitrobenzene anionprepared by alkali-metal reduction in an ethereal solvent gave a spectrumexhibiting a large splitting from one nitrogen (9.0 gauss) but a very smallsplitting (0.29 gauss) from the other.In contrast, electrolytic reductionin a solvent of high dielectric constant yields a spectrum showing equalsplitting (4-68 gauss) from both nitrogen atoms. It has always been sup-posed that the unsymmetrical spin distribution measured by Ward is aresult of ion pairing, and strong evidence that this is the case has now beenprovided by Blandamer et &.GO They find that reduction of m-dinitrobenzeneby potassium in 1,2-dimethoxyethane, followed by partial removal of thesolvent and addition of acetonitrile, results in a spectrum virtually identicalwith that obtained by electrolytic reduction.The sym-trinitrobenzene anion in solvents of low dielectric constant 59also shows an anomalous spin distribution because of ion association,although electrolytic reduction in acetonitrile 61 results in a spectrum in-volving hyperfine interaction with three equivalent nitrogen atoms andthree equivalent ring protons.A careful study e2 of the trinitrobenzeneanion in dimethylformamide reveals that, in this solvent, the presence ofalkali-metal cations makes little difference to the spectrum, but Ca2+ andBa2f ions cause an abrupt change to a spectrum showing interaction withone nitrogen only. Similar experiments reveal that the original inter-pretation of the p-dinitrobenzene anion spectrum is incorrect ; pronouncedalternation of line width disguises the appearance of the pattern.Ultraviolet irradiation of nitrobenzene in tetrahydrofuran yields a6 8 N.M. Atherton and A. E. Goggins, MoE. Phys., 1964, 8, 99.R. L. Ward, J . Amer. Chem. SOC., 1961,83, 1296; J . Chem. Phys., 1962,36, 1405.6o M. J. Blandamer, T. E. &ugh, J. M. Gross, and M. C. R. Symons, J . Chem.P. H. H. Fischer and C. A. McDowell, Mol. Phys., 1964, 8, 357.6* S. H. Glarum and J. H. Marshall, J . Chem. Phys., 1964, 41, 2182.Soc., 1%4, 53634 GENERAL AND PHYSICAL CHEMISTRYneutral radical which has a spectrum similar to that of the nitrobenzeneanion but with an additional proton doublet splitting;63 it has been provedthat the extra hydrogen comes from the solvent, but the precise structureof the radical is uncertain.Similar effects have been observed with g m -trinitr~benzene.~~ Ultraviolet irradiation in ethereal or alcoholic solventsseems to be an effective method of reducing strong electron-acceptors.65Luckhurst and Orgel g6 find that, whereas the spectrum of benzil anionfrequently shows additional splitting from the counter-ion, the 2,2,5,6-tetra-methylhexane-3,4-dione anion (7) never does. They suggest that steric(CH,),C*CO*CO*C(CHs)3 (7)hindrance restricts the molecule to the configuration in which the carbonylgroups are trans ; strong ion-association is therefore unlikely. Relevant tothis remark is the observation 137 that the o-benzosemiquinone ’anion formscomplexes with metal ions, even in aqueous solution.Although in the caseof alkali-metal cations, additional hyperfine structure from the metalnucleus is not observed, the ratio of the two ring-proton triplet splittingsvaries according to the heat of hydration of the counter-ion. Associationwith the rare-earth cations, Y3+ and La3+, does result in additional metalhyperfine structure. Ion-association involving the p-benzosemiquinoneanion has also been studied; 68 in some cases the ring protons giveunequal splittings. Attention is also drawn to Reddoch’s studies 6B of theazulene-Li+ system, where temperature and concentration changes inducequite large variations in the ring-proton splittings.There is continued interest in the solvent-dependence of proton hyper-fine couplings.Corvaja and Giacometti’s studies 70 of the m-nitrophenolanion in 50% aqueous dimethylformamide are of particular interest. At0°C they observe a complex hyperfine pattern which can be interpreted as asuperposition of two spectra with different nitrogen couplings. At roomtemperature the spectrum is simpler and readily interpreted in terms of arapid time average of the spectra from differently solvated anions. Relatedto these studies is the observation 71 that the o-nitrophenol anion in aceto-nitrile shows hyperfine splitting from the hydroxyl-proton, whereas the meb-and para-derivatives do not. Luckhurst and Orgel 72 have measured theproton splittings of the fluorenone lietyl in alcohol-dimethylformamidesolvent mixtures. The spectra in pure ,methanol and pure dimethylform-amide are very different from each other ; detailed studies in solvent mixturesreveal large changes in the coupling constants as the mole fraction of methanolasR.L. Ward, J . Chem. Phys., 1963, 39, 2588.64 C. Lagercrantz and M. Yhland, Acta Chem. Scand., 1962, 16, 1043.66 R. L. Ward, J . C h m . Phys., 1963, 39, 852; P. B. Ayscough, F. P. Sargent,and R. Wilson, J . Chem. SOC., 1963, 6418; G. A. Russell and E. J. Geele, TetrahedroizLetters, 1963, 1333.66 G. R. Luckhurst and L. E. Orgel, Mol. Phys., 1963-64, 7 , 297.67 D. R. Eaton, Inorg. Chem., 1964, 3, 1268.E. A. C. Lucken, J . Chem. SOC., 1964, 4234.1 3 ~ A. H. Reddoch, J . Chem. Phys., 1964, 41, 444.70 C. Corvaja and G. Giacometti, J . Amer.Chem. Soc., 1964, 86, 2736.71 K. Umemoto, Y. Deguchi, and T. Fujinaga, Bull. Ohm. Xoc. Japan, 1963, 36,78 G. R. Luckhurst and L. E. Orgel, MoZ. Phys., 1964, 8, 117.1639CARRINGTON : ELECTRON' SPIN RESONANCE 35increases from zero to 0.1, but a relatively small change from 0.1 to 1.0.The results are interpreted semiquantitatively in terms of an equilibriumbetween solvated ketyl molecules and hydrogen-bonded ketyl-alcoholadducts.Evidence for strong intramolecular hydrogen bonding is obtained fromstudies of the 1,4-dihydroxy-5,8-naphthaquinone anion (8). For aqueousalkaline solutions the spectrum shows hyperfine interaction with fourequivalent ring protons and two hydroxyl-pr0tons.7~ In concentrated0sulphuric acid the radical exists 7* as the fully protonated cation (9); how-ever, the shape of the spectrum is highly temperature-dependent owing torotation of the hydroxyl groups with respect to the rings.Quantitativeanalysis of the variations in line width by means of a theory 76 based onthe Bloch equations shows that the barrier to rotation is 4 kcal./mole.Preservation of the hydroxyl hyperhe splitting indicates that the mechanisminvolves breaEng and re-forming of intramolecular hydrogen bonds, andnot proton exchange with the solvent.A notable advance in the study of metal-amine solutions is the obser-vation of hyperhe structure in some of these systems.T6 Thus potassiumin alkylamines shows potassium structure ; lithium in ethylamine exhibitsa sharp line attributed to solvated electrons, plus a nine-line pattern arisingfrom four equivalent nitrogen atoms.The multiplet pattern is thought tobe due to lithium monomer, and conclusions are drawn about the size of themonomer. Among other recent studies of metal solutions, attention isdrawn to spin-echo determinations of electron relaxation times,77 andmeasurements of the changes in g value brought about by addition of alkalihalides to solutions of metals in liquid ammonia.78Nearly all e.s.r. spectra obtained for theliquid phase show variations in the widths of the hyperfine lines, and theunderlying theory has been developed in great detail. Asymmetric andsymmetric line broadening arises from the fact that the anisotropic partsof the g and nuclear hyperfine tensors, combined with the random tumblingof the molecules in the liquid, constitute a time-dependent Hamiltonianperturbing the spin system.The matrix elements of this Hamiltonianaveraged over all orientations vanish, but their squares do not vanish.73 J. H. Freed and G. K. Fraenkel, J . Chem. Phys., 1963, 38, 2040. '* J. R. Bolton, A. Carrington, and P. F. Todd, Mol. Phys., 1963, 6, 169.75 A. Carrington, Mol. Phys., 1962, 5, 425.76 K. Bar-Eli and T. R. Tuttle, J . Chem. Phys., 1964, 40, 2508.7' D. Cutler and J. G. Powles, Proc. Phys. SOC., 1963, 82, 1.' 8 R. Catterall and M. C. R. Symons, J . Chem. SOC., 1964, 4343.(iv) Line shapes and widths36 GENERAL AND PHYSICAL CHEMISTRYMcConnell 79 first drew attention to this effect and his theory was extendedto free radicals by Stephen and Fraenkel and by Kivelson.81 Carringtonand Longuet-Higgins 82 generalised the theory to allow for the fact that theprincipal axes of the hyperfine tensors for different nuclei are not necessarilyparallel.They neglected purely nuclear relaxation effects, however, andthis procedure is unjustified in the light of subsequent work. Freed andFraenkel 83 have developed a comprehensive theory, based on the densitymatrix methods of Redfield.84 They draw attention to the problems thatarise in the case of sets of equivalent nuclei. The four ring-protons in thep-benzosemiquinone anion, for example, are equivalent in the sense thatthey have the same isotropic splitting but are not compEeteZy equivalent inthe sense that the instantaneous value of the anisotropic interaction maybe different for some of them.As a result, the line widths can be obtainedonly by diagonalising the complete relaxation matrix and it then becomesapparent that a hyperfine line arising from transitions which are degeneratein the strong-field approximation actually consists of superimposed Lorent-zian components which can have different widths; Kivelson S5 has come toBimilar conclusions, and detailed studies 86 of the tetracyanoethylene anionconfirm the main ideas.It is possible to use line-broadening effects to obtain information aboutthe g tensor or about the signs of isotropic hyperfine couplings. De Boerand Mack~r,~' for example, have deduced that the aJ3C coupling in thenaphthalene anion is positive, whilst the PJ3C coupling is negative.Theseconclusions depend on certain assumptions concerning the components ofthe g tensor; in a similar study of the p-dinitrobenzene anion, however,Freed and Fraenkel88 have shown that the sign of the isotropic nitrogencoupling may be obtained through consideration of the electron-nucleardipolar interaction alone. The signs of some of the coupling constants inthe dihydropyrazine cation have also been deduced on similar grounds.89A particularly neat application of line-width studies is to the assignmentof the 1% hyperfine couplings in the anthracene ions;go the method dependsupon the fact that the line broadening from dipolar interactions is pro-portional to the square of the n-electron density on the carbon of interest,whereas the actual magnitude of the splitting is not directly related to thisdensity.It is also possible to accommodate time-dependent modulations of theisotropic coupling within the framework of the Freed and Fraenkel theory.83Such a modulation frequently gives rise to line-width alternation,9l now a7 9 H.M. McConnell, J. Chem. Phys., 1956, 25, 709.8oM. J. Stephen and G. K. Fraenkel, J . Chem. Phys., 1960, 32, 1435.81 D. Kivelson, J . Chem. Phys., 1960, 33, 1094.8 3 A. Carrington and H. C. Longuet-Higgins, Mol. Phys., 1962, 5, 447.8s J. H. Freed and G. K. Frmnkel, J . Chem. Phys., 1963, 39, 326.8 4 A. G. Refield, I.B.M.J. Research and Development, 1957, 1, 19.e5 D. Kivelson, J . Chem. Phys., 1964, 41, 1904.86 J.Gendell, J. H. Freed, and G. K. Frmnkel, J . Chm. Phys., 1964, 41, 949.S 7 E. de Boer and E. L. Mackor, J . Chem. Phys., 1963, 38, 1450.8 8 J. H. Freed and G. K. Frankel, J . Chem. Phys., 1964, 40, 1815.89 B. L. Barton and G. K. Fraenkel, J . Chem. Phys., 1964, 41, 1455.90 J. R. Bolton and G. K. Fraenkel, J . Chem. Phys., 1964, 41, 944.9l J. R. Bolton and A. C&gton, MoE. Phya., 1962, 5, 161CARRINGTON : ELECTRON S P I N RESONANCE 37very commonly observed phenomenon. The dinitrodurene anion exhibitsline-width alternation due to modulation of the nitrogen coupling, and thisis interpreted in terms of either fluctuating solvent effects or internal rotationsof the nitro-groups. 92 Similar effects are observed for the nitromesityleneanions,gS and we have already drawn attention to line-width alternationdue to ion-association or rotational isomerism.The Freed and Fraenkel theory is not easy to apply to complicatedradicals and there is still room for simpler, if less exact, methods.McLachlan 94 has described a method in which one calculates a single line-width paxameter for each line in the spectrum, regardless of whether it arisesfrom degenerate transitions or not. The theory includes nuclear-relaxationeffects and can be applied to a radical as complicated as the tetracene cation.The theory has also been applied to systems with X > Q where the dominantrelaxation mechanism involves the zero-field splitting tensor ; for these casesthe line-width expressions are identical with those derived from the relaxationmatrix method.95Free Radicals in Solids.-(i) Organic crysihk. Our knowledge of thehyperfine coupling tensors for ci- and p-protons is now fairly complete, andrecent attention has been concentrated on radicals showing hyperfine struc-ture from nuclei other than hydrogen. A number of papers have describedfluorine-containing radicals. X-Irradiation of single crystals of fluoro-acetamide results in the formation of oriented -CHF.CO-NH, radicals.96The principal components (in Mc./sec.) of the proton coupling tensor are-96, -63, -31, and the fluorine tensor has principal components of +530,- 11, and -45. The largest value is obtained in a direction perpendicularto the radical plane and this indicates that the 2pn spin density on fluorineis approximately 0.1.Carbon-fluorine double bonding is, therefore, ofsome importance. The -O,CCF,.CF(CO,-)* radical shows hyperfine splittingfrom all three fluorine atoms; the principal components of the a-fluorinetensor are +421, +165, +11 Mc./sec and the @-fluorine atoms are notquite equivalent, the principal tensor components having values of + 176,+64, +52, and +ZOO, +75, +64 Mc./sec., severally. These results 97indicate considerable delocalisation of the odd electron, the /?-fluorine Zpn-spin density being approximately 0.03.Interesting examples of hydrogen-deuterium isotope-exchange reactionshave been reported. ?-Irradiation of *CHMe*ND,.CO,D results in orientedradicals of type Me-CHR- which initially show hyperfine structure fromboth a- and p-protons.However, by following the changes in the e.s.r.spectrum,98 it is found that all four protons are exchanged for deuteronswithin 10 hours at 150". Weiner and Koski 99 find that +H,NCH,.CO,-and +H3N.CD,*C0,- give identical spectra on y-irradiation, and they question9 2 J. H. Freed and G. K. Fraenkel, J. Chem. Phys., 1964, 41, 699.93 I. Bernal and G. K. Fraenkel, J . Amer. Chem. SOC., 1964, 86, 1671.e4A. D. McLachlan, Proc. Roy. Soc., 1964, A, 280, 271.96A. Carrington and G. R. Luckhurst, Mol. Phys., 1964, 8, 125.96 R. J. Cook, J. R. Rowlands, and D. H. Whiffen, Mol. Phys., 1963, 7, 57.07M. T. Rogers and D. H. Whiffen, J . Chem. Phys., 1964, 40, 2662.9g K. Itoh and I. Miyagawa, J . Chm. Phys., 1964, 40, 3328.09R. F.Weiner and W. S. Koski, J. Amer. Chem. SOC., 1963, 85, 87338 GENERAL AND PHYSICAL CHEMISTRYthe earlier interpretation by Ghosh and Whiffen loo who identified theradicals present as *CH(NH,+)CO,- and *CH2*C0,-. Weiner and Koskisuggest that NH, is formed, but Morton lol has now studied artificially en-riched +H,N-13CH,.C0,- and shown that the original interpretation iscorrect. The results on +H,N-CD,CO,- can be interpreted only by assum-ing that the initially formed -CD(NH,+)*CO,- radical undergoes rapid ex-change of its deuteron for NH3+ protons in undamaged molecules.The radical Me3N*+ has been identified in y-irradiated Me,N+Cl- 102 andalso in electron-irradiated betaine hydrocMoride.lo3 y-Irradiation of 2-furoic acid Io4 and thiophen-2-carboxylic acid lo5 results in the formationof oriented radicals (10) and (1 l), respectively.In each case a large isotropicH Q$, $=$Co2H(10) ( 1 1)splitting (80-90 Mc./sec.) is observed from the protons at position 5. Theprotons at positions 4 and 3 give isotropic splittings of -25 and +6 Mc./sec.in (10) and -24 and +6 Mc./sec. in (1 1) ; the anisotropic interaction is alsosimilar for the two radicals. One deduces that the hetero-atom has verylittle effect on the spin distribution.Cole, Kushida, and Heller106 have discussed the advantages and dis-advantages of studying free radicals in zero magnetic field. The mainadvantage is that it is not necessary to work with single crystals; the zero-field e.s.r. spectrum of randomly oriented *CH( C02H), radicals yields principalcomponents of the a-proton tensor which are almost identical with thosederived from conventional high-field experiments.Zero-field spectra are,however, very complicated (a radical with two non-equivalent protonsshould give twenty-eight absorption lines) and it is not possible to obtainany information about the signs of the tensor components.Further studies concerning the angular dependence of p-proton couplingshave been reported. The *CH(CO2-).[CH2],-CO2- radical shows a markedlytemperature-dependent #I-proton coupling which is interpreted in terms ofanharmonic oscillation of the CH, group next to the radical site about theG C bond.107 A general discussion of p-proton couplings, including theeffects of rocking or twisting, has been given by Morokuma and Fukui lo*and by Stone and Maki.109 y-Irradiated 6-hexanolactam yields the radical(12) which shows hyperfine coupling from nitrogen, the NH proton, theCH proton, and one of the p-methylene protons.llo The absence of a second100 D.K. Ghosh and D. H. Whiffen, MoE. Phys., 1959, 2, 285.101 J. R. Morton, J . Amer. Chena. SOC., 1964, 86, 2325.102 A. J. Tench, J . Chem. Phys., 1963, 38, 593.Io3 G. Schoffa, J . Chem. Phys., 1964, 40, 908.104 R. J. Cook, J. R. Rowlands, and D. H. Whiffen, Mol. Phys., 1963, 7, 57.105 N. Eda, R. J. Cook, and D. H. Whiffen, Tram. Faraday SOL, 1964, 60, 1497.106 T. Cole, T. Kushida, and C. Heller, J . Chem. Phgs., 1963, 88, 2915.108 K. Morokuma and K.Fukui, Bull. Chem. Soc. Japan, 1963, 36, 531.lo9E. W. Stone and A. H. Maki, J . Chern. Phys., 1962, 37, 1326.I1o M. Kashiwagi and J. Kurite, J . Chem. Phys., 1964, 40, 1780.M. Kashiwagi and Y . Kurita, J . Chem. Phys., 1963, 39, 3165CARRINGTON : ELECTRON S P I N RESONANCE 39@-proton coupling suggests that the radical has the boat and not the chairconformation.HCHoc /N\Two methods of obtaining partially oriented radicals have been described.Single crystals of inclusion compounds of urea and various long-chain alkylesters can be X-irradiated to yield radicalslll of type CH(CO,R)CH,R'.The radicals undergo motions in the tubular cavities of the crystal and theb-proton couplings are often temperature-dependent. y-Irradiation of asingle crystal of /I-propiolactone monomer leads to forrqation of the polymer 112containing partially oriented radicals of type -CH,-CH.CO-.y-Irradiated single crystals of XeF4 and KrF4yield the oriented radicals XeF1ls and KrF,l14 respectively.The XeFradical shows fluorine hyperhe structure (principal values 2649, 540,540 Mc./sec.) and xenon structure (principal values 2368,1224,1224 Mc./sec.).These results, and also the g tensor components (g,, = 1.9740, gL = 2.1251)indicate that the unpaired electron occupies an antibonding 0-orbital, formedprincipally by overlap of the fluorine 2p2 and xenon 5p, orbitals. Theanisotropy in the fluorine structure suggests 47% of fluorine 2p character.The fluorine interaction is larger in KrF, indicating that the fluorine Zp, and2s character in the antibonding 0-orbital is greater in KrF than in XeF.It,therefore, follows114 that the a-bonding orbital in KrF has less fluorinecharacter than has the corresponding orbital in XeF.Morton 115 has studied the PF, radical in irradiated polycrystalline andsingle crystals of NH,PF,. The fluorine interaction is very large andsecond-order splitting is easily detected. Further studies by Atkins andSymons 116 have revealed that the well-resolved spectrum obtained byMorton at room temperature all but disappears at 210'9 and is replaced byan extremely complicated spectrum at still lower temperatures. Theseobservations are interpreted in terms of distortions of the PF, moleculewhich are rapid at room temperature but slow at low temperatures.?-Irradiation oflead nitrate crystals 11' yields NO, molecules, which appear to be rotatingrapidly in the crystal, and NO,* radicals.The unpaired electron in NO,*occupies a non-bonding molecular orbital ; nitrogen hyperfine structure isnot observed but there is a very small splitting due to interaction with sur-rounding lead atoms. y-Irradiation of sodium nitrite also results in the(ii) Inorganic crystals.Further work on oxyanion radicals has been reported.ll1 0. H. GrifEth, J . Chem. Phys., 1964, 41, 1093; 0. H. Griffrth and A. L. Kwiram,lla S. I. Ohnishi, S. I. Sugimoto, K. Hayashi, and I. Nitta, Bull. Chem. SOC. Japan,lla J. R. Morton and W. E. Falconer, J . Chem. Phys., 1963, 39, 427.11* W. E. Falconer, J. R.Morton, and A. G. Streng, J . Chem. Phys., 1964, 41, 902.115 J. R. Morton, Canad. J . Chem., 1963, 41, 706.llaP. W. Atkins and M. C. R. Symons, J. Chem. SOC., 1964, 4363.11' R. M. Golding and M. Henchman, J . Chem. Phys., 1964, 40, 1554.J . Amer. Chem. Soc., 1964, 86, 3937.1964, 37, 52440 GENERAL AND PHYSICAL CHEMISTRYformation of two radica1s.lls One is identified as NO,; the other shows ane.8.r. spectrum with a quintet hyperfine structure and is identified as N,O,-.The radicals *ASO,~- and *SeO,- have also been observed in irradiatedcrystals of Na2HAs0,,7H,0 119 and NaHSe0,,12* respectively. Atkins,Symons, and Trevalion 121 have shown that after ultraviolet irradiation ofpotassium persulphate an e.s.r. spectrum consisting of a single line flankedby two doublets is observed.The radical present is *SO,- and the doubletstructure is thought to be due to dipolar coupling between pairs of *SO,-radicals which are 13-19 ,k apart in the crystal.(iii) Randomly oriented radicals. An interesting new technique fortrapping free radicals has been described.122 Alkali-metal atoms are fireda t a revolving drum which is continuously coated with a suitable substratemaintained at a low temperature. The radical-containing deposit can thenbe collected and its e.s.r. spectrum examined. Initial experiments weredirected at the reactions between alkali metals and organic halides; benzylchloride, for example, reacts to produce trapped benzyl radicals. To a largeextent, techniques for trapping organic radicals at low temperatures havebeen rendered obsolete by recent liquid-phase irradiation and flow-systemstudies.However, a particularly interesting application of the rotatingcryostat is to the reaction between sodium or potassium atoms and ice at7 7 " ~ . At this temperature a single line, thought to be due to hydratedelectrons, is obtained; on warming to 1 4 0 " ~ ~ five hyperfine components areresolved. Replacement of water by deuterium oxide confirms the view thatthese lines are due to proton interaction, and no interaction with the alkali-metal nucleus is detected. The reported g value (2.0008) is perhaps surpris-Trapped electrons are also thought to be present 123 in y-irradiatedaqueous alkali-metal hydroxides at 77°K. The formation of an intense bluecolour is accompanied by a sharp e.s.r.line.X-Irradiation of cyclohexene at 77 OE yields a radical giving an unresolvede.s.r. line;124 a t 1 4 7 " ~ motional narrowing results in resolution of hyperfinestructure which is assigned to the radical (13) with hyperfine couplingconstants (in gauss) as shown. Continuous electron-irradiation of solidingly low.cyclohexane at -8O"c results in the formation of cyclohexyl radicals (14).The a-proton splitting is 21.3 gauss ; two /3-protons give a 39-4 gauss splitting11* J. Tateno and K. Gesi, J . Chm. Phys., 1964, 40, 1317.llS W. C. Lin and C. A. McDowell, MoZ. Phys., 1963-64, 7, 223.lZo R. J. Cook, J. R. Rowlands, and D. H. Whiffen, MoZ. Phys., 1964, 8, 195.lal P. W. Atkins, M. C. R.Symons, and P. A. Trevalion, Proc. Chem. Soc., 1963, 222.122 J. E. Bennett, B. Mile, and A. Thomas, Nature, 1964, 201, 919; J. E. Bennett123 M. J. Blandamer, L. Shields, and M. 0. R. Symons, J . Chm. Soc., 1964, 4352.124 S. I. Ohnishi and I. Nitta, J. Chem. Phys., 1963, 39, 2848.lzs S. Ogawa and R. W. Fessenden, J . Chern. Phys., 1964, 41, 994.and A. Thomas, Proc. Roy. Soc., 1966 A, 279, 123CARRINGTON : ELECTRON SPIN RESONANCE 41and two others produce a 5-3 gauss splitting. At 0"c ring inversion causessome of the hyperhe lines to disappear and careful study of this processsuggests that the activation energy for ring inversion is 4.9 0.5 kcal./mole.Photolysis of acetylene in a solid argon matrix at 4.2'9 results in theformation of trapped G C H radicals which show a proton doublet splittingof 16.1 gauss.126 Photolysis of hydrogen iodide in the presence of acetyleneat low temperatures, however, yields the vinyl radical as a result of additionof a hydrogen atom to acetylene.If dideuteroacetylene is employed it isfound that the resulting radical is exclusively that in which the two deuteriumatoms are trams to each other.Experiments designed to study free-radical migration in irradiatedpolymers have been de~cribed.l2~ Polyethylene is irradiated at 77 OK, thenwarmed to room temperature, and the kinetics of free-radical decay arerelated to the rate of hydrogen-gas evolution. The results suggest thatradical migration is effected through the consecutive reactions :R + H 2 - + RH + HH + R H - + H , + RAttention is also drawn to the stabilisation of free radicals by adsorptionon solid surfaces,l28 and to further discussions of line shapes in randomlyoriented ~ 0 l i d s .l ~ ~The origin of the e.s.r. signals obtained from organic charge-transfercomplexes is still obscure. Complexes of aromatic hydrocarbons withtetracyanoethylene, prepared by crystallisation from methylene dichloride,show relatively weak resonances whose intensities are not reproducible. Ithas now been found, however, that after the complex has been melted andresolidified, a much higher and reproducible spin concentration is obtained.130Progress in this field is hampered by the lack of detailed experimental work,and the recent single-crystal study by Benderskii et aZ.131 is particularlywelcome. They fmd that single crystals of the chloranil-p-phenylenediaminecomplex exhibit a single e.s.r.line and, from a study of its intensity-depend-ence on temperature, conclude that the resonance arises in part from localiseddefects and in part from triplet excitons.Triplet States.-One of the most rapidly developing areas of e.s.r. is thestudy of organic molecules in triplet ground or excited states. Hirota,Hutchison, and Palmer 132 have described details of the hyperhe structureof naphthalene in its lowest excited triplet state. Measurements on naph-thalene and various deuterionaphthalenes in a single crystal of dureneindicate that the carbon 293, spin densities at positions 1, 2, and 9 are126 E. L. Cochran, F.J. Adrian, and V. A. Bowers, J . Chem. Phys., 1964, 40, 213.128 D. N. Stamires and J. Turkevich, J . Amer. Chem. SOC., 1964, 86, 749; I. I.Chkheidze and N. Buben, Zhur. strukt. Khim., 1962, 3, 709; V. A. Tolkachev, I. I.Chkheidze, and N. Buben, Doklady Akad. Nauh S.S.S.R., 1962, 145, 643.lz9 J. H. Weil and H. G. Hecht, J. Chem. Phys., 1963, 38, 281; Ya. S. Lebedev,Zhur. strukt. Khim., 1963, 4, 22; G. Vincow and P. N. Johnson, J . Chem. Phys., 1963,39, 1143.lao W. S1oug.h. Tram. Farccdccv Soc., 1963. 59. 2445.M. G. Ormerod, Polymer, 1963, 4, 451.V. A. Bgnderskii, I. B. Shgvdunko, and L.*A. Blyumenfel'd, Optika i Spektro-lssN. Hirota, C . A. Hutchison, and P. Palmer, J . Chem. Phys., 1904, 40, 3717.skopiya, 1964, 16, 46742 GENERAL AND PHYSICAL CHEMISTRY+0*219, +0-062, and -0.083, respectively. The spin distribution in thetriplet state thus closely resembles that in the naphthalene anion, as mightbe expected.Hornig and Hyde133 have made measurements on naph-thalene in durene at 4'H and 1 . 5 " ~ ; the temperature-dependence of absorp-tion intensities enables them to show that the zero-field splitting parametersD and E are positive and negative, respectively.It is not easy to find suitable host crystals for triplet studies, and theonly other recent single-crystal study is that by Vincent and Maki 134 whohave observed the lowest n-z* triplet of quinoxaline in a durene crystal.The values of D and E (0.1007 and 0.0182 cm.-l) are similar to those fornaphthalene. Hyperfine structure from the two nitrogen atoms and fromthe proton at position 5 can be resolved at certain crystal orientations.De Groot and van der Waals 135 have continued their elegant studies ofthe so-called Am = 2 transitions of randomly oriented triplets.The lineshape indicates that benzene in its lowest triplet state no longer possesseshexagonal symmetry and self-consistent field calculations suggest thepossibility of distortion to a structure having D2h symmetry. The lineshape is temperature-dependent, indicating that tunnelling between differentequivalent distorted configurations occurs at a frequency of lO9-lO10 sec.-l.The spectra of excited triptycene and tribenzotriptycene show evidence ofintramolecular excitation transfer between the three ring systems.Intriptycene the transfer rate is very fast but in tribenzotriptycene, excitationtransfer between the three naphthalene subsystems is slow enough to affectthe line shape which, indeed, varies with temperature. At very low tem-peratures the excitation is localised on one ring.Whilst most experiments are carried out on low-temperature glasses,Thornson136 has drawn attention to the advantages of using poly(methy1methacrylate) its host. It is possible to study both triplet lifetime and zero-field splitting over a large temperature range. D usually decreases veryslightly as the temperature is increased but unambiguous interpretation ofthis effect is diffcult to provide.The energies of the Am = 1 transitions have maximum or minimumvalues when the magnetic field is parallel to a principal axis of the zero-fieldsplitting tensor.Because of this it is possible to observe Am = 1 absorptionlines even from randomly oriented triplet molecules ; consequently theelements of the zero-field splitting tensor can be determined with an accuracywhich approaches that of single-crystal measurements.137 This fact has beenexploited with great ingenuity by Wasserman and his colleagues in a series ofpapers discussing, organic molecules with triplet ground states. In theirinitial experiments 138 they showed that ultraviolet photolysis of diazophenyl-methane in a suitable matrix at low temperatures results in the formationlSs A. W. Hornig and J. S. Hyde, Mol. Phys., 1963, 6, 33.lS4 J. S. Vincent and A.H. Maki, J . Chem. Phys., 1963, 6, 3088.la5 M. S. de Groot and J. H. van der Waals, Mol. Phys., 1963, 6, 545.lS6 C. Thornson, J . Chem. Phys., 1964, 41, 1.W. A. Yager, E. Wasserman, and R. M. R. Cramer, J . Chem. Phys., 1962, 37,138 R. W. Murray, A. M. Trozzolo, E. Wasserman, and W. A. Yager, J . Amer.1148; P. Kottis and R. Lefebvre, ibid., 1963, 39, 393.Chem,. Xoc., 1962, 84, 3213CARRINGTON : ELECTRON SPIN RESONANCE 43of diphenylmethylene which has a triplet ground state. In subsequentwork 139 they describe the spectra of the triplet molecules, fluorenylidene (15),cyclopentadienylidene (16), and indenylidene (17). In each case one un-(1 5 ) (16) ('7)paired electron is localised at the bivalent carbon atom and occupies anin-plane a-orbital. The second electron occupies a n-orbital and is, to vary-ing extents, delocalised over the ring system.Zero-field splitting para-meters for radicals (16) and (17) are D = 0.4089, E = 0.0120, and D = 0.3777,E = 0-0160 cm.-l, respectively, smaller D values indicating increaseddelocalisation of the n-electron. A most interesting observation is that theratio E / D should be proportional to the fraction of s-orbital character forthe in-plane o hybrid orbital, so that it is possible to estimate the angle8 formed by the two occupied hybrids forming the C-C o bonds. E/Dshould be zero for 8 = 180" and 1/3 for 8 = 120". The observed ratio forradical (16) suggests that 8 is greater than 135". Since it would be unreason-able to suppose that the actual C-C-C bond angle is greater than 135", theobservations suggest that the C-C a bonds are '' bent ".The same con-clusion emerges from consideration of 13C hyperfine interaction in radical (15).Whilst the methylene radical still eludes observation, two closely relatedspecies have been studied. The proton splitting 139 in benzylidene, Ph-CH:,is less than 15 Mc./sec., indicating that the C-C-H bond angle is certainlymuch less than 180". The cyanomethylene radical :C*H.Ca, is formedby photolysis of diazoacetonitrile 14O in polychlorotrifluoroethylene at-196". One e.s.r. line a t high field is observed and interpreted as beingthe lowest-energy Am = 1 transition. This assignment leads to a D valueof 0.889 cm.-l compared with the theoretical value 141 of 0.9055 cm.-l forCH2 itself.Photolysis of benzene- 1,4-diazo-oxide 142 dissolved in p-dichlorobenzeneat low temperatures results in the formation of the triplet molecule (18).0 0 0(18)Even though the radical is not oriented, the e.s.r. spectrum exhibits hyperfineinteraction from the two protons adjacent to the bivalent carbon atom andit is possible to obtain the principal values of each hyperhe tensor (8-7, 6.6,10.6 gauss) from the structure of each Am = 1 absorption line.The zero-field splitting parameters are D = 0-3179, E = 0.0055 cm.-1. The valuelaS E. Waaserman, A. M. Trozzolo, W. A. Yager, and R. W. Murray, J. Chem. Php.,1964, 40, 2408; E. Wasserman, L. Barash, A. M. TrozzoIo, R. W. Murray, and W. A.Yager, J . Arner.Chem. SOC., 1964, 86, 2304.R. A. Bernheim, R. J. Kemp, P. W. Humer, and P. S. Skell, J . Chem. Phys.,1964, 41, 1156.lrll J. Higuchi, J . Chem. Phys., 1963, 88, 1237.lr13 E. Wrtsserman and R. W. Murray, J . Amr. Chem. SOC., 1964, 86, 420344 GENERAL AND PHY8ICAL CHEMISTRYof D is determined largely by the n-electron density ( p ) on the bivalent carbonand one deduces p 0.4, suggesting that the n-electron distribution inradical (18) is very similar to that in the phenoxy-radical. The protonhyperfine coupling is expected to be positive and to arise mainly from thefact that there is a large spin density in the a-orbital on the bivalent carbonatom. However, the n spin densities a t the adjacent ring positions willpresumably be negative, thus giving an additional positive contribution tothe isotropic proton splitting (8.6 gauss).Whilst photolysis of diazo-compounds yields carbene derivatives, organicazides give rise to nitrenes, derivatives of NH, having triplet ground states.Wasserman, Smolinsky, and Yager143 have studied a number of alkyl-nitrenes; they invariably have D values in the range 16-14 cm.-ln-Propylnitrene, for example, has D = 1.607, E = 0.0034. cm.-1, the verysmall E value indicating that the spin distribution is essentially cylindricallysymmetrical.The D values for alkylnitrenes are only slightly smaller thanthat for :NH itself, determined as 1.86 cm.-l from the ultraviolet spectrumof Aash-photolysed HNCO. In contrast the value of D for phenylnitrene,PhN: is 0.99 cm.-l, indicating that one unpaired electron is delocalised intothe phenyl ring.Experiments have also been performed in which diazidesand bisdiazo-compounds are phot01ysed.l~~ Benzene-I ,4-diazide yields thedinitrene (19) with a triplet ground state. The pentaphenylcyclopentadienylcation has also been shown to have a very low-lying triplet state.145The clearest examplesare still to be found in the ion-radical salts of tetracyanoquinodimethane,l46but it has now been found 14' that single crystals of Wurster's Blue perchlorateexhibit behaviour characteristic of triplet excitons below 1 8 6 " ~ . Spin-exchange interactions between triplet excitons result in collapse of the e.s.r.fine structure to a single line,14S and the appropriate line-shape theory hasnow been developed by Lynden-Bell149 using density matrix methods.Halford and McConnell l5* have studied the effect of mechanical pressure onthe triplet exciton resonance in the 1 : 1 complex Morpholinium+TCNQ- ;D increases by -1 % and E by -1.6% for an increase in pressure of lo3 atm.,Interest in triplet excitons continues to grow.E.Wasserman, G. Smolinsky, and W. A. Yager, J . Amer. Chem. SOC., 1964,86, 3166.144 A. M. Trozzolo, R. W. Murray, G. Smolinsky, W. A. Yager, and E. Wasserman,J . Amer. Chem. SOC., 1963, 85, 2526.145 R. Breslow, H. W. Chang, and W. A. Yager, J . Amer. Chem. SOC., 1963, 85,2033.D. B. Chesnut and W. D. Phillips, J. Chem. Phys., 1961, 85, 1002.H. M. McConnell, D. Pooley, and A. Bradbury, Proc. Nat. Acad.Sci. U.S.A.,1962, 48, 1480; D. D. Thomas, H. Keller, and H. M. McConnell, J . Chem. Phys., 1963,89, 232.148 M. T. Jones and D. B. Cheanut, J . Chem. Phys., 1963, 38, 1311.149 R. M. Lynden-Bell, Mol. Phys., 1964, 8, 71.lsoD. Halford and H. M. McConnell, J . Chem. Phys., 1964, 41, 898CARRINGTON : ELECTRON SPIN RESONANCE 45this result suggesting that the dominant contribution to the zero-fieldsplitting arises from intermolecular spin-spin interactions.Experimental studies of triplet states have been accompanied by anincreasing number of theoretical investigations. McLachlan 151 has provideda rigorous derivation of the usual effective he-structure Hamiltonian,starting from the Hamiltonian for electron-spin dipolar interaction. Severalauthors l52 have discussed the calculation of zero-field splittings.It is clearthat, in the case of n-n* triplets in which both electrons are delocalised,zero-field splittings are not easy to calculate accurately; more rehed theoriesdo not necessarily yield the best results. On the other hand, the much widerrange of D values observed for triplets in which one electron is localisedenables valuable and interesting structural information to be obtained.Finally one should record that z-z* excited triplet states of certainnucleic acids have been measured 153 by e.s.r.Ga~~phage Free Radicals,-Electron resonance experiments in the gasphase continue to present problems. Atoms are, of course, readily detectedand several papers have described the spectra of H, 0, and N atoms inflames.154 McDonald 155 has, however, now added to the small list of mole-cules which have been observed by describing the spectra of SHY SD, and SO.SH('II3,2) radicals are produced by adding hydrogen sulphide to discharge-dissociated water at the entrance to the microwave cavity. A twelve-linespectrum is observed, arising from electric dipole transitions between theZeeman levels of the J = 3/2 rotational state.Weaker lines are ascribedto SO, with a 3E ground state, and this interpretation has been confirmedby Daniels and Dorain156 who produced SO by a microwave discharge insulphur dioxide. Some of the relaxation problems encountered in gas-phase work have been discussed by Freed.ls7Theoretical Studies.-The number of spin-density calculations continuesto increase rapidly although the precise relationship, if any, between carbonspin densities and proton hyperfine constants has yet to be established.Thesimple and valuable Mcconneu equation 158 (aH = Qpc) which relates thesplitting aH to the spin density pc on the adjacent carbon atom, has beenextended by Colpa and Bolton.159 They show that the splitting depends onthe charge density, as well as on the spin density, and derive an equationaH = (& + Ke)pc, where Q and K are negative constants and e is the excess161 A. D. McLachlan, MoE. Phys., 1963, 6, 441.lS2 S . A. Boorstein and M. Goutemm, J. Chem. Phys., 1963, 39, 2442; Y.-N. m u ,dbid., p. 2749; H. Sternlicht, ibid., 1963, 38, 2316; J. Higuchi, ibid., 1963, 39, 1847;J. Higuchi, ibid., p.1339; G. Smolinsky, L. C. Snyder, and E. Wassennain, Rev. Mod.Phys., 1963, 35, 376.lS8 R. 0. Rahn, J. W. Longworth, J. Eisinger, and R. G. Shulman, Proc. Nat.Acad. Sci. U.S.A., 1964, 51, 1299.154 C. C. McDonald, J . Chem. Phy8., 1963, 39, 3159; V. P. Balakhnin, I. M. Gem-henzon, V. N. Kondratiev, and A. B. Nalbandian, Doklady Akad. Nauk S.S.S.R., 1964,154, 883; A. A. Westenberg and N. De Haas, J . Chem. Phys., 1964, 40, 3087; G. A.Sachyan and A. B. Nalbandyan, Izvest. A k d . Nauk S.S.S.R., OtdeZ khim. Nauk, 1964,1340.155 C. C . McDonald, J . Chem. Phys., 1963, 39, 2587.ls6 J. M. Daniels and P. B. Dorain, J . C h m . Phyg., 1964, 40, 1160.lS7 J. H. Freed, J . Chem. Phya., 1964, 41, 7.168H. M. McConneU, J .Chem. Phys., 1956, 24, 764.J. P. Colpa and J. R. Bolton, MoZ. Phys., 1963, 6, 27346 GENERAL AND PHYSICAL CHEMISTRYcharge density on the carbon atom. Their investigations go some way to-wards explaining the differences between the e.8.r. spectra of the cation andthe anion of the same hydrocarbon.It has earlier been pointed out that the Q value representing spin polarisa-tion in the C-H bond should vary according to the hybridisation of thecarbon atom;160 hence some dependence of the proton coupling on bondangle might be expected. Most of the subsequent experimental evidencehas tended to contradict the original theory, which has now been carefullyre-examined by Higuchi.lsl He shows that it is not easy to relate the bondangle and the proton splitting directly; if one takes into account the polarityof the C-H bond, one can account for the smallness of the effect.The thorny problem of hyperconjugation as a mechanism for isotropic,%proton couplings seems to have been finally resolved by Colpa and deBoer.162 They have dealt particularly with methylene couplings in aromaticsystems (the cyclohexadienyl radical and pyracene cation 164 being goodexamples) and have considered the possible sources of contact hyperfbeinteraction from a molecular-orbital viewpoint.They conclude that hyper-conjugation is the dominant mechanism and that spin polarisation in theo-bonds makes only a small contribution to the splitting. Valence-bondcalculations of methylene splittings have also been described.165The g values of aromatic radicals are always very close to the free-spinvalue and they have not aroused much interest in the past.Stone 166 hasnow derived a gauge-invariant Hamiltonian for spin systems and hasapplied his theory to aromatic ions and semiq~inones.1~7 The differencesbetween positive and negative aromatic ions are accounted for and theeffect of hetero-atoms is also understood. The theory predicts that theisotropic part of the g tensor for odd alternant radicals should have the value2.00257; experimental information is scarce but the ally1 radical’ hasg = 2-00254, in good agreement with the theory. Glarum 168 has alsodiscussed spin-orbit coupling in simple radicals (CH,, NH,, CH,) andestimated its contributions to the g tensor and zero-field splitting.Many spin-density calculations involving the molecular-orbital methodhave appeared; Huckel theory continues to be the most useful for radicalswhere negative spin densities are not involved; of the more sophisticatedtheories, McLachlan’s approximate self-consistent field method 169 continuesto find wide application. Karplus and his collaborators have furtherextended their valence-bond calculations for aromatic ions l 7 0 and havedeveloped perturbation methods for dealing with substituent effects in16oM.Karplus and G. K. Fraenkel, J. Chm. Phys., 1961, 35, 1312.162 J. P. Colpa and E. de Boer, MoZ. Phys., 1963-64, 7 , 333.169 R. W. Fessenden and R. H. Schuler, J . Chem. Phys., 1963, 38, 773.164E. de Boer and E. L. Mackor, MoE.Phys., 1963, 5, 493.16sR. B. Ingalls and D. Kivelson, J . Chem. Phys., 1963, 38, 1907; H. Fischer,ibid., p. 1023; S. Ohnishi and I. Nitta, ibid., 1963, 39, 2848; P. Nordio, M. V. Pavan,and G. Giacometti, Theor. Chim. Acta, 1963, 1, 302.lB6 A. J. Stone, Proc. Roy. Soc., 1963, A, 271, 424.A. J. Stone, MoZ. Phys., 1963, 8, 509.lB8 S. H. Glanun, J . Chem. Phys., 1963, 39, 3141.16@ A. D. McLachlan, MoZ. Phys., 1960, 3, 233.170T. H. Brown, M. Karplus, and J. C. Schug, J . Chem. Phys., 1963, 38, 1749.J. Higuchi, J . Chem. Phys., 1963, 39, 3455CARRINGTON : ELECTRON SPIN RESONANCE 47benzene anion derivatives. They also show how thermal averaging overnearly degenerate levels may be taken into account .171Instrumental Developments.-One or two papers seem likely to lead toimportant developments in the future.Hyde and Maki172 have carriedout successful ENDOR experiments on a free radical in solution. It ispossible to obtain exceedingly accurate proton splitting constants and todetect differences in splittings as small as 100 kc./sec. (3.6 x gauss).have discussed the use of a ‘‘ computer of averagetransients ” which, by repetitive scanning of the spectrum and eliminationof random noise, can bring about a substantial enhancement in signal-to-noise ratio. One of the commercially available instruments which performsthis averaging procedure also has a secondary (and possibly more sinister)facility. If supplied with a set of hyperfine coupling constants, appropriateinformation about nuclear spins, and line widths, it produces a first derivativespectrum which is indistinguishable from the genuine article.Allen and Johnson171 J.C. Schug, T. H. Brown, and M. Karplus, J . Chem. Phys., 1961, 35, 1873;J. C. Schug, T. H. Brown, and M. Karplus, ibid., 1962, 37, 330; T. H. Brown andM. Karplus, ibid., 1963, 39, 1115.17* J. S. Hyde and A. H. Maki, J . Chem. Phys., 1964, 40, 3117.173 L. C. Allen and L. F. Johnson, J . Amer. Chem. SOC., 1963, 85, 26684. HOLECULAR ENERGY TRANSFERBy A. B. Callear(Department of Phyaical Chemistry, The University, Cambridge)Introduction.-When two molecules collide, they may exchange translationalenergy, rotational energy, vibrational energy, or electronic energy. Theseprocesses are fundamental to an understanding of hydrodynamics, photo-chemistry, reaction kinetics, and electric discharges.Electronic-energytransfer in molecular collisions provides a means of achieving populationinversion in gas lasers. The simplest examples of energy transfer are thosewhich occur in the gas phase. The collision complex is isolated and, becausethe partition functions are known, gaseous systems are amenable to mathe-matical analysis. The subject was recently reviewed by Cottrell.1 Sincethat time there have been several papers on energy-transfer studies withestablished techniques of shock-wave and ultrasonic measurements. Thesemethods have now been rather extensively applied, yielding practically ourentire knowledge of rotational and vibrational relaxation. It is likely thatspectroscopic methods will become more important and will lead to a broaderconcept of molecular energy transfer.Although vibration-translation relaxa-tion is now understood in considerable detail, the other types of energytransfer have not yet been systematically investigated. The first object inthis Report will be to d e h e logically the different types of molecular energytransfer, the discussion being confined almost entirely to the true energy-transfer processin which there is neither chemical reaction nor exchange of charge. Inprinciple, energy-transfer processes can be divided into two categories : first,those in which the energy remains substantially of the same kind; and,secondly, those in which the energy is converted from one form into another.A well-known example of the first type is the exchange of electronic energybetween helium atoms and neon atoms (helium-neon laser) :He(23S,) + Ne(2lrSO) = He(llrS,) + Ne(28)An example belonging to the second category is the spin-orbit-vibrationalprocess whereby nitrogen deactivates selenium :N,(u = 0 ) + Se(43P,,) = N2(v = 1) + Se(4'P2)Considering the four types of molecular energy, it is convenient to classifya total of ten different kinds of energy transfer, though, except for therare case of exact resonance, some energy is always converted into transla-tion.We understand in detail only one of these ten types, namely vibra-tion-translation relaxation, because of the circumstance that vibrationalquanta are comparable with kT in a workable temperature range.Severalof the possible types of energy transfer, as defined above, are as yet un-explored, for example, intermolecular exchange of rotational energy andA + B* =A* + BT. L. Cottrell, Ann. Reports, 1961, 58CALLEAR: MOLECULAR ENERGY TRANSFER 49interchange of rotational and electronic energy. Ultrasonic dispersion andabsorption have been applied extemively to the measurement of the ratesof tramlation-vibration, tramlation-rotation, and tramlation-translationenergy transfer. The velocity of sound ( Y ) is related to the ratio of thespecific heats (y), the molecular weight ( M ) , and the absolute temperature(T) of the medium by the equation V2 = yRT/M. At high frequencies,excitation and de-excitation of internal molecular motion may be too slowto contribute to the specific heat, and consequently the specific heat increasesand therefore the sound velocity rises.From the variation of velocity withfrequency, the relaxation time can be determined. Thus measurement ofthe velocity of sound is a convenient method of determining the apparentspecific heat. In a dispersion region, energy is released out of phase and themedium becomes very inelastic. Therefore, measurement of the variationof the absorption coefficient with frequency also yields the energy-transferrelaxation times. The frequency corresponding to the absorption maximumis roughly equal to the reciprocal relaxation time.2, Relaxation of transla-tional energy can be observed by ultrasonic absorption at very high frequencyand low pressure, and also from the structure of the front of a shock wavein a monatomic gas.It requires approximately two collisions and is ofimportance in the determination of intermolecular forces.Rotation-Translation Energy !hamfer.-Ultrasonic measurements innitrogen and oxygen show that the probability of rotation-translation energytransfer is about 0.1 per collision. Similar results have been obtained byCowan and Hornig and by Levitt and Hornig? who investigated the structureof shock fronts in these gases. A light beam is partially reflected from ashock front because of the refractive-index gradient and, by recording thevariation with time of a photomultiplier signal, it can be shown that therotation-translation relaxation, slow compared with translational relaxation,distorts the shock front. -om the form of the intensity-time curves, aprobability of 4 .1 per collision was deduced, representing an average overa set of transitions involving a range of J states. At room temperature inoxygen, the levels J = 6 and 7 have the highest populations. Theoreticalcalculations with the distorted-wave approximation predict that, in sym-metric molecules, AJ = 2 transitions should have the highest probability,and, in unsymmetric molecules, transitions with AJ = -+1 are the mostprobable. Broida and Carrington have recently observed rotational re-laxation of nitric oxide in the A2Z+(v = 1) state, by populating a singlerotational level with an atomic resonance line at 2144 A.The source was aspecially constructed cadmium lamp, excited with an electrodeless radio-frequency discharge. With a low nitric oxide pressure and in the absence offoreign gases, only a single line in each branch was observed. Addition ofK. F. Herzfeld and T. A. Litovitz, “Absorption and Dispersion of Ultrasonica T. L. Cottrell and J. C. McCoubrey, “ Molecular. Energy Transfer in Gases ”,G. C. Cowan and D. F. Hornig, J . Chem. Phys., 1950, 18, 1008; B. P. Levitt andH. P. Broida and T. Carrington, J. Chem. Phys., 1963, 38, 136; cf. R. Holmes,Waves ”, Academic Press, Inc., New York, 1959.Butterworths, London, 1961.D. F. Hornig, ibid., 1963, 36, 219.G. R. Jones, N. Pusat, and W. Tempest, Trans. Paraday SOC., 1962, 58, 234250 GENERAL AND PHYSICAL CHEMISTRYargon or nitrogen produced rotational transitions of the A2E+(v = 1) state,observed by a spreading of the branches in the fluorescence spectrum.How-ever, the results could not be interpreted on the sole basis of Av = &1transitions. Multiple quantum transitions occurred with high probability,though it was not possible to measure the rate as a function of AJ.No measurement has been made of the rate of exchange of rotationalenergy in molecular collisions. Conservation of the angular-momentumvector would be rather restrictive on orientation. Any effects due to rota-tional exchange tend to be obliterated by the rapid rotation-translationrelaxation. Broida and Carrington did not record any marked differencesbetween the effects of nitrogen and argon so far as inducing the rotationalrelaxation of nitric oxide A2Z+(v = 1) was concerned (cf.Holmes et u Z . , ~who made ultrasonic measurements in oxygen and oxygen-helium mixtures).Vibration-Translation Energy !I!rans€er.-There are considerable experi-mental data on vibration-translation relaxation and, except for some minoraspects, they can be understood in terms of simple physical principles.Landau and Teller ti pointed out that the probability of vibration-translationenergy transfer depends on the exponential of the ratio of the period ofvibration to the duration of a collision: P M exp ( -YZ/V), where Y is thevibrational frequency, I is a length characteristic of the interaction potential,and v is the relative velocity [this is a special form of the more general resultP rn exp (-AEZ/hv)].If the repulsive potential is steep, the collidingmolecule rebounds before the oscillator has completed a single cycle, andenergy transfer has a high probability. The other extreme is a shallowinteraction potential which changes only slowly with distance. In this casethe collision occurs over a long time during which there is a gradual conversionof kinetic energy into potential energy. The process is ultimately reversedas the particles recoil and separate. In the latter case the probability ofexcitation or de-excitation of vibration is small, because the oscillator hastime to adjust itself as the colliding molecule approaches. The sameprinciple applies to all energy-transfer processes.The problem can betreated quantitatively by the method of distorted waves, whereby theamplitude of the inelastically reflected component is determh~ed.~ Thisdepends on J YmrYndr, where \Tm and Yn are the initial and final vibrationaleigenfunctions, respectively, and r is the internuclear displacement. Thusthe selection rules are identical with those for infrared transitions, Le.,Av = -+1 and PV++-1) = vP1+0,for the harmonic oscillator. is the probability of deactivation fromv = 1 to v = 0, per gas kinetic collision, and is approximately proportionalto exp -4(O’/T1/3), where 8’ is proportional to y2Z2,u, and p is the reducedmass. A similar result can be obtained by integrating the Landau-Tellerequation 6 over the Maxwell-Boltzmann velocity distribution, and a detailedaccount has been given by Schwartz, Slawsky, and Herzfeld (S.S.H.theory).’The last few years have shown the S.S.H. theory to be remarkably successful,both for vibration-translation relaxation and for vibrational exchange.6L. Landau and E. Teller, Phys. 2. Sowjetunion, 1936, 10, 34.7 R. N. Schwartz, Z . I. Slawsky, and K. F. Herzfeld, J. Chem. Phys., 1952, 20,1591; R. N. Schwartz and K. F. Herzfeld, ibid., 1954, 22, 767CALLEAR: MOLECULAR ENERGY TRANSFER 51Deactivator H,Z,,, (286'9) 2 x lo6 Izlv0 (calc.) 1 x 103can be predicted within a factor of about 5, over a wide temperaturerange, provided there is not a large disparity between the masses. of the twomolecules. Further discussion of the theory has been given by Widom,8 byNikitinYg and by Dickens and Ripamonti.loIf p is small (light molecules), the relative velocity is large and thecollision is of short duration.Then energy transfer has a high probability.The effect of varying ,u is shown by the experimental data in Table 1, takenfrom a paper by Millikan et aZ.11 on vibration-translation relaxation ofcarbon monoxide. Z1+o is the reciprocal of Pl+o. Clearly the S.S.H.theory overestimates the efficiency of relaxation by light molecules ; similarHD D, ~e I Ne_ _ ~ _ ___ __ ___3.4 x lo6 3.8 x lo' 3-3 X 10' 2-3 X lo8 -10'____100 , 4.3 x 103 1-2 x 103 1.0 x 104 I 3 x 107ITABLE 1results for relaxation of oxygen have been obtained by Parker.12 Millikan'sresults were obtained with a new and ingenious technique.Carbon monoxideflowing at one atmosphere and 10 cm./sec. was excited by infrared radiationfrom a methane-oxygen flame. Resonance fluorescence was observed down-stream, corresponding to a vibrational temperature of 993°K. From theincreased rate of decay of the fluorescence, due to relaxation by added gases,the probabilities were determined. Abnormal effects of collisions of oxygenwith carbon monoxide are discussed below.Millikan and White l3 have recently reviewed and systematised shock-tube data on simple systems. Their presentation led to the empiricalequation :where P = pressure in atm., z = relaxation time in sec., p = the reducedmass, and 8 = the characteristic temperature (OK), This equation repro-duced the observed relaxation times within about 50% for systems as diverseas nitrogen, iodine, and oxygen-hydrogen.Similar systematic correlationshave been described by Losev and 0sip0v.~~ Relaxation of oxygen byoxygen is five times faster than relaxation by argon. Millikan and White l3suggested that this difference may arise because of the possibility of vibra-tion -rotation-translation energy transfer for oxygen-oxygen collisions,log,, ( P ~ ) = 5 x 1 0 - 4 ~ 1 ~ 3 [ ~ - 1 ~ 3 - o.oi5p1/*1 - 8,B. Widom, Discuss. Faraday Soc., 1962, 33, 37.E. E. Nikitin, Discuss. Faraday Soc., 1962, 33, 14.lo P. G. Dickens and A. Ripamonti, Trans. Faraday SOC., 1961, 57, 735.l1 R. C. Millikan, J . Chem. Phys., 1963, 38, 2855; cf. D. J.McCaa and D. Williams,l2 J. G. Parker, J . Chem. Phys., 1961, 34, 1763.l3 R. C. Millikan and D. R. White, J . Chem. Phys., 1963, 39, 3209.l4 S. A. Losev and A. I. Osipov, Uspekh; Fiz. Nauk, 1961, 74, 393; Soviet Phye.J. Opt. Xoc. Amer., 1964, 54, 326.Uspekhi, 1962, 4, 62552 GENERAL AND PHYSICAL CHEMISTRYoriginally predicted by Nikitin.15 Rdaxation of oxygen has also beeninvestigated recently by Wray and Freeman l6 and G-enemlov.17Gaydon and Hurle18 have described progress in application of thetemperature-reversal method to the study of relaxation and dissociation inshock-heated gases. The temperature of a hot gas can be measured byfocusing a black-body source through it on to the slit of a spectrograph.If the light source and the flame subtend the same solid angle to the detector,when they have the same temperature, the flame does not affect the lightflux falling from the block body on to the detector.Gaydon and his co-workers have shown that if reversal of a strong atomic resonance line isobserved, then the apparent electronic-relaxation time is equal to thevibrational-relaxation time (this is discussed below in the section on electronic-vibrational energy transfer). In this way, the vibrational temperature andvibrational-relaxation time in a shock-heated gas can be measured directly.The results for nitrogen and carbon monoxide and dioxide are in satisfactoryagreement with those obtained by other methods.It has now been established that vibration-translation relaxation ofnitric oxide is abnormally fast, by using shock-wave methods,lS ultrasonicabsorption,20 and flash photolysis.2l P130is about 3 x at ~OO'K,which is to be compared with an S.S.H.value of -lo-*. The mostsatisfactory explanation of this abnormal rate is in the theory of Nikitin 22who suggests that when two nitric oxide molecules collide a singlet or tripletcomplex may be produced, the splitting corresponding to a vibrationalquantum. Thus the transition is effectively vibration-electronic translation.Wray l 9 has shown that the experimental data for nitric oxide a t low tem-perature are interpreted by Nikitin's theory, and a t high temperature bythe S.S.H. theory.Vibrational relaxation in carbon dioxide has been reported by Withman,%particularly in relation to intramolecular energy transfer.He concludesthat internal energy transfer from the bending to the stretching mode is atleast 10 times faster than vibration-translation relaxation of the bendingmode. Theoretical aspects of this problem were discussed by Her~feld,~~and further experiments have also been described.25Vibration-Vibration Energy Transfer.-Exchange of vibrational energybetween complex molecules such as hydrocarbons is known to occur atpractically every gas-kinetic collision and can be qualitatively investigatedl5 E. E. Nikitin, Doklady Akad. Nauk S.S.S.R., 1962, 4, 525.l6 K. L. Wray and T. S. Freeman, A.V.C.O. Everett Research Dept., 1963, 169.lT N. A. Generalov, V'estnik: Moscow Univ., Ser. 111, Fiz. Astron., 1962,17, No.2, 15.A. G. Gaydon and I. R. Hurle, 8th Symp. Combustio?' Williams and Wilkins,Baltimore, 1962, p. 309; E. F. Greene and J. P. Toennies, Chemical Reactions inShock Waves", Edward Arnold, London, 1964.Is F. Robben, J. Chem. Phys., 1959, 31, 420; W. L. Wray, ibid., 1962, 38, 2597.$0 H. J. Bauer, H. 0. Kneser, and E. Sittig, J. Chm. Phys., 1959, 30, 1119.21 N. Basco, A. B. Callear, and R. G. W. Norrish, Proc. Roy. SOC., 1961, A, 260,23 E. E. Nikitin, Opt& and Spectroscopy, 1960, 9, 8.ar K. F. Herzfeld, Discuss. Faraday SOC., 1962, 33, 22.35 J. Daen and P. C. T. de Boer, J. Chem. Phys., 1962, 36, 1222; T. G. Winter,459.W. J. Witternan, J. Chem. Phys., 1962, 37, 655.ibid., 1963, 38, 2753CALLEAR: MOLECULAR ENERGY TRANSFER 63by ultrasonic dispersion in gas mixtures.It is difficult to measure the ratesof vibrational exchange by ultrasonics or shock waves. Both methods yieldthe relaxation time for interconversion of translational and vibrationalenergy, and for gas mixtures the ratedetermining step is usually vibration-translation relaxation of the component with the lowest vibrational frequency.Lambert, Edwards, Pemberton, and Stretton S6 have measured ultrasonicdispersion in mixtures of pairs of polyatomic gases which have near-resonantvibrational levels (fundamental vibration modes of almost identical fre-quency). All these mixtures showed a linear dependence of reciprocalrelaxation time on molar composition, which is required whether or notintermolecular exchange of internal energy occurs.However, the resultsshowed clearly that in a mixture of A and B, in which B has the lowervibrational frequency, A is excited from B by intermolecular vibrationalexchange. Energy-level diagrams were given for various mixtures, and itwas concluded that exchange of vibrational quanta occurs at approximatelyevery collision. Vallee and Legvold27 reached similar conclusions on thebasis of similar experiments. McCoubrey, Milward, and Ubbelohde 28 inves-tigated catalysis of energy transfer by water and deuterium oxide in a varietyof substances.Vibrational exchange between diatomic molecules with a comparativelyhighvibrational frequency has been reported by Basco, Callear, and N o ~ ~ i s h . ~ Nitric oxide X21s(v = 1) can be excited by flashing nitric oxide under iso-thermal conditions.The decay of the excited molecules and the effect ofadded gaseswere observed bykinetic spectroscopy. Nitric oxide X211(v = 1)is deactivated rapidly by carbon monoxide, and the spectroscopic detectionof vibrationally excited carbon monoxide provided direct evidence for theexchange :NO@ = 1) + CO(v = 0) = NO(u = 0) + CO(v = 1)To obtain a rate of vibrational exchange a t very close resonance, Callear andSmith 30 measured the exchange between nitric oxide A2X+ and nitrogenXIC+,. Table 2 lists the quantitative results for vibrational exchange (allexothermic), and it has been demonstrated that the number of collisions forvibrational exchange depends on the exponential of the change in internalenergy.51The last result in Table 2 is taken from the work of Millikan 11 on infraredfluorescence.It was shown that oxygen was “abnormally effective ” indeactivating carbon monoxide and the observed rate constant may corre-spond to the exchange process of Table 2.It was shown that water is extremely efficient at deactivating nitric oxideJ. D. Lambert, A. J. Edwards, D. Pemberton, and J. L. Stretton, Discuss. FurduySoc., 1962, 33, 61; cf. J. D. Lambert, D. G. Parks-Smith, and J. L. Stretton, Proc. Roy.SOC., 1964, A , 282, 380.27L. M. Vallee and S. Legvold, J. Chem. Phys., 1962, 36, 481.28 J. C. M.cCoubrey, R. C. Milward, and A. R. Ubbelohde, PTOC. Roy. SOC., 1962,A, 269, 456.28 N. Basco, A. B. Callear, and R. 0. W. Norrish, Proc. Roy. SOC., 1963, A, 269,180.A.B. Gllear and I. W. M. Smith, Trans. Faraday SOC., 1963, 59, 1720, 1735.a1 A. B. Callear, Discuss. Faraduy SOC., 1962, 33, 2854I NO(A 2X+)-N2(X12+0)I I NO(X2n)-CO(X1C+)GENERAL AND PHYSICAL CHEMISTRY80010,000TABLE 2Process j z , AE (cm.-l)I-- ~NO (X X'X+g)co(x'~+)-o,(x3X-g)-~ -_500,0004,600,00012267_______4547-1[X2n(u = l)], 2 at 300"~ being 140. At first sight, and in light of Table 2,it appears that the catalytic effect of water is not explicable in terms ofvibrational exchange, since AE = 282 cm.-l. However, it was recentlyshown,32 by following closely Herzfeldand Litovitz's calculation,2 that Z( calc.)is 200, in good agreement with experiment. The main reason why water isso effective is that in a hydride molecule the hydrogen atoms carry practicallyall the kinetic energy.Collision with the heavy end of the molecule is with-out effect, but the hydrogen atom is extremely vulnerable to energy-transferring collisions. The effect of this is evident in the pre-exponentialmass function of the S.S.H. equations and appears t o be the main reasonfor the general catalytic efficiency of water in vibrational-energy transfer.The following qualitative observations have been made on the inter-molecular exchange of vibrational energy between simple molecules.Morgan, Phillips, and Schiff 33 produced vibrationally excited nitrogen in adischarge tube by the reaction, N + NO = N,? + 0. lo3 wall collisionswere required for vibrational relaxation (surprisingly inefficient), and relaxa-tion was catalysed by addition of nitrous oxide and carbon dioxide.Thecatalytic effects are consistent with a vibrational-exchange mechanism.Flash-photolysis of carbon disulphide-oxygen mixtures produces vibration-ally excited SO which can be relaxed by exchange with 0xygen.5~Basco and Norrish 35 produced highly vibrationally excited nitric oxideby flashing nitrosyl chloride. Relaxation was catalysed by exchange on addi-tion of nitric oxide. Findlay and 901anyi,~6 in a study of the vibrationallyexcited hydrogen chloride produced by the reaction, H + C1, = HCl+ + C1,observed effects due to vibrational exchange between the hydrogen chloridemolecules. For example, the observed 2 for the exchangewas 5000.This is a fairly slow process because of 610 cm.-l anharmonicity(in the absence of anharmonicity such an exchange between hydridm wouldoccur at every collision). The anharmonicity thus " protects " the initialJ. E. Morgan, L. F. Phillips, and H. I. Schiff, D&?cw8. Furaday SOC., 1962, 38,HCl(v = 6) + HCl(v = 1) = HCl(V = 7) + HCl(v = 0)82 A. B. Callear, J . Appl. Optics, Suppl. on Chemical Lasers, 1964.84 A. B. Callear, Proc. Roy. SOC., 1963, A , 278, 401.86 N. Basco and R. G. W. Norrish, Proc. Roy. SOC., 1962, A , 268, 291.8 6 F . D. Findlay and J. C. Polanyi, Cunud. J. Chem., 1964, 42, 2176.118CALLEAB: MOLECULAR ENERGY TRANSFER 55distribution. Millikan and White s7 have shown that vibrational exchangebetween nitrogen and carbon monoxide is very fast in a shock-heated gasmixture.The infrared emission was monitored from nitrogen containing atrace of carbon monoxide (S.S.H. method A was preferred to method B inthe interpretation of the results).The selection rules for vibrational exchange have been investigated forthe nitric oxide (A2Z+)-nitrogen system.30 More than 85% of transitionsz , , 0.1 z , , ; O,l Z L O ; on1___.~ ___TABLE 3z1:o 091 (S.S.H.)200 400 7- 2000 56 GENERAL AND PHYSICAL CHEMISTRYdue to acceleration through the potential hole. It therefore presents aconsiderable challenge to create order out of the experimental results andconfusions. The logical route to solution of some of these problems is toinvestigate low-lying electronic stabs which differ from the ground stateonly by orientation of electron spin with the orbital angular momentum.Such electronically excited species have no vacant orbital and may beexpected to have only van der Waals interaction, a t least with the inert gasesand some of the stable diatomic molecules.The classical spin-orbit relaxation of mercury ( 63P) has recently receivedcloser scrutiny.MatlandS9 has shown that the activation energy of theprocessis equal to the discrepancy between the spin-orbit splitting and the funda-mental of nitrogen, thereby providing direct evidence that the nitrogen isvibrationally excited. Callear and Williams 4o have, however, investigatedthe quenching of Hg(63P,) by a large number of molecules, and have shownthat only nitrogen, carbon monoxide, water, and deuterium oxide causespin-orbit relaxation.Practically all other simple molecules quenchHg(63P,) to the ground electronic state. It was shown that there is nocorrelation between the efficiency of quenching and the energy which cannotbe converted into vibration. Dickens, Linnett, and Sovers4l have givena formal mathematical treatment of the resonant transfer of electronic tovibrational energy for diatomic molecules. They concluded that the rateshould fall off with increasing energy discrepancy, but should also be depend-ent on the steepness of the intermolecular repulsion. Thus the quenchingby deuterium oxide and water, where the intermolecular force is fixed,may be consistent with their treatment. Bykhovskii and Nikitin 42 recentlypointed out that any calculation of the quenching of Hg(63P1) shouldtake account of the removal of the three-fold degeneracy during a collision.Interaction of 3P1 with a quenching molecule produces three molecularspecies, only one of which can undergo a radiationless transition to the" (3P0) complex." The efficiency of quenching would then depend, noton the change in internal energy (energy discrepancy), but on the energyseparation of the potential surfaces in the transition complex.However,their treatment predicts a substantial temperature coefficient, which is notfound experimentally. In fact, Hg( 63P,) probably interacts chemically( E - 10 kcal. mole-1) with all the quenching species, and the situation maybe more complex than either of the theoretical models suggests.To obtain further information about this type of process, Callear andTyerman 43 investigated spin-orbit relaxation of selenium ( 43P).Prelim-inary results show that the rates of the processesvary systematically with the change in internal energy.Hg(6'PJ + N, = Hg(6'pO) + N z fSe(43P0) + M = Se(43P,) + M38 C. G. Matland, Phys. Rev., 1953, 92, 637.roA. B. Callear and G. J. Williams, Trans. Paraday SOC., 1964, 80, 2158.41 P. G. Dickens, J. W. Linnett, and 0. Sovers, Di8cuss. Farday SOC., 1962,33, 52.48 V. K. Bykhovskii and E. E. Nikitin, Optics and Spectroscopy, 1964, 18, 111.43 A. B. Callear and W. J. R. Tyerman, Nature, 1964, 202, 1326CALLEAR: MOLECULAR ENERGY TRANSFER 57A very interesting problem in energy transfer is to determine the yieldof vibrational energy when a substantial conversion of electronic energyoccurs. A well-known example is the quenching of sodium (32P), whichoccurs at almost every collision by any gas, with the exception of the inertgases,4a e.g.,Na(3,P) + N, = Na(3,S) + N2At one time it was believed that such processes occurred because of resonance,the nitrogen taking up all the electronic energy as vibration.It is now fairlyobvious that this is incorrect.32 Dickens, Linnett, and Sovers 41 have shownthat the probability of multiple- quantum vibrational transitions by resonanceis vanishingly small. Karl and Polanyi 45 have observed infrared emissionfrom vibrationally excited carbon monoxide, produced byAlthough the initial distribution of vibrators has not yet been worked outit is obvious that the yield of vibrational energy is < 50%.Quenchingoccurs because of chemical interaction which brings together the potentialcurves of the initial and the final state of the system in the transition complex,the fragmentation of which produces a low yield of vibrational energy, tend-ing towards a random distribution amongst the available degrees of freedom.At first sight it is difficult to see how the observations by Gaydon et aZ.18can be consistent with random fragmentation. However, it was recentlysuggested that, if collisional quenching of an electronically excited moleculeproduces a finite yield into any one of the vibrational levels of the quenchinggas, then the apparent electronic relaxation time will be identical with thevibrational-relaxation time.However, the electronic and the vibrationaltemperature should be quite different .32Vibration-Rotation Energy Transfer.-A few fragments of informationhave recently come to light which suggest that efficient interconversion ofvibrational and rotational energy may be possible. Nikitin’s postulate l5and Millikan and White’s l3 results were mentioned above. There maybe evidence to support the view that oxygen relaxes oxygen more rapidlythan argon does, because of the possibility that some fraction of the energyis transferred through rotation in the former case. Millikan and Osburg 46have shown that there is a significant difference between ortho- and para-hydrogen, in their ability to deactivate vibrationally excited carbon mon-oxide ; this was demonstrated by the infrared method, para-hydrogen beingcompared with an ortho-para mixture; they suggest that the difference maybe due t o participation of rotation in the overall energy-transfer mechanism,though why this should be is not clear.Cottrell and his colleagues 47 have shown that the vibrational-relaxationtime of methane is less than that of tetradeuteriomethane, notwithstanding44 P.Pringsheim, “ Fluorescence and Phosphorescence”, Interscience Publ., Inc.,45 G. Karl and J. C. Polanyi, J . Chem. Phys., 1963, 38, 271.p6 R. C. M i l l h and C. A. Osburg, J. Chem. Phys., 1964, 41, 2196.New York, 1949.T. L. Cottrell and A.J. Matheson, Trans. Furaduy sbc., 1962, 58, 2336; 1963,59, 824; T. L. Cottrell, R. C. Dobbie, J. McClain, and A. W. Read, ibid., 1964,80, 24158 GENERAL AND PHYSICAL CHEMISTRYthe higher vibrational frequencies of the former. They suggest that moleculeswith a small moment of inertia are able to fulfil the Landau-Teller conditionfor interaction of vibration with rotation, because of their high peripheralspeeds of rotation. By a semi-classical calculation, theoretical values forthe ratio of the relaxation times of methane and tetradeuteriomethane werederived and agreed with experiment. Similar results and conclusionsresulted from experiments with PH3-PD,, and SiH4-SiD,. The vibrational-relaxation time of ammonia is apparently about one-sixth of that of tri-deuterioammonia, and ammonia relaxes abnormally rapidly according tothe Lambert-Salter plot.49 In this case Cottrell and Matheson47 put for-ward the interesting view that the abnormally fast rate of relaxation ofammonia is due to inversion during collision, which has an impulsive effecton intermolecular repulsion ; trideuterioammonia has a smaller probabilityof inversion during collision, and this may account for the difference invibrational-relaxation times. Cottrell, Dobbie, McClain, and Read 47 in-vestigated AsH,-AsD,, and again found evidence for vibration-rotationrelaxation.Some recent observations by Brown and Klemperer indicate 48that interconversion of rotation and vibrational energy is improbable.Electronic-Translation Enera Transfer.-The interchange of electronicand translational energy has not yet been systematically investigated. Ina recent review 32 of the few existing results, it was suggested that the datamay be consistent with the Lambert-Salter pl0t.~9Phelps50 has shown that collisional transitions are important in thedecay of metastable neon atoms [Ne(ls)] produced in an electric discharge.The lack of a systematic variation of rate with AE was attributed to differ-ences in the interaction potentials.Chapman, Krause, and Brockman 51have measured the cross-section for the spin-orbit relaxation of potassium:ArK(4%/2) II K(42G/JThe cross-section corresponded to relaxation at every collision and appearedto be the same in either direction.Hectronic-Electronic Energy Transfer.-The formal theory of the ex-change of electronic energy between atoms has been reviewed by Masseyand B~rhop.~2 If the change in internal energy is small and the transitionsare optically allowed for both species, then long-range resonance interactionshould result in a large cross-section for excitation transfer, which mayapproach 5 x 10-14 cm.2 Although such long-range excitation transfer iswell known for complex molecules, it is as yet unknown for atom-atomcollisions (except in ionisation processes).The theory predicts a sharpdecrease of cross-section with increasing energy discrepancy. If the transi-tions in each atom are associated with a quadrupole, the cross-section forAE = 0 falls to 10-15 cm.2, which is approximately the gas-kinetic cross-48 R.L. Brown and W. Klemperer, J . Chem. Phys., 1964, 41, 3072.49 J. D. Lambert and A. J. Salter, Proc. Boy. SOC., 1957, A , 253, 280.61 C. D. Chapman, L. Krause, and I. H. Bro$nan, Can. J . Phys., 1964, 42, 535.68 H. S. W. Massey and E. H. S. Burhop, Electronic and Ionic Impact Phe-A. V. Phelps, Phys. Rev., 1959, 114, 1011.nomena”, Clarendon Press, London, 1952CALLEAR : MOLECULAR ENERGY TRANSFER 59Colgrove, Schearer, and Walterss3 have shown that the cross- section.section for the exchangeHe(2%',) + He(lW,) = He(lW,,) + He(23S,)is 1O-l' cm.2 at 4.2'9.Research on optical masers has revived interest in excitation transferbetween atoms. Rautian and Sobelman 54 postulated that the sharingbetween the 928 and the 82.2' state in mercury-photosensitised sodiumfluorescence should be according t o the scheme+ Hg(6lXo)I8"a(82P) + w61Xo)I rNa(g Hg( 63P1) + Na( 3%')-This is apparently based on the assumption that the cross-section dependson exp (-AE/kT).Frish and BochkovaS5 claim, however, t o havedemonstrated that the 8P state is produced only in low yield. This maybe due to the effect of interatomic interaction on the course of the energytransfer. However, the conclusions were based on stationary concentrationsin the two levels rather than on rates of production into the levels. A moredetailed examination of the problem would be worthwhile. According toFrish and Bochkova, the cross-section for excitation to the 8P state, theprocess with the smallest energy discrepancy and for which the opticaltransitions of both atoms are allowed, is smaller than the cross-section intothe 98 state, which is optically forbidden for the sodium.Recent laser research provides our only quantitative information aboutelectronic-excitation transfer between atoms.In an electric discharge inhelium containing a trace of neon, energy transfer occurs from metastablehelium atoms to neon and causes population inversion. For pure helium,Phelps and Brown 560bservedthe decay of He(238,), He(21S,),a.ndHe,(a3~+,),following a pulsed d.c. discharge. The metastable species were detectedphotoelectrically. Javan, Bennett, and Herriott 57 employed Phelps andBrown's method to observe the increased rate of decay of He(23S1) in thepresence of neon, and recorded a cross-section of 0.5 x 1O-l' cm.2 Theyproved that transfer occurred to the neon, by observing the 2s-+2pemission lines during the afterglow.Apparently all four 2s levels are directlypopulated, though the individual cross-sections have not yet been reported.Benton, Matson, Ferguson, and Robertss8 employed the same method tomeasure the rate of excitation from He(2l8,) to neon. Transfer occurspredominantly to the 38, state,s9 with a cross-section of -4 x 10-ls cm.2The helium-neon system does not show systematic behaviour in either thelevels excited or the variation of cross-section with AE.32Finally, a summary is recorded of miscellaneous observations of energytransfer involving electronically excited states of complex molecules.Parmenter and Noyes 60 have investigated vibrational-energy transfer fromelectronically excited acetaldehyde vapour : dissociation and intersystemcrossing account for most of the energy dissipation. Williams and Gold-smith studied the fluorescence of naphthalene vapour and concluded thatthe excess of vibrational energy is distributed among the vibrational modesin a time that is short compared with the radiative lifetime. Evidence forthe existence of a triplet state of benzene was described by Dubois andCox.62 Fluorescence of biacetyl was sensitised by a variety of organicmolecules in cyclohexane (exchange between singlets), the rate being diffusion-controlled ; in rigid media, phosphorescence of biacetyl was observed, beingdue to energy transfer from the benzene triplet.Triplet-singlet transfer,and the interconversion of electronic and vibrational energy in complexorganic molecules, were discussed by Ermolaev and Sveshnikova.63 Theabsence of a solvent effect for triplet-triplet transfer in rigid glasses wasdemonstrated by Siegel and Judeikk6* Daxe and Weller,65 and Holloway,Kestigian, and Newman,66 have investigated energy transfer between rare-earth ions in solution. Benz and Wolf 67 measured fluoreecence and energytransfer in phenanthrene crystals. A curious example of intramolecularenergy transfer has been described by Schnepp and Levy? anthracene andnaphthalene units were joined together by saturated alkane chains of 1, 2,and 3 carbon atoms; the naphthalene group alone was excited, with appro-priately filtered light, but the fluorescence was characteristic of anthracene ;absolute quantum efficiencies for intramolecular-energy transfer were deter-mined.Phillips 69 has shown that electronically excited nitrogen, producedin an electric discharge, exchanges excitation with metal atoms, e.g. :PbCl + N,('C+g) + Pb* + C1 + Ng('X+g)Reaction and energy-transfer mechanisms in mercury-photosensitisedreactions have been reviewed.THE emphasis in this subsection is on the measurement of heats of formationof stable chemical substances, mainly by calorimetric methods. Althoughthe main stress is laid on work published during 1964, reference is made tosome of the major developments since 1960, when the last Report on thissubject appeared.In recent years there have been notable advances in the techniques ofexperimental thermochemistry.Rotating-bomb calorimetry and fluorine-bomb calorimetry have extended the usefulness of the combustion bomb toa much wider range of compounds. Several novel calorimeters have beendesigned for measuring heats of reaction other than combustion, and thesehave been described 2 in detail. Microcalorimeters for measuring very smallheats are now available. The apparatus designed by Benzinger and hisco-workers is finding increasing application> and Calvet and R a t reviewdevelopments of the Calvet microcalorimeter, an instrument in which heatsof very slow reactions can be measured. Higher temperatures are beingused in study of reactions, either calorimetrically, or by a variety of methodswhich yield equilibrium data, from which AH terms can be calculated; someof these developments in thermochemistry have been reviewed in a shortarticle.An outstanding publication 7 is that of the eight plenary lectures presentedat the Symposium on Thermodynamics and Thermochemistry, held inLund, Sweden, in 1963.Thermochemical papers published during 1963 havebeen reviewed in detail by Skinner.8Heats of Combustion in Oxygen.-Hydrocarbon. Evaluation of strainand stabilisation energies in ring systems continues to receive attention.The difference between fhe heats of combustion of an isomeric pair is a directmeasure of the relative strain energies of the compounds. For example,trans-syn-trans-perhydroanthracene (l), in which the central ring has thechair form, is more stable by 4-8 kcal./mole than the truns-anti-trans com-pound (2), which has a skew-boat ring.g exo-2-Cyanobicyclo[2,2,l]heptane(3) is more stable than the endo-compound (4) by 1.6 0.4 kcal./mole.loFor the corresponding 2-methyl-7-oxabicyclo[2,2,l]heptane isomers thefigure is 0.85 &- 0.23 kcal./mole.ll In a bond-energy approach, heats ofcombustion of 2,2-p-cyclophane (5), acenaphthene, acenaphthylene (6))and fluoranthene (7) yield strain energies of 30, 1, 6, and 6 kcal./mole,respectively.12 Strain energies in the following spirocycloalkanes may becalculated from reported l3 heats of combustion : spiro[4,5]decane (€9,spiro[5,5]undecane, and spiro[5,6]dodecane.The directly measured gas-phase heat of hydrogenation of bicyclo[2,2,2]octa-2,5,7-triene (9) to thediene (10) is -37.6 kcal./mole, a figure which indicates that steric strainmust exceed any stabilisation effects.l* The heat of hydrogenation of cyclo-tetradeca- 1 ,8-diyne, C14H2*, to cyclotetradecane, derived from heats ofcombustion,l5 is close to that expected for two acetylenic bonds, whichrules out transannular interaction between these bonds.Carbon-hydrogen-oxygen compounds. The adaptation of the flamecalorimetric technique to volatile liquids, by Pilcher, to obtain reliable heatsof combustion for diethyl ether, ethyl vinyl ether, divinyl ether,16 dimethylether, ethyl methyl ether, methyl propyl ether, and isopropyl methyl ether l7is especially important: reliable heats of formation for these simple compoundshave not been available previously.The calculated heats of hydrogenationof divinyl ether and ethyl vinyl ether have been compared with those ofthe corresponding hydrocarbons, in which -0- has been replaced by4H,-, and n-conjugation energies of the unsaturated ethers are calculated.The heats of combustion of the four cyclic ethers, ethylene oxide, trimethyleneoxide, tetrahydrofuran, and tetrahydropyran, in which the ring size increasesfrom 3 to 6 members, have also been measured.18 Strain energies in thesering systems, and the corresponding ones in which the oxygen atom isreplaced by CH,, S, or NH are calculated.The AH,” value of m-, o-, and p-ethylphenol, measured l9 at the NationalChemical Laboratory, show that in the gas phase the meta- is more stablethermochemically than the ortho-isomer, which is more stable than the para-isomer.For the three toluic acids the order, for the crystalline state, isalmost reversed in that it is p > m > 0. These heats of combustion, to-gether with those of many other alkyl-substituted benzoic acids have beenreported by Colomina and his co-workers.2*Heats of combustion of some long-chain, aliphatic acids, R*CO,H,peroxyacids, R*C03H, and t-butyl peroxy-esters, R*CO,*OBut, whereR = n-C7H1,, n-CQHlQ, n-CI1H23, n-C13H27, n-CljH31, and n-C17H35, havebeen measured.21 The derived heat of the gas-phase oxidation0 0 His lower than expected, because hydrogen bonding twists the 0-0 bond,which increases lone-pair electron repulsion.The heat of combustion of ethyl methyl ketone, recently measured,22 is ingood agreement with that calculated from its heat of hydrogenation tobutan-2-01 and the heat of formation of this compound.A review of the heats of formation of C-H-0 compounds, availableup to 1961, has been gi~en.~3Organohalogen compounds.The application of rotating-bomb calori-metry to these compounds is well established. The Bartlesville group haveobtained AHc0 values for 2,2’-difluoro-, 2,2’-dichloro-, 4,4’-difluoro, and 4,4’-dichloro-biphenyl, which indicate that the 4,4‘-isomers are more stable thanthe sterically hindered 2,2’-isomers by - 1.3 k~al./mole.~* In work 25 on2,3,5,6-tetrachloro-1,4-xylene, hydroxylamine hydrochloride was found tol7 G.Pilcher, A. S. Pell, and D. J. Coleman, Tram. Faraday SOC., 1964, 60, 499.l8 A. S. Pell and G. Pilcher, Tram. Farday SOC., 1965, 61, 71.l9 D. P. Biddiscombe, R. Handley, D. Harrop, A. J. Head, G. B. Lewis, J. F.2o M. Colomina, R. Phrez-Ossorio, M. L. Boned, and C. Turribn, Symposium on21 H. A. Swain, Jr., L. S. Silbert, and J. G. Miller, J . Anzer. Chem. Soc., 1964,2 2 G. C. Sinke and F. L. Oetting, J. Phys. Cheni., 1964, 68, 1354.23 J. H. S. Green, &%art. Rev., 1961, 15, 125.24 N. K. Smith, G. Gorin, W. D. Good, and J. P. McCullough, J . Phys. Chem.,25 N. K. Smith, D. W. Scott, and J. P. McCullough, J. PFYys. Chem., 1964, 68, 934.Martin, and C. H. S. Sprake, J. Chem. SOC., 1963, 5764.Thermodynamics, Lund, Butterworths, London, 1963.86, 2562.1964, 68, 94064 GENERAL AND PHYSICAL CHEMISTRYbe unsatisfactory for reducing chlorine, formed on combustion, to chlorideions, as it was catalytically decomposed by the platinum lining of the bomb ;arsenious oxide, which is oxidised to arsenic acid, H,AsO,, can be used suc-cessfully.An important thermochemical correction here is the heat ofionisation of the acid, which is now known.26From combustion studies 27 carried out at the National Chemical Labor-atory, p-fluorobenzoic acid and pentafluorobenzoic acid have been recom-mended as comparison standards for the combustion of organic compoundshaving low and high fluorine content, respectively. Standard-state cor-rections for the combustion of organofluorine compounds can now be mademore easily.28 The heat of formation of hexafluorobenzene, C6F6,AHf" = -219.7 kcal./mole, is some 38 kcal.less than that calculated, by usingbond energies, from the heat of formation of benzene and fluorobenzene,27so that hexafluorobenzene appears to have considerably less stabilisationenergy than benzene itself. The AH," of octafluorocyclobutane is rep~rted.~"A review of the thermochemistry of organofluorine compounds has beenpublished.*OThe controversy about the heat of formation of the CF, radical continues.Measurements 31 of the appearance potential of the C1+ ion in the processCHF2C1 ---+ C1+ + CF, + H, makes possible the calculation of valueAHfo(CF,,g) = -20 kcal./mole, based onHowever, evidence from the kinetics of pyrolysis of this compound givesAHfo(CF2,g) = -53 & 7 k~al./mole.3~ A general study of the appearancepotential of the CF,- ion formed in the impact process of a number offluorocarbons yields a lower value of AHfo(CF,,g) = -35 kcal./mole.sPRecent measurements 35 of the appearance potential of the CF,+ ionfrom CHF, and CH,F2 yields a consistent value of 14-7 & 0.4 ev, whichprovides values for AHfo(CF2+) of 240 & 10 and 234 10 kcal./mole, basedon known heats of formation 36 of CHF, and CH2F,, respectively.Appear-ance potential studies of CF,+ from tetrafl~oroethylene,~: and the heat offormation 3t3 of C,F,, lead to the relationAHf(CF2+) + AHf(CF2) < 197 kcal./mole,whence AHfo(CF,) = -43 kcal./mole.AHfo(CF,,g) = -43 f 10 kcal./moleseems at present to be the best.AHfo(CHF2Cl,g) = - 112 kcd./mole."A value of*6 P.Sellers, S. Sunner, and I. Wadso, Acta C h m . Scand., 1964, 18, 202.2 7 J. D. Cox, H. A. Grundy, and A. J. Head, Trans. Paraday Soc., 1964, 60, 653.28 J. D. Cox and A. J. Head, Trans. Faraday SOC., 1962, 58, 1839.2 9 V. P. Kolesov, D. G. Talakin, and S. M. Skuratov, Zhur.fiz. Khim., 1964, 38,30 C. R. Patrick, Adv. Fluorine Chem., 1961, 2, 1.3lD. L. Hobrock and R. W. Kiser, J . Phy. Chem., 1964, 68, 575.32 S. M. Skuratov and V. P. Kolesov, Zhur. $2. Khim., 1961, 35, 567.33 F. Gozzo and C. R. Patrick, Nature, 1964, 202, 80.34 J. R. Majer and C. R. Patrick, Nature, 1964, 201, 1022.s5 w. c. Steele, J. PhJ8. Chem., 1964, 68, 2359.36 G.A. Neugebauer and J. L. Margrave, J . Phys. Chem., 1958, 82, 1043.3 7 J. L. Margrave, J . Chem. Phys., 1959, 31, 1432; C. Lifshitz and F. A. Long,38 G. A. Neugebauer and J. L. Margrave, J . Phys. Chem., 1956, 60, 1318.1701.ibirE., 1963, 67, 2463MORTIMER : THERMOCHEMISTRY 65The combustion of these compounds yieldssulphuric acid, so that derived heats of formation depend ultimately on theaccuracy with which the heat of formation of sulphuric acid is known. Therehave been three independent determinations of AHf"(H2S04,1 15H20).Two are based on the heat of combustion of sulphur and yield severally-212.10 &- 0.06 kcal./mole 39 and -212.24 -J= 0.07 kcal./rn~le.*~ Thethird41 depends on measurement of the heat of oxidation, by gaseouschlorine, of aqueous sulphur dioxide to form sulphuric acid, and gives-212.11 -J= 0.07 kcal./mole.A measurement of the heat of oxidation, bybromine, of both aqueous SO, and aqueous As20, has led to a new valueAHfo(HBr,1250H,0) = -29-00 k~al./mole.~lThe heats of formation of isothiocyanic and deuterioisothiocyanic acidhave beenReviews of the thermochemistry 43 and thermodynamic properties 44 ofmore than a hundred organosulphur compounds have been given.A critical discussion of carbon-sulphur bond dissociation energiesD(R-X), where X = SHY SR, SO-R, and SO,*R, which have been derivedfrom kinetic or electron-impact studies has been given." Once these valueshave been established, they may be used, in conjunction with known heatsof formation, to derive values for the heats of formation of the radicals Xby using the thermochemical equationThe values D(Ph-SH) = 53 & 2 and D(Ph.CH,-SMe) = 51.5 2 kcal./molehave been used to obtain the heats of formation AHfo(SH,g) = 34.6 5 4 andAHfo(SMe,g) = 25.5 -+ 3 kcal./mole.These can then be used, togetherwith known heats of formation of organosulphur compounds, to calculatethe bond-dissociation energies D(Me-SH) = 73 & 5 and D(Pri-SMe) =69Bills and Cotton 46 have measured AHfo oftetraethylgermane, Et,Ge, using a rotating-bomb calorimeter containingaqueous hydrogen fluoride. The heat of formation of the final solutionof H,GeF, was found from the heat of solution of germanium in an aqueoussolution of both hydrogen fluoride and hydrogen peroxide.47 The valueAHfo(Et,Ge,liq.) = -50.0 & 1.9 kcal./mole was obtained.From the heatof solution of germanium dioxide in aqueous hydrogen fluoride the heat offormation AHfo(Ge02,cryst.,hexa.) = - 132.2 & 1.2 kcal./mole was found.This is close to the previous value,48 when the latter is corrected by usingW. D. Good, J. L. Lacina, and J. P. McCullough, J . Amer. Chew. SOC., 1960,82, 5589.40 M. Mknsson and S. Sunner, Actu Chem. Scund., 1963, 17, 723.41 W. H. Johnson and J. R. Ambrose, J. Res. Nut. Bur. Stand., Sect. A, 1963,67, 427; W. H. Johnson and S. Sunner, Acta Chem. Scund., 1963, 17, 1917; S. Sunnerand S. ThorBn, Symposium on Thermodynamics, Lund, Butterworths, London, 1963.Organosulphur Compounds.D(R-X) = AHf"(R,g) + AHfo(X,g) - AEfo(RX,g).5 kcal./mole. Values for other sulphur bonds are also given.45Organometallic compounds.42 H.Mackle and P. A. G. O'Hare, Trans. Faraduy SOC., 1964, 60, 666.44 H. Mackle, Tetrahedron, 1963, 19, 1159.45 H. Mackle and R,. T. B. McClean, Trans. Faruday Soc., 1964, 60, 669; H. Mackle46 J. L. Bills and F. A. Cotton, J. Phys. Chem., 1964, 68, 806.*'J. L. Bills and F. A. Cotton, J . Phys. Chem., 1964, 68, 802.48 W. L. Jolly and W. A!!. Latimer, J. Amer. Chem. Soc., 1952, 74, 5757.H. Mackle and P. A. G. O'Hare, Tetruhedron, 1963, 19, 961.and P. A. G. O'Hare, ibid., p. 50666 GCENERSL AND PHYSICAL CHEMISTRYmore accurate ancillary data.49 Pope and Skinner 50 obtain AH," values of-48.4 & 0.8 and -72.7 kcal./mole for liquid tetraethyl- and tetrapropyl-germane, respectively, from static combustion measurements, based on thesame AH," value for germanium dioxide.Pope and Skinner have also obtained AH," and AHf" values for Me,Sn,E t,Sn, Me ,E t Sn, Pr4Sn, Me ,PhSn, Me ,Sn*CH:CH,, Ph*CH,*SnMe,,Me,Sn*SnMe,, Me,SnBr, Bu,SnBr, and Me3SnI,51 together with those forPh,Sn, Ph,SnBr, and Ph,SnBr,.52The AH," of triphenylarsine in oxygen has been measured 5, in a rotatingbomb charged with sodium hydroxide solution, when the final solutioncontained sodium arsenite, arsenate, and carbonate, and an excess of sodiumhydroxide.The heat of combustion of tri-isobutylaluminium has also beenmeasured 54 and the value AHfo(AIBui,,liq.) = - 69.9 kcal./mole calculated.Lautsch et have reviewed the available AH," data for organometalliccompounds.Heats of combustion of seven octahedral iron@) complexes with/3-diketones, in their en01 form R*CO*CH=CR'*OH, have been reported.56The oxygen-bomb calorimeter has also been used to determine the heats offormation of other metal compounds.These include the molybdites, SrMO,and BaMoO, (ref. 57), the hydrides and deuteride, MgH, (ref. 58), ZrH, andZrD, (ref. 59), the nitride, UN, and the carbides, HfC and HfC,., (ref. 60),and (ref. 61). In the case of such non-stoicheiometriccompounds, it is the accuracy with which the composition is known, ratherthan the uncertainty attached to the thermochemical measurements, whichlimits the usefulness of the results.e2 The heats of formation of Eu203(ref.63) and Ta205 (ref. 64) have also been determined from the heat ofcombustion of the metal in oxygen.The value AHf"(VCl,,liq.) = - 136.2 kcal./mole is preferable to that obtainedThe heats of formation of M- and p-Be3N2, -136.5 & 1.4 and -140.8-J= 1.0 kcal./mole,86 have been obtained from the heats of chlorination ofberyllium and its nitride and the heat of reaction of the metal with ammonia :a- or B-Be,N,(cryst.) + 3cl,(g) + 3a-BeC12(cryst.) + N,(g)3Be(cryst.) + BNH,(g) + a-Be,N, + 3H,Be(cryst.) + Cl,(g) + a-BeC1,The value for #?-Be,N, agrees well with that obtaineds7 from a study ofdecomposition pressures for Be,N, -+ 3Be + N, at 1450-1650"~.Schafer and Liedmeier 88 have measured the heats of combustion ofniobium and tantalum metals and of their oxides and oxyhalides, andreport AHf" values for NbO, NbOCl,, NbCl,, Nb,C18, NbCl,.,,, TaCl,.,,and TaC1,.Heats of Explosion.-The heats of formation of trisilane, Si3H8, andtrigermane, Ge,H,, have been determined,89 as an extension of previouswork on silane, disilane, germane, and digermsne,90 by measuring the heatof explosion when mixed with stibine in a copper-block cal~rirneter.~~ Itis noteworthy that the heat of formation of trisilane, obtained in this way,+259 kcal./mole, differs considerably from that derived from the heat ofcombustion in a static bomb.92 The bond energies E(M-H) and E(M-M),where M = Si or Ge, are calc~lated.8~ Appearance potentials of ions formedfrom these hydrides have also been measured 93 and bond-dissociationenergies D(M-H) and D(M-M) have been determined.Gunn has also measured the heats of formation of hydrogen selenideand telluride, by the explosion method, and has published 94 a table of thegas-phase heats of formation of the simple hydrides MH,, MH,, MH,, andMH, where M represents elements from Groups IV, V, VI and VII.Forthe third-, fourth-, and fifth-period elements, differences between heats offormation both horizontally and vertically are very regular.By means of a spherical bomb of Monel metal (10-1. capacity), the heatsof explosion of some fluorine-chlorine-substituted methanes have beendetermined,95 and the heats of formation calculated as :CF,, -220.4 f 1.4; CF3C1, -166.2 -& 2.2;CFCl,, -66.4 f 2.1; and CCl,, -24.6 f 1.9 kcal./mole.liminary value AHf"(solid) = +147.7 & 6.0 kcal./mole obtained.Heats of Other Reactions.-Hydrogenution.The heats of hydrogenationof isomeric propyl chlorides and bromides have been measured a t Boulder,by Lacher and his co-w~rkers,~~ with an isothermal flow calorimeter. Thesedata, with previous results, are used for a general comparison of the heatsof the reaction RX + H2 + RH + HX, where R = Me, Et, or Pr", andX = C1, Br, Me, OH, OMe, SH, SMe, or NH,.The heat of hydrogenation of benzyl bromide to toluene, by means oflithium aluminium hydride in ether, has been measured,98 together withthe heat of bromination of the hydride in ether. The calculated heat of4Ph*CHzBr + LNH, + 4PhMe + LiBr + AlBr,formation of benzyl bromide depends only on the difference between theheats of these two reactions and the heat of formation of toluene.Theheat of formation of the hydride has been found by Fasolino 99 from theheat of solution of LiAlHJcryst.) in 4~-hydrochloric acid, which, com-bined with the measured heat of solution of aluminium and lithium in thesame solution yields AHfo(LiAIH,,cryst.) = -24.7 & 2.2 kcal./mole. Theassociated uncertainty is too large for useful comparison with the value of-26.4 & 0.4 kcal./mole, found by Davies et aZ.loO However, this assumesCoughlin's 101 value for the heat of solution of aluminium in 4 . 3 6 ~ HC1(-127.05 & 0.12 kcal./moIe) which is 1.2 kcal. less negative than Fasolino'smeasured heat of - 128.27 &- 0.03 kcal./mole.LiAlH, + 2Br, --+ LiBr + AlBr, + 2 8 ,Reduction.The heat of formationARf"(RuO,,cryst.) = -57.6 & 1.3 kcal./molehas been determined 102 from its heat of solution in liquid ammonia at 5 and10 atm. pressure, when the reaction .is3Ru0, + 8NH3- 3Ru + 12H20 + 4 N 2Gunn and Williamson lo3 measured the heat of reaction of xenon tetra-fluoride with aqueous potassium iodide, the fluoride being quantitativelyreduced according to the two reactions:XeF, + 41---+ Xe + 4F- + 21,XeF, + 2Hz0 -+ Xe + 4HF + 0,The value AHfo(XeF,,cryst.) = -60 kcal./mole was obtained.heat of explosion of xenon trioxide, XeO,, Gunn lo* also obtainedAHfo(Xe03,cryst.) = 96 f 2 kcal./mole.The heat of formation of xenon hexafluoride is also available,l03 and withFrom thedata for the heat of sublimation,1°5 the mean bond-dissociation energiesD(Xe-F) = 32 (in XeF,) and 30.5 kcal./mole (in XeF,) and fi(Xe-0) =28 kcal./mole have been derived.Hydrolysis.Measurement of the heats of hydrolysis of inorganiccompounds by solution calorimetry continues to be an important approachto obtaining their heats of formation. The measured 106 heat of the hydro-lysis of vanadium tetrafluoride to give an aqueous solution of V02+, F-, andHf ions, when combined with the heat of hydrolysis of the tetrachloride(which also gives V02+ ions), and the heat of formation 84 of the tetrachloride,has yielded the value AH,"(VF,,cryst.) = -321 1.5 kcal./mole. Theheat of hydrolysis of vanadium pentafluoride in alkali has been used t ocalculate AHfo(VF5,1iq.) = -352 -)= 4 kcal./mole.los This value is lesswell founded since its derivation assumes that the vanadium appears onlyas metavanadate ions, V3093-, and it may be that other species are presentin the alkaline solution.The heats of hydrolysis, in 0.718~-sodium hydroxide, of tungsten hexa-and penta-bromide (in the presence of bromine) have been measured: lo*WBr,(cryst.) + 8NaOH(aq.) = Na,WO,(cryst.) + GNaBr(aq.) + 4H20(liq.)WBr,(cryst.) + +Br,(aq.) + 8NaOH(aq.)= Na,WO,(cryst.) + BNaBr(aq.) + 4H20(liq.).These data lead to values hHf0298(WBrG,~ry~t.) = -92.1 & 1.1 andAHfo2Q8(WBr,,cryst.) = -84.6 -J= 1.2 kcal./mole.The heat of the reactionWBr,(cryst.) = WBr,(cryst.) + $Br2(g) is calculated asAH = 11.2 f 1.8 kcal./moIe.The heats of solution of the oxide bromides, W02Br2 and WOBr,, have giventheir heats of formation as -179.7 & 0.5 and -139.2 & 0.8 kcal./mole,respectively.10Q Other examples of the determination of heats of formationfrom heats of hydrolysis include studies on the iron strontium oxides,3Sr0,Fe203, 2Sr0,Fe20,, and %Sr0,Fe20, (solution in ~N-HCI) l10 and onFe,SiO, (solution in 20% aqueous HF); ll1 and a large body of work onthe selenites and selenates.112One is of an isother-mal type,l13 for measuring the heats of solution of metals in acids, and theother is of adiabatic type and has been used for measuring the effects ofTwo new solution calorimeters have been described.lo5 J.Jortner, E. 0. Wilson, and S. A. Rice, J .Amer. Chem. SOC., 1963, 85, 814;C. L. Chernick, " Noble Gas Compounds ", ed. H. H. Hyman, University of ChicagoPress, Chicago, 1963.lo6 R. G. Cavell and H. C. Clark, Trans. Paraday SOC., 1963, 59, 2706.lo' R. G. Cavell and H. C. Clark, J. Chm. Soc., 1963, 3890.l o 8 S. A. Shchukarev and G. A. Kokovin, Zhur. neorg. Khim., 1964, 9, 1309.loo S. A. Shchukarev and G. A. Kokovin, Zhur. neorg. Khim., 1964, 9, 1565.110 F. Masazzs and R. Fadda, Ann. Chim. (Italy), 1964, 54, 95.ll1 A. F. Kapustinskii and K. K. Samplavskaya, Trudy Moskou. Khim-Tekhnol.Inst., 1962, 38, 7.112 N. M. Selivanova et al., Trudy Moskou. Khim.-Teckhnol. Inst., 1962, 38, 21, 26,30, 37; Izvestia Vysshikh. Uchebn. ZavedemG, Khina. i Khim.-Tekhnol., 1963, 6, 631;Zhur. neorg. Khim., 1963, 8, 2428; 1964, 9, 259; Zhur.priklad. Khim., 1964, 37;Zhur. $2. Khim., 1964, 38, 972.I l a G. C. Fitzgibbon, D. Pavone, E. J. Huber, Jr., and C. E. Holley, Jr., U.S.Depart. Comm. Office Tech. Sew., Report LA3031, 196472 GENERAL AND PHYSICAL CHEMISTRYirradiation on ceramic materials from their heats of solution in aqueoushydrogen fluoride.ll4Choice of a secondary standard for reaction calorimetry of fast exo-thermic reactions is still under active consideration, and it seems likelythat tri[ (hydroxymethyl)amino]methane, THAM, will be selected.115Thermal decomposition. E'urther measurements have been made of theheats of the thermal decompositions :MClO,(cryst.) + MCl(cryst.) + f 0,,where M = Na or K, and n = 3 or 4, a sealed microcalorimeter beingused;116 thus were derived the AHfo(cryst.) values :NELCIO~, -85.52 f 0.26; KC103, -92.96 f 0.26;NaClO,, -90.53 f 0.28; KCIO,, -101.63 f 0.18 kcal./mole.The values for the perchlorates agree more closely with those of Skuratovet ~2.l~' than with those of Johnson and Galliland.llg These data are usedto derive AHf" values for the C10,- and C103- ion in aqueous solution.The heat of formation of the chlorite ion, ClO,-, has also been determined.119Hitherto, differential thermal analysis has been used extensively for thequalitative studies of the heats of phase changes. Speros and Woodhouse 120and Sherwin and Dickins l 2 1 now report the realisation of quantitativedifferential thermal analysis, and also the results 122 of a study of the systemCaO + CO, = CaCO,.CompZex formation.If a metal ion, M, can bind n ligands, L, to form acomplex, ML,, the complex is generally built up by stepwise reactions. Ata given concentration of free ligand, the metal is distributed over all thespecies in a way that depends only on the equilibrium constants. It isuseful, therefore, to perform a calorimeteric titration in which the heatevolved in each step of the titration is measured. A calorimeter suitablefor this purpose has been described,123 and a computing method has beenapplied to the calculation of the heats of stepwise reactions from the calori-metric data.124This calorimeter has been used by Grenthe125 to measure the heats offormation of lanthanide complexes, in which the ligands are acetate,glycollate, thioglycollate, diglycollate, or dipicolinate ions.The lanthanideions form a unique series for a study of the influence of the size of the centra,lion on complex formation. The 4f orbitals are well screened from theinfluence of external ligand fields, so that effects caused by lack of sphericalsymmetry of this electron shell are small. The general shape of a plot ofthe heat of complex formation against atomic number of the lanthanide isthe same for each of these ligands and similar to that found by Staveleyand his colleagues for the complexes with nitrilotriacetic acid.126 Theseauthors have used a differential calorimeter to avoid a number of inherentthermochemical difficulties.From measurements of heat of solution, the heats of formation of thesolid chloro-complexes [NMe4],[MWl4] and [NEt4],[M1ICl4], where M = Mn,Fe, Co, Ni, Cu, or Zn, have been determined. When corrections are madefor the ligand-field stabilisation energies a plot of the M-C1 bond-dissociationenergies against atomic number is nearly linear (except for the distortedcopper ion complex).This is similar to the behaviour shown by the heats offormation of octahedral amine complexes, and also the heats of hydration ofsimple metal ions.lZ7 The theoretical explanation of this type of behaviourhas been considered by Schuit,12* who has, in the main, used only thethermochemical data available up to 1959, reviewed by George andM~Clure.1~~Blake and Cotton 130 have measured the heats of solution of the seriesof compounds [AsP~,M~],[M~~C~,], where M = Mn, Fe, Co, Ni, Cu, or Zn,and have discussed the stabilities of the [MCl4I2- ions relative to the[M(H,O) J2+ ions.Other complex chloro-ions investigated include [MvC1,]-,where M = Ta or Nb,131 and the [CrClJ3- and [Cr,C1J3- ions.132Anderegg 133 has measured the enthalpy changes for the stepwise form-ation of proton and metal complexes of the ligands 1 ,lo-phenanthroline and2’,2’-bipyridine, to form complexes [M1*Ln], where M = Mn, Co, Ni, Cu, Zn,and Cd, and n = 1,2, and 3. A plot of AH against atomic number is similarto that with diethylamine as ligand. The formation of the ferrouscomplexes [FeL3I2+, is accompanied by a very large heat change,AH = -28-5 kcal./mole, connected with a change from a high- to a low-spincomplex.The heat change in the formation of proton and metal complexesof ethylenediamine- and diaminocyclohexanetetra-acetic acids, of the typeLa have been measured.la Heat data are also available for the formationof nitriloacetic acid complexes of the same metals.135Becker et ~ 1 . l ~ ~ have described a thermometric-titration apparatus andits application to the study of the two-step equilibrium systems:Ag+ + 2py = [Ag(py),]+; and HgBr, + 2Br- = [HgBr4]2-. Kaputinskiiand Pakhorukov 13‘ have determined the heat of formation of the complexes[ C O ( ~ , ) ~ ] [ C ~ ( C , ~ , ) ~ ] , ~ H , O . Guzzetta and Hadley 138 have measured theheat of complex-formation of cyanide ions with bivalent ions of V, Cr, Mn,Fe, Co, and Zn, and with tervalent iron ions in aqueous solution.Theheats of association of copper(u) and nickel@) ions with ar-hydroxyimino-alkylamines are reported.lsgClosely allied are measurements of the heats of protonation of theligands, 1, lO-phenanthr~line,~~~ 2,2’,2”-triaminotriethylamine, NNN’N’-tetra - (2 - aminoethy1)et h ylenediamine ,la and o - hydr oxy b enzaldehyde .142The heat of ionisationof water, H20 -+ H+ + OH-, is now well established by two recent andindependent measurements, AH = -13.332 & 0-016 kcal./mole l43 and-13.334 -J-- 0-016 kcal./mole, severally.lM These values agree well withearlier calorimetric values rather than with that of - 13.50 & 0-05 kcal./molefound by Paphe, Canady, and Laidler.145 However, many of the heats ofionisation in the literature are based on the value of -13.50 kcal./mole.The heats of ionisation of a number of weakly acidic thiols of biochemicalinterest have been measured,146 and also the heats of the first and secondionisation stages of salicylic acid.147 Heats of neutralisation of the strongacids, fluorosulphuric, perchloric, and sulphuric acid, have been determined.14*Molecular addition compounds.Stevens, Park, and Oliver 149 havemeasured the heats of gas-phase dissociation of GaEt ,-NMe3 (17.2 kcal./mole)and GaEt,-SMe, (6.0 kcal./mole), which confirm the relative donor strengthsof nitrogen and sulphur previously suggested by Coates.l50 The dissociationheat of 21.0 kcal./mole for (CH,:CH),Ga-NMe, is greater than for thecorresponding triethylgallium compound, and this may be due to moleculardimerisation of the vinyl compound in the gas phase, or to steric and elec-tronic effects of the sp2 carbon atom. Heats of formation of adducts betweenantimony pentachloride, as acceptor, and various ketones and carboxylicesters, as donors, have been given.161 Lindqvist 152 has reviewed the workin this field up to the beginning of 1962. Heats of reaction153 of siliconand germanium tetrahalides, AX,, with pyridine and isoquinoline suggestthat the order of acceptor power is AF, > ACl, > ABr, towards isoquinoline.With pyridine the results are more diEicult to interpret, since SiC14,2py andSiBr4,2py are cis-octahedral, but SiF4,2py is truns-octahedral.Similar work, involving the heats of addition of quinoline, ar-picoline,and dimethylphenylamine to antimony pentachloride, tin tetrachloride, andtitanium tetrachloride has been carriedThe heats of formation of the complexes, 1,4-dioxan,Br2 and l,Fdioxan,I,(from gaseous dioxan and halogen to form a solid complex), have beendetermined 155 as -26.2 &- 0.3 and - 28.6 &- 0.3 kcal./mole, respectively.The results have been confirmed by spectroscopic studies of the equilibriabetween the halogens and dioxan.In a preliminary note, Block and Jackson 156 reportthe use of a calorimeter to measure the heat of conformational change of thecc-helix to the random-coil form of the polypeptide, poly-(y-benzyl-L-glutam-ate).The standard heats of combustion of the amino-acids, glycine, alanine,valine, leucine, phenylalanine, serine, and tryptophan, have been used tocalculate the heats of formation of peptides made up from them.157 Heatsof solution of a number of amino-acids in water and in 6~-urea solutionhave been determined.Is8The heats of hydrolysis, in aqueous solution, of o- and p-acetoxybenzoicacid and of o- and p-acetylthiobenzoic acid, AcX*C6H,*C02H where X = 0or S, which are of biological interest, have been measured.159Heats of Formation from Equilibrium Studies.-Boron, aluminium, andberyllium compounds.Blauer and Farber 160 have examined the reactionbetween B203 and water to form (HOBO),, in a transpiration cell:Biological reactions.3B,O3(liq.) + 3H,O(g) = 2(HOBO),(g)The heat of formation AHfo[(HOBO),,g] = 545.8 & 2-0 kcal./mole wasderived.of the vapour-phase equilibrium inthe B20,-BC13 system at 1234-1389"~ has also been made.From theAn experimental investigation151 G. Olofsson, A:ta Chem. Scand., 1964, 18, 11, 1022.lS2 I. Lindqvist, Inorganic Adduct Molecules of Oxo-compounds ", Springer-153 J. M. Miller and M. Onyszchuk, Proc. Chem. SOC., 1964, 290.154 R. C. Paul, P. S. Gill, and J. Singh, Indian J . Chem., 1964, 2, 219.155 G. A. Goy and H. 0. Pritchard, J . Phys. Chem., 1964, 68, 1250.156 H. Block and J. B. Jackson, Proc. Chem. SOC., 1963, 381.15' T. A. Alekseeva, and V. V. Ponomarev, Zhur. $2. Khim., 1964, 88, 1337.lssG. C. Kresheck and L. Benjamin, J . Phys. Chem., 1964, 88, 2476.159 L. Nelander, Acta Chem. Scand., 1964, 18, 973.161 J.Blauer and M. Farber, Trans. Faraday SOC., 1964, 60, 301.Verlag, Berlin, 1963.J. A. Blauer and M. Farber, J . Phys. Chem., 1964, 68, 235776 GENERAL AND PHYSICAL CHEMISTRYcalculated heat of the reaction B203(liq.) + BCl,(g) = 3BOCl(g), the valueAHf"(BOC1,g) = -75-3 & 7 kcal./mole is obtained.Using Knudsen-type effusion cells and mass spectrometry, Porter andGupta 162 have measured the heats of other reactions involving B203:B2°3(g1ass) + 4B2H6(g) = B3°3H3(g)B,O,(liq.) + BCl,(g) = B,O,Cl,(g)4B203(liq.) + 4BCl,(g) = 3B40,Cl,(g)B303H,(g) + nHCl(g) = B303H3-,Cl,(g) + nH2(g)The heats of formation of gaseous B303H3-,C1, and B404C14 can be cal-culated in terms of the heats of formation of B203 and B,H,. It is interest-ing that the gas-phase reaction B,03C13 * 2B404C14 is endothermic(AH = +8 kcal./mole), indicating weaker bonding in the eight-membered-B-O-B- ring than in the six-membered ring, or possibly some majorstructural change.Mono- and di-hydroxyborine, H,B*OH and HB(OH),, are formed in thereaction between diborane and boric acid.The heats of formation of thesecompounds, which have been proposed as intermediates in the hydrolysisof diborane and in the oxidation of borines, have also been e~tab1ished.l~~In a study of the equilibrium B(cryst.) + BF,(g) = 3BF(g) in thetemperature range 1307-1505 OK, by means of transpiration at pressuresbelow 300 p, the heat of formation, AHfo,,,(BF,g) = -29.0 & 2-6 kcal./molehas been obtained.164The heat of formation of boron phosphide has been determined from ELstudy of the reaction 2H2 + 4BBr + P4 = 4BP + 4HBr, in a flow system.le5Elemental boron is so reactive at high temperatures that values of itsvapour pressure and heat of sublimation from experimental studies withthe element are subject to great errors arising from reactions between thesample and other parts of the system. Robson and Gilles 166 have overcomethese difficulties by measuring the vapour pressure, using a Knudsen tech-nique, of a sample of boron carbide which decomposed according to theequation :B,C(cryst.) = C(so1id) + 4B(g)They obtained a value AH = 138.0 & 0.1 kcal./g.-atom of boron.Usinga torsion effusion technique, Hildebrand and Hall 16' obtained a value of138.7 -J= 1.2 kcal./g.-atom, for the same reaction.If a value of-82.2 IJr 2.2 kcal./mole 168 is taken for the heat of formation of boroncarbide (based on the new heat of formation of amorphous B,O, of-299.74 kcal./mole), the heat of formation AHfoZ9&B,g) = 136.0 0.7kcal./g.-atom is obtained.The disproportionation reaction 6HBC1, = 4BC1, + B,H, was followedlB2 R. F. Porter and S. K. Gupta, J . Phys. Chem., 1964, 88, 280.lBa R. F. Porter and S. K. Gupta, J . Phys. Chem., 1964, 68, 2732.lBP J. Blauer, M. A. Greenbaum, and M. Farber, J . Phys. Chena., 1964, 88, 2332.lisS Z. S. Medvedeva and Ya. Kh. Grinberg, Zhzcr. neorg. Khim., 1964, 9, 491.lBB H. E. Robson and P. W. Gilles, J . Phys. Chem., 1964, 88, 983.lB7 D. H. Hildebrand and W. F. Hall, J .Phys. Chem., 1964, 88, 989.16* D. Smith, A. S. Dworkin, and E. R. Van Artsdalen, J . Amer. Chem. SOC., 1955,77, 2654MORTIMER : THERMOCHEMISTRY 77spectrophotometricaly in the infrared region, and from the equilibriumconstant the heat of formation AHfo(HBC1,) = -60.57 & 0.05 kcal./molewas ca1culated.lThe heats of formation A~fo208(&oc~,g) = -84 & 5 kcal./mole hasbeen determined170 from a study of the reactionA1203(liq.) + AlCl,(g) = 3AlOCl(g)a t 2400"~; a method of molecular flow effusion was used.The equilibrium 2AlF2(g) = A1F3(g) + &F(g) has been studied overthe range 1243-1301"~.171 From known heats of formation of AlF, andAIF, one calculates h~fo20,(All?2,g) = -149.2 & 4 kcal./mole. The step-wise dissociation energies in AlF3 are then derived as D(AlF,-F = 156,D(AlF-I?) = 106, and D(Al-F) = 159 kcal./mole, which shows a decreasein bond strength in AIF,.The measurement172 of the heat of the reaction2BeCl(g) = BeCl,(g) + Be(1iq.)leads to the value AHfoBeCl(g) = 3.7 & 3.8 kcal./mole.Equilibriumpressures over mixtures of green MnS and graphite were measured a t 1400"by the effusion method.Metal oxides, sulphides, selenides, tellurides, and chlorides.From the heat of the reaction,MnS(S) + C(graphite) = %(g) + CS(g)AHfo,,,(CS,g) = 55.0 & 1-0 kcal./molewas deterrnined.lT3 From a study174 of the vapour in equilibrium withsolid SnSe and SnTe, a number of reaction heats have been measured andused to derive AHf",,,(SnSe,s) = -21.5 rf: 1.7 and AH,",,,(SnTe,s) = -146& 1.3 kcal./mole, whence the dissociation energies D(Sn-Se) = 95 & 1-4and D(Sn-Te) = 79.9 These energies agreewell with spectroscopic values, and the heat of formation of SnSe is close tothat obtained from combustion -21.7 0.1 kcal./mole.A similar studyl76 of GeTe gave AHfo2,,(GeTe,s) = -6.0 & 2-3 andD(Ge-Te) = 93.5 -3: 0.5 kcal./mole.Colin et aZ.l77 have also examinedthe sulphides CaS, SrS, and Bas and obtained the dissociation energiesD(Ca-S) = 73.7 & 4.5, D(Sr-S) = 74.1 & 4.5, and D(Ba-S) = 94.7 & 4.5kcal./mole. As part of this work, the equilibrium S, = 2 s was investigated :the derived value D(S-S) = 97 -J= 5 kcal./mole supports the higher valuefor the heat of formation of sulphur atoms favoured by Mackle and O'Hare.431.4 kcal./mole are derived.169 L.Lynds and C. D. Bass, Inorg. Chem., 1964, 3, 1147.170 M. A. Greenbaum, J. A. Blauer, M. R. Arshadi, and M. Farber, Trans. Furaduy171 T. C. Ehlert and J. L. Margrave, J. Amer. Chem. Soc., 1964, 86, 3901.172 M. A. Greenbarn, M. L. Avin, M. Wong, and M. Farber, J. Phys. Chem., 1964,173 H. Weidemeier and H. Schaefer, 2. anorg. Chem., 1964, 326, 235.17* R. Colin and J. Drowart, Trans. Faradizy SOL, 1964, 60, 673.176 S. N. Gadzhiev and K. A. Sharifov, Doklady ALud. Nauk Azerb., 1960, 16, 659.176 R. Colin and J. Drowart, J . Phys. Chem., 1964, 68, 428.177 R. Colin, P. Goldfinger, and M. Jeunehomme, Trans. Paraday SOC., 1964, 80,Soc., 1964, 60, 1592.68, 791.30678 CJENERAL AND PHYSICAL CHEMISTRYThe heats of the following dissociation processes have been determinedfrom vapour-pressure measurements :2OsCl,(s) = 2Os(s) + 3C12(g),STaCl,(s) = BTaCl(s) + TaCl,(s),= -43.1 & 1.0 kcal./mole (ref.178)= 41.9 & 2.0 kcal./mole (ref. 179)By using Knudsen effusion and mass spectrometry the dissociationenergies D(Zn-0) < 66, and D(Zn,O) < 127 kcal./mole are derived.lsOThe dissociation energy D(Y-0) = 168.3 & 2-3 kcal./mole has also beenfound from a study of Y203.181The effusion method has also been useful in determining theheats of formation of metal atoms; e-g., the saturation vapour pressure ofmanganese a t 1036-1175" was used lS2 to calculate AHf0,,,(Mn,g) = 69-3& 0.5 kcal./g.-atom. Vaporisation of samples of the metals from a Knudsencell have led lS3 to the dissociation energies D(M-M): M = Sc, 45.5;Y, 37.6; and La, 51.5 kcal./g.-atom.Measurement of the dissociationpressures of MCI, a t 600-950" have been determined1B4 and yield theAHf0298(M,g) values; M = Sm, 203; Eu, 217; Yb, 186; Pr, 163; Nd, 163.2;Er, 150; and Se, 145 kcal./g.-atom. Kant la5 has shown that the Ni, mole-cule exists ip the vapour phase over liquid nickel a t 2000"~; from effusionand mass spectrometry the dissociation energyD(Ni-Ni) = 54-5 f 5 kcal./moleis derived. A recent survey of the heats of vaporisation of elements anddissociation energies of known homonuclear diatomic molecules has beengiven.la6Bond Energies.-Skinner 187 has developed a bond-energy scheme, origin-ally proposed by Allen, which takes account of steric repulsions and hasbeen applied successfully to predict the heats of formation of gaseous alkanes,cycloalkanes, cycloalkenes, and also, to a more limited extent, of alcohols,alkyl bromides, and alkylamines.A least-squares analysis of the thermo-chemical data has been used to improve the reliability of these methods.la8It was Dewar and Schmeising189 who suggested that the energies ofC-C single bonds depend on the state of hybridisation of the carbon atoms,and who proposed a bond-energy scheme for unsaturated hydrocarbons. Itwas obviously very desirable that such a scheme should be extended beyondthis class of compounds, and a move in this direction was made by MackleMetals.THE last full Report on this subject was in 1958 although it was brieflymentioned in the following year.2 This neglect does not reflect the extentto which work has been done in this area; it has recently been estimated 3that several thousand papers per year are being published in electrochemistryand electroanalytical chemistry, consequently an attempt will be made hereonly to survey the more important aspects and to mention helpful reviews.New journals include the Journal of Electroanalytical Chemistry (Elsevier,from 1959) covering the field from the fundamentals to analytical applica-tions, also Corrosion Science (Pergamon, from 1961) and ElectrochemicalTechnology (Electrochemical Society, from 1963) covering applied electro-chemistry.Electroanalytical Abstracts, which started in 1961 in associationwith the Journal of Electroanalytical Chemistry, became independent in 1963.Many symposia have been held, including four meetings of C.I.T.C.E.(Cornit6 International de Thermodynamique et de Cin6tique Electro-chimique) : 12th (Brussels, 1961), 13th (Rome, 1962), 14th (Moscow, 1963),and 15th (London, 1964).Most of the papers presented there have beenor are being published in Electrochimica Acta. The proceedings of an inter-national meeting in Australia (Sydney and Hobart, Pebruary, 1963) are inthe press. The Faraday Society held a discussion on oxidation-reduction 4in Newcastle in 1960. The first Gordon Conference on Electrochemistrywas held in Santa Barbara (February, 1964). The first of a series of meetingswas held at the Central Electrochemical Research Institute in Karaikudi(S.India) in 1960. The Electrochemical Society continues to hold Springand Autumn meetings every year covering a wide range of electrochemicalinterests. The third I.D.C.B. (Inter-Departmental Committee on Batteries)symposium on batteries in Bournemouth (1962) has been publishedY5 anda fourth symposium was held in Brighton (October, 1964). The proceedingsof the fourth Soviet Conference on Electrochemistry (Moscow, 1956) havebeen published in English translation.6In few of the many books published during the last six years are attemptsmade to cover the vast field. The most general are those of Milazzo,'Lange and GOhr,* and Hampel.9 The electrochemistry of non-aqueoussolutions is emphasised in Izmailov’s book,lO and there are several books onmolten salts.ll All electrochemists are indebted to the authors of threebooks l 2 on equilibrium properties of electrodes, which contain large storesof useful information.On the fundamentals of electrode kinetics, an im-portant comprehensive work13 has been published, although it must benoted that by the time this Report is published, ten years will have elapsedsince the main work on the text was completed; neglect of double-layerproblems in this book is only partially redressed by a slim volume l4 on the#-scale (rational potential scale). This gap will be more effectively filledby a, book by Delahay to be published early in 1965. An excellent transla-tion into English of Levich’s classic l5 is very welcome.The formation ofoxide films l6 and semiconductor electrochemistry l7 have also formed thesubjects of recent books, and several books l8 on polarography and electro-analytical chemistry repay study.The vast increase in work on fuel cells is reflected in the initiation of twoseries of the Advances ty-pe.l9 A marriage between pure and applied electro-chemistry is the aim of a new series.2O The “ pure ” volumes cover muchthe same field as the already established “ Modern Aspects ” seriw whichhas just reached its third volume.21 Together these two provide excellentup-to-date reviews for the research electrochemist.The Double Layer at Electrodes.-Although objections have been voiced,22the thermodynamic theory of the double layer is widely assumed to be wellestablished.Reversible electrodes have been discussed,23 as well as thepossibility of partial charge transfer to specifically adsorbed ions.24 Themain advances consist of the development of theoretical models of the doublelayer and attempts to test these models experimentally. Three generalreviews of double-layer problems have appeared.25The diffme hyer. The deficiencies of the Gouy-Chapman theory havebeen recognised for many years and various attempts have been made toallow for the effects of the ionic size, dielectric saturation polarisation ofthe ions, formation of ion pairs, and the self-atmosphere. An attempt hasbeen made 26 to take into account all these effects by using the local thermo-dynamic method developed by Prigogine, Mazur, and Defay.27 As Grahameshowed earlier,28 dielectric saturation seems to be unimportant, althoughthe opposite view has also been expressed.29 The effect of ionic size is smallbut electrostriction plays an important part.The relation between theindividual ionic adsorptions and the total charge in the diffuse layer isvirtually identical with that given by the Gouy-Chapman theory, butrelations involving the potential at the outer Helmholtz plane aremodified. This may affect the rate of an electrode reaction by a factor ofup to 2.A more molecular point of view 30 of the diffuse layer confirms the ideathat the Gouy-Chapman theory is a good limiting law, but emphasises theimportance of the discrete nature of the charge at the concentrations whichare normally used experimentally.The capacity of the diffuse layer hasalso been calculated31 for a similar molecular model. The value found isin good agreement with that calculated from the Gouy-Chapman theory atconcentrations below 0 . 1 ~ for a 1 : 1 electrolyte. At higher concentrationsthe deviation from the Gouy-Chapman value increases rapidly, the improvedvalue being about 60% the greater at 0 . 5 ~ . This deviation is f i c u l t todetect experimentally because at the higher concentration the diffuse layermakes a very small contribution to the measured capacity. A more stringenttest of diffuse-layer theory was attempted by studying simultaneous non-specific adsorption of two cations carrying different charges.32 The resultscould be explained by invoking different distances of closest approach orion-pairing.In the most concentrated solutions the statistical-mechanicalmodel 30 predicts that the local charge density is an oscillating function ofthe distance from the outer Helmholtz plane. A similar result is foundfor the double layer in molten salts by a different method 33 and providesan explanation for the experimental results,34 especially the temperature-dependence.In the absence of specific adsorption theproperties of the inner layer depend on the nature of the solvent moleculeswhich populate it. The effect of the structure of water has been discussedby three groups of workers.35 It is generally agreed that, owing to restrictedrotation, water in the inner layer has a much lower dielectric constant thanin the bulk; over much of the experimental range of potential the dielectricconstant may be reduced to the distortional value of about 6, while themaximum value may be about twice this.The maximum in the capacity-potential curve, known as the “ hump,” which usually occurs at a smallpositive charge, has been attributed 3~ to a maximum in the relation ofdielectric constant to field strength in the inner layer, but evidence has alsobeen presented 3 5 c 9 36 suggesting that the position of maximum freedom ofthe adsorbed water (which should correspond to a maximum dielectricconstant) occurs at a small negative charge. The position and magnitudeof the hump in the measured capacity curve is strongly dependent on thenature of the anion in solution, and it has been suggested that the wateris oriented by the specifically adsorbed anions 37 or that the hump is entirelydue to the interaction between adsorbed ani0ns.3~~ A detailed analysis ofthe inner-layer capacity38 leads to the conclusion that there is a residualhump which remains after allowance has been made for the specificallyadsorbed anions.Capacity measurements in non-aqueous solutions appearto confirm the existence of a dielectric hump. Thus a hump is observed informamide 39 and methylf~rmamide,~~ which have dielectric constants higherthan that of water, but not in dimethylformamide,39 acetonitrile,39 orrnethan01,~l which have lower dielectric constants.Specific adsorption ofpotassium fluoride is absent from the formamides,42 and the temperature-dependence of the capacity is greatest at the top of the hump,*o, 45 in agree-ment with the dielectric explanation. On the other hand, the temperaturecoefficient of the hump in aqueous solution is asymmetric.44 The steeprise of the capacity in fluoride solutions at high positive charges has beenascribed to (a) specific adsorption of fluoride,35b (b) specific adsorption of( c ) impurities,& and ( d ) adatoms of mer~ury.~5~ A furtherexperimental study 46 leads to that view (a) is probably correct, althougheffects ( b ) and (c) may contribute to the discrepancies found between differentworkers' results. Some doubt is thrown on the connexion of the hump inaqueous solutions to the dielectric properties of water by the observation 47that the adsorption of aliphatic molecules with different polar groups is amaximum at a charge of about -2 pc cm.-2. This is interpreted 350 in termsof a model in which the hydrocarbon chain is present in the inner .layer andthe adsorption energy is primarily determined by the energy of replacementof water molecules.Thus the water layer has a minimum energy at thischarge, in agreement with an orientation of water at zero charge with theoxygen towards the metal.36 Recent work 48 on the pressure-dependence ofthe capacity tends to support this assignment of orientation. Acceptanceof this view, however, means that the hump is due, not to a dielectric effect,but perhaps to specific adsorption.Recent measurements on liquid galliumelectrodes *tw have given results differing from those obtained earlier byGrahame and have been interpreted in the light of evidence that water ismore strongly bound to gallium than to mercury. This work shows promiseof adding considerably to our present ideas of structure of metal-waterinterphases, as well as showing the marked effect of small quantities ofimpurity in the metal.The effect of adsorbed ions and molecules on the properties of the inter-face has been intensively studied both theoretically and experimentally.Two principal approaches have been followed : the discrete-charge model andthe adsorption-isotherm method. The former starts from the Esin andShikov, and the Ershler and Grahame, models (for a review see ref.25). Theions in the inner layer are assumed to form an infinite, two-dimensional,hexagonal lattice,S1, 49, or, alternatively, the interaction of one ion withthe rest of the layer is represented in the form of a charge in the centre ofa hole in a plane of uniform charge density (cut-off approximation).s1 Thevalidity of assuming perfect imaging of the adsorbed ions in the outerHelmholtz plane is still uncertain,50 but it is generally agreed 319 49-52 thatthe constant-field approximation is limited to very low densities of adsorbedions. This seems to be in agreement with experiment.53 Non-electrolyteadsorption has been included only to a small extent in this type ofThe adsorption-isotherm approach is complementary; the aim is to fit anadsorption isotherm .to experimental results so that, so far as possible,adsorbent-adsorbate interactioiis may be distinguished from adsorbate-adsorbate interactiow.An important condition for this is the choice of theelectrical variable mhich is held constant for the study of the slope of theadsorbate-concentration-bulk-concentration relation. About ten years agoit was suggested54 that the charge on the electrode was more suitable forthis use than the potential of the electrode; this has not been disputed forionic adsorption, but arguments have been presented for both charge 35c, 55and potential 56 as appropriate variables in the adsorption of neutral mole-cules; at present no final conclusion can be drawn, although it may be notedthat the choice has little effect on the shape of the adsorption isotherm ofthe least polar adsorbate^.^^The nature of the specific adsorption of inorganic ions has been discussedin terms of a detailed molecular model 57 leading to a quantitative calcula-tion of heats and entropies of adsorption.The model used is purely electro-static and it is suggested that chemisorption of ions of this type does notoccur. The interaction of ions adsorbed on the electrode surface is alsotreated electrostatically 35a (cf. ref. 58), and an isotherm is derived whichfits the experimental data for adsorption of iodide on merc~ry.~s Adsorbedionic layers have also been treated as two-dimensional imperfect gases byusing a virial equation to the second term,59 but in the period under reviewmore attention has been paid to the adsorption of large organic ions whichmay reasonably be considered together with neutral species.A compre-hensive review of the problem has been published,60 in which the versatilityof the adsorption isotherm proposed by Frumkin in 1926 is demonstrated,and this has been followed up in a series of papers.61 In order to fit theyukina and B. B. Damaskin, Izvest. Akad. Nau86 GENERAL AND PHYSICAL CHEMISTRYisotherm over the whole range of potentials it is necessary to alIow theinteraction constant to vary. This is not unreasonable, but no model hasyet been proposed to account for it. I n alternative approaches the Langmuirisotherm (which is the ideal isotherm for mixed adsorption 55, 5 0 ) is modifiedeither by introducing two-dimensional condensation 62 or by adding termsto allow for the interaction of ions, dipoles, or polarisable molecules.63 Itis evident 55, 62 that capacity measurements provide more evidence for thedistinction between adsorption isotherms than do electrocapillary results,since the former depend on the isotherm slope while the latter depends onthe integral.However, the former also depend on the second derivativeof the potential dependence, and it is by no means easy to extract thedesired information. The assumption of a definite isotherm 61, 62 or of amodel 64 can lead to an excellent fit of experimental curves, but it is difficultto reverse the procedure in order to deduce the correct isotherm and potential-dependence directly from the experimental curves.The concentration-dependence of the capacity a t constant charge is the most promising meth0d,~5and curves obtained in this way which are asymmetric appear to rule out asimple Langmuir or Frumlrin isotherm. For adsorbates of molecular sizediffering from the solvent, application of volume-fraction statistics leads toa useful analogue 5l, 65 of the Langmuir equation, which may be modified 55to an analogue of Frumkin’s and gives capacity-concentration plots of anasymmetry depending on the size ratio. Further analysis of systems ofwidely varying size ratio is required to confirm the usefulness of thisapproach.The study of adsorption on solid metals ingeneral has been pursued with increasing vigour, and techniques capableof higher accuracy have been developed. These fall into three groups,namely, those involving the use of radiotracers, optical techniques, orelectrical measurements.Adsorption of labelled compounds may be measured directly by using athin-foil electrode directly on the window of the counter,66, 67 but this isrestricted to metals which can be fabricated in very thin foil.In an alterna-tive method 65, 68 a, tape is passed successively through a cleaning solution,the active solution, a thin slit to remove the excess of solution, the heads oftwo proportional counters, and a proximity meter to measure the thicknessAdsorption on solid metuk.S.S.S.R., Otdel. k h h . Nauk, 1963, 1022; B.B. Damaskin, Electrochim. Acta, 1964,9,231; R. Lerkkh and B. B. Damaskin, Zhur.Jiz. Khim., 1964,38,1154; B. B. Damaskin,I. P. Mishutushkina, V. M. Gerovich, and R. I. Kaganovich, ibid., p. 1797; R. S. Hansen,D. J. Kelsh, and D. H. Grantham, J. Phys. Chem., 1963, 67, 2316.6a W. Lorenz, F. Mockel, and W. Miiller, 2. p h p . Chem. (Pmnkjurt), 1960, 25,145; W. Lorenz and W. Muller, ibid., p. 161.6s E. Blomgren and J. O’M. Bockris, J . Phys. Chem., 1959, 63, 1475; B. E. Conwayand R. G. Barradas, Electrochim. Acta, 1961, 5, 319, 349.e4M. A. V. Devanathan, Proc. Roy. SOC., 1961, A , 264, 133; 1962, A , 267, 256.6 5 J. O’M. Bockris and D. A. J. Swinkels, J . Electrochem. SOC., 1964, 111, 736.66 H. D. Cook, Rev. Sci. Instr., 1956, 27, 1081.137 E.A. Blomgren and J. O’M. Bockris, Nature, 1960, 186, 305; H. Dahms andM. Green, J . Electrochem. SOC., 1963,110, 1075; H. Wroblowa and M. Green, Electrochim.Acta, 1963, 8, 679; H. Dahms, M. Green, and J. Weber, Nature, 1962, 196, 1310.6 8 M. Green, D. A. J. Swinkels, and J. O’M. Bockrk, Rev. Sci. Imtr., 1962, 33,18; J . Electrochem. Soc., 1964, 111, 743PARSONS: ELECTRODE DOUBLE LAYER AND REACTIONS 87of the adhering liquid film. This method is suitable for very soft p-radiationsuch as that from 14C. Harder radiation can be used in another method 69 inwhich the cell is mounted next to a scintillation crystal with a, thin layerof solution between the latter and the electrode. Labelled compounds mayalso be used to determine the concentration change in the bulk of the solutioncaused by adsorption, and this method has been extensively used by theRussian school lo, '1 who have shown that the ionic double layer on platinumplays a small part in determining its properties compared with the adsorbedlayers of hydrogen and oxygen. Determination of adsorption from changesin the bulk concentration, by electrometric titration, has been exploited anewfor reversible systems (especially silver iodide 72) to obtain surface excessesof the ionic and the non-ionic components of the solution.Bulk-concentration changes as a result of adsorption have also beendetermined by absorption spectrophometry,73 but direct observation ofadsorbed species by reflectance spectra 74 or ellipsometry 76 seems possibleand may develop into a powerful method.Electrical methods for the study of adsorption on solid metals have beenused increasingly in recent years, although the principles involved are notalways so new.The a.c. method has been used in the bridge form 76 andalso by separating the real and the imaginary component of the potentialdifference across the electrode." Pulse methods 78 have been found par-ticularly useful for semiconductor electrodes.79 Adsorption has been studiedby observing the potential shift which ocours as a result.80 A variety ofmethods has developed from the study of charging curves in which thecharge used to form the adsorbed layer is determined. These include thepotentiostatic-sweep method,81 the galvanostatic method,S2 and the potentio-static method.83The largest amount of work has been done on platinum electrodes, nodoubt because of their interest as good catalysts for electrode reactions.However, the interpretation of the results is not easy because these electrodesare very sensitive to their pre-treatment.Various chemical and electro-chemical pre-treatments have been used, anodic activation 84 being the mostsuccessful in producing a surface with reproducible properties. There seemslittle doubt that a more precise scheme of pre-treatment would be preferable,and a start in this direction has been made 85 in the “ multi-pulse potentio-dynamic” (MPP) method; in this the electrode is automatically held at aseries of potentials for predetermined times before the measurement isautomatically carried out.The second S c u l t y with platinum electrodesis due to the chemisorption of hydrogen and oxygen, as well as of ions, fromthe solution. An excellent review of the hydrogen region is available,86 butit may be added that adsorption of anions,87 ethanol and methanol,88 carbon89 ethylene,90 cobalt comple~es,~~ etc., has since been studied.The importance of the chemisorbed layers for the double-layer structure hasbeen further emphasised92 by the suggestion that desorption of organiccompounds may be caused by the onset of adsorption of hydrogen or oxygen.Adsorption of oxygen on platinum has been extensively discussed, but nofinal conclusion about the state of oxygen on the surface has yet beenreached.Laitenen and Enkeg3 gave a review of earlier work and alsocarried out extensive coulometric and capacity measurements. They sug-gested the formation of adsorbed OH and 0 which are strongly bound to theplatinum. This is essentially confirmed in more recent work 94 by the MPPmethod, although it is suggested that PtO, exists at higher anodic potentials.The kinetics of oxidation of organic compounds 96 suggest the existence ofthree types of oxide film, but these do not correspond well to the potentialregions proposed earlier ; in particular, it is necessary to postulate adsorbedoxygen at very much lower potentials than can be seen by the usual transientmethods. Measurements in carefully degassed s y ~ t e m s , ~ ~ however, confirmthe existence of such oxide films.Less extensive measurements of a similar type have been made ongold,67, 97 silver,70, 98 73 lead,6*, 99 iron,100 cadmium,lO1 zinc,lO2 andmetals of the platinum group.lo3Kinetics of Electrode Rea&ions.--General accounts of the problems w i l lbe found in Vetter’s book l3 and in three review articles.20* 21t lo4 A usefulcompilation of kinetic parameters for electrode reactions has been pub-lished ;104O it excludes hydrogen- and oxygen-evolution and organic reactiom,but is nevertheless the most complete tabulation available. A survey of eleo-trode processes mb for 1956-61 emphasises hydrogen- and oxygen-evolution.Theory o j electrode reactions.The theory of electron-transfer reactionsinvolving weak overlap between the orbitals of the electrode and the reactingspecies is closely analogous to homogeneous electron-transfers of the “ outer-sphere ” type.An excellent review of the present state of this theory hasjust been given,lo5 so that little can usefully be added here. Advance isslower in the quantum theory of reactions in which stronger bonds areformed. Horiuti lo6 has returned to the statistical-mechanical calculationof the rate of hydrogen evolution, improving the calculation of repulsionbetween adsorbed hydrogen atoms and showing that the combinationmechanism can give a = Q over a range of potentials, where a is the transfercoefficient. A similar result is obtained by considering the non-uniformityof the surface (see also ref. 108). The constant value of thepre-exponentialfactor is interpreted in terms of the same mechanism.log The formal relationbetween the overvoltage and the affinity of the reaction has been discussedin terms of the Marcelin-De Donder method.ll0 The significance of a for anelementary reaction has also been reviewed and discussed 1100 with particularemphasis on hydrogen evolution.Considerably more work has been done on the problem of multi-stepreactions. A general treatment for a complex sequence of reactions, includ-ing transport to the electrode, has been described ll1 and applied to oxygenevolution.l12 It has also been shown how the complete set of possiblemechanisms can be derived from the assumption of a given number ofintermediate species in a particular reaction.118 If no restrictions areincluded a very large number of mechanisms is found for reactions withmore than two intermediates. Mechanisms can be generated in this waywith the aid of a digital computer.l14 Complete numerical solutions forconsecutive electron-transfer reactions have been obtained 115 and used toshow that high precision is needed in experimental results to obtain a reliableinterpretation.When parallel reactions occur, the situation is rather morecomplex. The decomposition of an intermediate in two different ways hasbeen discussed both for diffusion-controlled and for activation-controlledreactions 11' in terms of the yields of each product, which may be determinedexperimentally. The yields in general depend on the potential, and a studyof this dependence may help to elucidate the mechanism.The discussions of multi-step reactions mentioned above ignore theproblem of adsorption of intermediate species, although they would remainvalid if the adsorption obeyed Henry's law (ie., at very small coverages)and if the adsorption were fast.More attention has recently been focusedon the kinetics of reactions with adsorbed intermediates and their dependenceon the properties of the latter, The general type of process considered is:0 ---+ oads (1)&as + ne -+ Baas (2)Baas ---+ R (3)lo7 T. Keii, J . Res. Inst. Catalysis, Hokkaido Uniu., 1959, 7, 99.109 J. Horiuti and H. Kita, J. Res. Inst. Catalysas, Hokkaido Univ., 1964, 12, 1, 14.110 P. Van Rysselberghe, Atti A d . naz. Lincei Rend., Class Sci.$s.mat. nat., 1961,31, 391; Electrochim. Acta, 1963, 8, 583, 709.ll0a S. G. Christov, Ber. Bunsen Gesellschaft Phys. Chem., 1963, 67, 117; see alsoN. E. Khomutov, Zhur. fiz. Khim., 1960, 34, 1788.111 A. C. Riddiford, J. Chern. SOC., 1960, 1176.112 A. C. Riddiford, Electrochim. Acta, 1961, 4, 170.113 J. Horiuti and T. Nakemura, 2. phys. Chem. (Frankfurt), 1957, 11, 358; P. C.I14A. R. Despic, 15th C.I.T.C.E. meeting, London, 1964.1lS R. M. Hurd, J . Electrochem. Soc., 1962, 109, 327.116 D. H. Geske and A. J. Bard, J . Phys. Chem., 1959, 63, 1057; A. J. Bard and11'E. GiIeadi and S. Srinivasan, J . Electroanalyt. Chem., 1964, 7, 452.M. I. Temkin, Zhur. fiz. Khim., 1941, 15, 296.Milner, J. Electrochem. SOC., 1964, 111, 229.J.S. Mayell, &bid., 1962, 66, 2173; A. J. Bard and E. Solon, ibid., 1963, 67, 2326PARSONS: ELECTRODE DOUBLE LAYER AND REACTIONS 91where 0 and R are the oxidised and the reduced species, respectively, andthe subscript “ ads ” indicates that the species is adsorbed on the electrodesurface. This reaction scheme has been described in formal pseudothermo-dynamic terrns,lls assuming only one specifically adsorbed species, whichobeys Temkin’s isotherm in the logarithmic approximation. Similar ideaswere developed for the kinetics of the adsorption step itself and are applicablein the absence of an electrode rea~tion.1~~ No application to experimentalresults has yet been published. Earlier work on the kinetics of adsorptionhas been reviewed.120 This work has led to a general approach to thekinetics of reactions involving adsorption, in terms of the impedance spectrumas measured with sinusoidal a.c.l2I The novel feature is that partial transferof the charge is allowed in each step of the above reaction scheme; thus afraction Ai of charge is transferred in the i’th reaction? which may be whatis conventionally considered an adsorption reaction; CAi = 1. With somesimplifying assumptions these charge-transfer coefficients may be evaluatedfrom the experimental impedance spectrum. For deposition of T1+ on theamalgam from M-sodium perchlorate,lZ2 AR = 0.7 & 0.1, A. = 0.3 & 0.1.The technique has also been applied to specific adsorption of thiourea123and of halide ions.1239124 For thiourea,l23 A is about 0.3 and for iodide 123about 0-2, approximately independently of base solution and of solvent(methanol or water) ; later work 124 gives A = 0.48 for iodide and 0.33 forbromide.This means that the effective charges of iodide and bromide inthe inner layer are -0.52 and -0.66, respectively. If this interpretationis correct, ideas about the structure of the inner layer must be revised.Similar results can be obtained by the pulse method 125 and show very smalladsorption in the case of Cd2f deposition on the amalgam from sodiumperchlorate or nitrate but appreciable quantities of a thallium intermediatewith a charge of +0.7.It has been emphasised 126 that the adsorption of reactants is especiallycommon when the electrode reaction involves organic compounds.If theorganic reactant is present at low coverages and obeys an isotherm with afree energy of adsorption which is quadratic in the potential? and if the rateof reaction is controlled by the electron transfer, then it can be shown 12‘that the observed rate of reduction passes through a maximum; and at themost negative potentials it decreases with increase of cathodic potential asthe reactant is desorbed frQm the surface. At these low coverages it isreasonable to assume that the rate is proportional to the coverage, but athigh coverages it may even decrease with increase of coverage. This hasbeen explained in terms of a swelling of the reactant as it passes through theactivated state.126 These ideas are particularly applicable to the evolutionof hydrogen catalysed by adsorbed organic bases (which has been reviewedrecently 128).The pseudocapacitance arising as a result of the adsorption of an inter-mediate in an electrode reaction has been discussed lag in terms of the Lang-muir and the Temkin isotherms.Formally, the Temkin isotherm introducesa constant capacity in series with the Langmuir capacity in the simplestanalysis. However, for reactions which are out of equilibrium in all steps,it is possible to obtain asymmetrical capacity-potential relations even witha simple Temkin isotherm.An up-to-date survey ofrelaxation techniques has recently been publishedl30 and there is also athorough account 131 of the use of these methods for study of fast reactions.No discussion is included, however, of Barker’s development of high-levelfaradaic rectification,l32 which is essentially a combination of the charge-injection (coulostatic) technique with faradaic rectification and permits themeasurement of rate constants of very fast homogeneous as well as hetero-geneous reactions. The operational classification of electrochemical tech-niques suggests a much needed systematisation, togetherwith the prospectof being able to predict the technique appropriate to a given problem.Theperiod under review has seen the rapid growth of the application of operationalamplifiers to electrochemical problems. A symposium on their use 134provides an invaluable introd~ction,~~~ as well as examples of more sophisti-cated instruments in which these versatile and now almost indispensableunits are used.The electronic polarograph 13* is but one example of theuse of more elaborate electronic techniques in electrochemistry. The designof potentiostats has been discussed l37 and many individual instrumentsTechniques for studying electrode reactions.128 S. G. Mairanovsky, J . Electroanalyt. Chem., 1963, 4, 166; Electrochim. Acto,1964, 9, 803.la@ B. E. Conway and E. Gileadi, Trans. Farraday SOC., 1962, 58, 2493; E. Gileadiand B. E. Conway, J . Chem. Phys. 1963, 39, 3420; B. E. Conway, E. Gileadi, andM. Dzieciuch, EZectrochim. Actu, 1963, 8, 143; B. E. Conway and E. Gileadi, Canad.J . Chem., 1964, 42, 90.130 W. H. Reinmuth, Analyt. Chem., 1964, 36, 211R.132 G. C. Barker and H.W. Nurnberg, Naturwiss., 1964, 51, 191, 192; G. C. Barker,H. W. Niirnberg, and B. J. Bowles, 13th Meeting of C.I.T.C.E., Rome, 1962; G. C.Barker, H. W. Niirnberg, and J. A. Bolzan, 14th Meeting of C.I.T.C.E., Mo,s,cow, 1963.Treatise on Analytical Chemistry , ed. I. M.Kolthoff and P. J. Elving, Part I, Vol. IV, Chapter 43, Section VII, Interscience Publ.,Jnc., New York, 1964; J. W. Ashley and C. N. Reilley, J. Electroanalyt. Chem., 1964,7,253., P. Delahay, ref. 20, Vol. 1, Chapter 5 .133 C. N. Reilley and R. W. Murray,134 Analyt. Chem., 1963, 35, 1769-1833.Is5 C. N. Reilley, J . Chem. Educ., 1962, 39, A853, A933.136 M. T. Kelley, H. C. Jones, and D. J. Fisher, Analyt. Chern., 1959, 31, 1475;1960, 32, 1262; R. A. Durst, J. W. Ross, and D.N. Hume, J . Electroanalyt. Chem.,1964, 7, 245.ls7 A. Bewick, A. Bewick, M. Fleischmann, and H. R. Thirsk, Electrochim. Actu,1959, 1, 83; A. Bewick and M. Fleischmann, ibid., 1963, 8, 89; G. L. Booman andW. B. Holbrook, Analyt. Chem., 1963, 35, 1793PARSONS: ELECTRODE DOUBLE LAYEB AND REACTIONS 93have been described for kinetic measurements l37, and for potentialcontrol in coulometric experiments.139A series of reviews on d.c. polarography 140 provides an excellent modernintroduction to classical polarography as well as more recently developedtechniques. Also included are sections on kinetic measurements 140b andadsorption phenomena.l4OG Perhaps the most interesting development ofclassical polarography is the use of current-time curves on single d r 0 ~ s .l ~ ~This technique has proved to be particularly valuable in the study of theeffect of adsorption on electrode rea~ti0ns.l~~ The theory and applicationof the rotating-disc electrode and its relations have been thoroughly reviewedin an article due soon.143Hydrogen and oxygen overvoltage. Hydrogen overvoltage has lost its pre-eminence as the only thoroughly studied electrode reaction; the presentstate of the problem has been well reviewed.86, 144 Two techniques havebeen revived recently: hydrogen-atom injection or removal, and isotopeseparation. The theory of the effect on the kinetics of introducing theintermediate species was discussed in detail 145 and applied by using atomichydrogen either produced in the gas phase 146 or diffusing through the elec-trode 14' made of, e.g., palladium or iron.Conversely, the rate of permea-tion 148 has been used to determine the variation of surface concentrationof atomic hydrogen with potential. The renewed interest in the separationfactor for hydrogen isotopes as a method of elucidating mechanisms appearsto date from a recalculation of this quantity for the discharge mechanism,149which suggests a minimum value of about 13 for the D/H factor. The D/Hseparation factors have been discussed for different mechanisms l50 and itwas concluded that 3 was a possible value for the discharge mechanism. Amore recent 151 calculation requires discharge within an interstitial site toreach this value. The model used for these calculations has been criticised 152on the grounds that the difference in the zero-point energies in the activatedstate was neglected. A recent calculation 153 of D/€€ and T/H separationfactors for three mechanisms (discharge, ion + atom, combination) includesthis difference and claims that inaccuracies in calculation are not sufficientto lead to serious doubts about the conclusions.The tunnel effect wasincluded in these calculations though its effect is not large (but see alsoref. 154). Experimental work has included the measurement of Tafel para-meters155 in pure D,O as well as of D/H l 5 7 and T/H158 separationfactors. The results in general seem to confirm the views already held bythe authors about the mechanism on each metal, but diffusion control ofthe reaction on metals such as platinum appears to be excluded.The mostsurprising fact observed is the strong dependence of the separation factoron potential and on the nature of the anion in the ele~trolyte.1~7 Not allthe work has been done under the best conditions, but the effect is undoubtedlyestablished. The heats of adsorption of hydrogen and deuterium on platinumare indisting~ishable,~~~ but deuterium appears to be slightly the morestrongly adsorbed.A brief review of the oxygen evolution is available.160 Although therehave been several experimental studies of the oxygen electrode,161 progressin elucidating the mechanism is not rapid. The use of the rotating-disc andring electrode has suggested that hydrogen peroxide is an intermediatein the reaction on platinum, i.e., the mechanism may be similar to that onmercury.This does not agree with earlier views or with more recent sug-gestions163 in the course of which it was observed that adsorbed oxygenaccelerated the reaction of oxygen reduction. More detailed analysis seemsto indicate 164 that only the reduction of hydrogen peroxide is accelerated,while the first step is actually retarded. Measurements of oxygen over-voltage 165 on palladium-gold alloys show no correlation with the d-bandstructure, probably owing to the presence of an oxide film on the surface,and they are interpreted in terms of dual control with film transport.16sInterest in fuel cells has stimulated arevival in this subject and fundamental advances have resulted.Most ofthe work has been done with platinum electrodes, and two summary papershave been published.167, 188 Although some general features are establishedthere is still disagreement in experimental results and their interpretation.There seems little doubt that the reaction involves oxygen in some formadsorbed on the electrode, but the precise role of the gas is uncertain. Itis claimed lG8 on the basis of potential sweep measurements that oxidationoccurs in three potential regions for a variety of compounds, the currenthaving maxima a t about +0.3, +0.9, and 3 - 1 . 3 ~ on the hydrogen scalein acid solution. In each region the ascending current (potential morenegative than that corresponding to the maximum) obeys Tafel’s equationand is of fractional order with respect to the reacting compound.Thecurrent then decreases as a result of inhibition by adsorbed oxygen, thecoverage of which increases with potential. The three regions are ascribedto the effect of three different forms of adsorbed oxygen or hydrogen, whichare stable in the different potential regions. The interpretation 169 of thekinetics is in terms of non-electrochemical, rate-determining production ofan adsorbed radical eitherRHads Ra& +Ha& (4)or, at more positive potential,RHa& + OHab + Rab +H.@ ( 5 )the adsorption following Temkin’s model.Steady-state experiments 16’ do not seem to show the first region and arenot extended to the third. Again a Tafel behaviour is observed, but witholefins the discharge of water or hydroxyl ion to form adsorbed hydroxyl isconsidered to be the rate-determining step.The drop in current beyond+0.9 v is ascribed to the conversion of adsorbed OH to 0, which retardsthis reaction.:7O The oxidation of the hydrocarbon is a surface reactionwith hydroxyl radicals. On the other hand, with oxalic acid a rate-determin-ing decomposition of adsorbed HO,C*CO*O* radicals formed from the un-dissociated acid is suggested.171 However, other evidence suggests thatanions are more often the reacting species. A~etylene,~'~ in contrast to theolefins, is more strongly adsorbed and the surface oxidation (s) becomes rate-determining. The effect of electrode material on ethylene oxidation wasstudied for five metals 173 and was discussed in terms of the extrapolatedrates at the point of zero charge.The significance of this type of comparisonhas been discussed in general terrn~.17~ A recent paper 175 on the oxidationof formic acid gives a fairly complete survey of previous work on this system.It is suggested that the measurement of adsorption by cyclic voltammetryand high-current chronopotentiometry276 is in error because of the slowadsorption of formic acid. Hence there is, in fact, a decreasing amount ofthe adsorbed species on the surface at the potentials corresponding to thelimiting current, which has been ascribed to surface saturation177 on thebasis of measurements in pure formic acid. Clearly the results for aqueoussolutions 175 do not exclude this mechanism for pure formic acid.The restpotential in this system, as in most systems of this type, is a mixed potentialalthough the mechanism proposed l 7 g has been criticised.l7Q Oxidation ofmethanol is said t o occur with the formation of carbon monoxide andreaction of the latter with adsorbed oxygen;lS0 but higher alcohols probablyreact in the form of an adsorbed radical 168* and evidence has been givenfor chemisorption of methanol on platinised platinum.182 Oxidation ofcellulose and lower carbohydrates has been reported but few details havebeen published. Electrochemical investigation of biochemical systems hasbegun 184 with the eventual aim of constructing it biochemical fuel cell.The interest in fuel cells has also stimulated work with porous electrodes170 H.Wroblowa, B. J. Piersma, and J. O'M. Bockris, J . Electroanalyt. Chem.,1963, 6, 401 ; M. Green, J. Weber, and V. Drazic, J. Electrochem. SOC., 1964, 111, 721.171 J. W. Johnson, H. Wroblova, and J. O'M. Bockris, Electrochim. Acta, 1964,9, 639.172 J. W. Johnson, H. Wroblova, and J. O'M. Bockris, J. EZectrochem. Soc., 1964,111, 863.17sH. D a b s and J. O'M. Bockris, J. Electrochem. SOC., 1964, 111, 728.174 R. Parsons, " Solid Surfaces ", ed. H. C. Gatos, North-Holland, Amsterdam,.176 S. B. Brummer and A. C. Makrides, J. Phys. Chem., 1964, 68, 1448.176 M. Breiter, Electrochim. Acta, 1963, 8, 447, 457.177 B. E. Conway and M. Dzieciuch, Canad. J. Chem., 1963, 41, 21, 38, 55.178 M. H. Gottlieb, J. Electrochem. Xoc., 1964, 111, 465.179 M.Breiter, J. Electrochem. SOC., 1964, 111, 1798.180 S. Gilman and M. W. Breiter, J. Electrochem. SOC., 1962, 109, 622, 1099; M. W.Breiter, ibid., 1963, 110, 449; Electrochim. Acta, 1963, 8, 973; S. Gilman, J. Phys.Chem., 1963, 6'7, 1898; 1963, 68, 70.la1 G. A. Bogdanovski and A. I. Shlygin, Zhur. $2. Khim., 1959, 33, 1769; 1960,34, 57; A. K. Korolev and A. I. Shlygin, ibid., 1962, 36, 314; R. A. Rightmire, R. L.Rowland, D. L. BOOS, and D. L. Beals, J . Electrochem. SOC., 1964, 111, 242.182 B. I. Podlovchenko and E. P. Gorgonova, Dolclady Alcad. Nauk X.S.S.R., 1964,156, 673.J. O'M. Bockris, B. J. Pierama, and E. Gileadi, Electrochim. Acta, 1964, 9, 1329.184 M. J. Allen, R. J. Bowen, M. Nicholson, and B. M. Vasta, Electrochim. Acta,1963, 8, 991; 31.J. Allen and R. L. Januszeski, ibid., 1964, 9, 1423; M. J. Allen, ibid.,p. 1429.1964, p. 418PARSONS: ELECTRODE DOUBLE LAYER AND REACTIONS 97and determination of the characteristics of electrode reactions under thesec0nditions.l8~Other organic reactiom. A general survey of the electrolytic reductionof organic compounds was published 186 in 1962. Preparative methods forreduction of acetylenic bonds 187 and for fluorination 188 were also reviewed.The interesting possibility of controlling the nature of the product of anorganic electrode reaction by programmed potentiostatic pulsing was con-sidered,l89 as well as the relation between quantum mechanics and organicelectrode reactions.190Particular attention has been paid to coupling reactions, both reductiveand oxidative. The possibility of obtaining high yields of adiponitrile fromacrylonitrile l91 is commercially attractive.The Kolbe reaction has beendiscussed in several reviews;lg2 there seems little doubt that radical inter-mediates are formed.177~ 193Spectroscopy is beginning t o provide useful information about intermedi-ates which are sufficiently stable to Muse into the solution.l9* The applica-tion of electron paramagnetic resonance spectroscopy for this purpose hasbeen reviewed recently.lg5It is necessary to distinguish the effects due to irradiationof the electrode itself from those due to photolysis of the solution. Theformer play an important role at semiconductor electrodes but their import-ance at other electrodes has been uncertain.Recent work lg6 suggests thata cloud of solvated electrons is formed around mercury electrodes whenthey are irradiated. The effective work function of the electrode decreasesas the electrode is made more negative. Similar effects are observed inphotopolarography,l97 but they must be distinguished from the radiolyticeffects which predominate with organic compounds in the solution 198 andoften involve the production of free radicals reacting at the electrode.199In the oxidation of formic acid at platinum the effect of X-rays is differenton each of the three peaks 200 (cf. ref. 168) and largely depends on the re-actions of the products of radiolysis of the solution (hydrogen and hydrogenperoxide), although an electrode effect is detectable on the third peak, beingprobably due to the oxide layer.The concept of the ‘‘ equivalent redoxpotential ” for a particular type of radiation has been discussed,201 and itis now clear that the main effects are due to the reactions of these productsof radiolysis with other species in the solution. Flash-photolysis has beenused 202 to generate radicals in solutions of inorganic ions ; the photo-effects 203on thin layers of phthalocyanine or chlorophyll on electrodes may provideinformation on the primary photosynthetic process. The reverse processof light emission as a result of electrolysis has also been observed.204Useful reviews have appeared on electrocrystallisation,205metal dissolution,2°6 semiconductor electr~chemistry,~~~ 207 anodic films,16, 208glow discharge electrolysis,209 and the effect of adsorption of non-reactantson the kinetics of electrode reactions ;259 12% 1429 2lO these topics are thereforenot discussed here.THE eight years that have elapsed since the last Report on adsorption andheterogeneous catalysis have seen so much progress tbat it is now impracticalt o cover the entire field in any one year.This Report treats catalysis bymetals to the exclusion of catalysis by oxides and other solid catalysts, andneglects studies of chemisorption where these have only remote implicationson catalysis; it is hoped to cover these subjects in future years.The publication of two new journals, both substantially concerned withcatalysis, has commenced in the period under review; these are JournaZ ofCatalysis and Kinetiku i Katulix, and the latter is being fully translated intoEnglish.Selwood’s book 2 provides a thorough account of the applicationof magnetic measurements to the study of adsorption and catalysis, whileanother book 3 has attempted to cover the whole field of catalysis by metalsat a moderately advanced level. Publication of the monumental seriesentitled “ Catalysis ”, edited by Emmett, concluded with Volume VII;4Advances in Catalysis continues to provide a series of readable and authorita-tive reviews, and the Annual Review of Physical Chemistry frequently containsreview articles concerned with catalysis and surface ~hemistry.~ There havebeen three International Congresses on Catalysis, and the Proceedings havebeen published.s This Report will concentrate on advances made sincethe publication of the last major review of the field.sPreparation and Morphology of Catalysts.-Many novel techniques ofmetal-catalyst preparation have been described.The direct examinationof metal catalysts by spectroscopic and diffraction techniques is yielding awealth of information on their detailed morphology; evaporated metal filmsand platinum-alumina have received particular attention, the latter becauseof its application in petroleum reforming.Two important studies of silver films have beenreported.‘, Electron microscopy has shown that separated silver crystal-lites are present in thin films, and that as the weight increases they graduallygrow, finally forming a coherent uneven layer;’ X-ray diffraction of thethicker films showed crystallite sizes between about 200 and 600 8.Fourtypes of silver film, differently prepared, were examined both by transmissionAdsorption and Collective Paramagnetism ”, Academic Press,Catalysis by Metals ”, Acaedmic Press, Inc., New York, 1962.P. H. Emmett (ed.), “ Catalysis ”, Reinhold Publ. Corp., New York, 1960,H. Taylor, Ann. Rev. Phys. Chem., 1961,12, 127; G.-M. Schwab and K. Gossner,(a) Adv. CutaZysk, 1956, 9; ( b ) “ Actes du Deuxibme Congrks Internationale de’ R. L. Moss, M. J. Duell, and D. H. Thomas, Trans. Parday Sy., 1963, 59,Evaporated rnetaZJiZms.C. Kemball, An:. Reports, 1956, 53, 60.a P. W. Selwood,Inc., New York, 19!2.* G. C. Bond,VOl. VII.ibid., 1963, 14, 177; R. L. Burwell and J, A. Peri, ibid., 1964, 15, 131.Catalyse ”, Technip, Paris, 1960, Vols. I and 11; (c) to appear.216.J. Bagg, H. Jaeger, and J. V. Sanders, J. Catalysis, 1963, 2, 449100 GENERAL AND PHYSICAL CHEMISTRYand by reflection electron microscopy, and concentrations of grain boundaries,stacking faults, and coherent twin boundaries, isolated dislocations, andnon-coherent twin boundaries were estimated. * However, points and linesof emergence of defects do not seem to affect the Arrhenius parameters ofdecomposition of formic acid. The same techniques have been applied tonickel and tungsten film^,^ and the first effect of sintering was shown to bethe removal of intercrystalline gaps.Electron and X-ray diffraction of ironand nickel films has a140 been reported.l* Palladium-silver alloy Nms havebeen prepared by (i) slow simultaneous evaporation from separate wires,(ii) by evaporation of an alloy wire, and (iii) by homogenising successivelydeposited layers of the two metals by heat;l1 the kinetics of oxidationof carbon monoxide on such films compared well with those found with thecorresponding alloy. The heterogeneity of nickel films has been assessed byadsorption and desorption of three isotopic variants of carbon monoxide.12Raney metals. Raney nickel continues to command much attention andthe question whether or not it contains “specially bound hydrogen” hasbeen hotly debated. Many workers claim that the high activity of Raneynickel is associated with dissolved hydrogen (see ref.13 for a summary ofviews expressed), although it has been shown unambiguously that hydrogenformed on heating results from the reaction of bound water with residualal~minium.~3 The slow release of hydrogen when Raney nickel is storedunder water or methanol is responsible for its retention of activity.l4 Forthe hydrogenation of acetone, however, its activity is increased by anodictreatment, which is thought to remove protonically dissolved h~dr0gen.l~The intermetallic compounds which can be formed between nickel andaluminium are : NU3, Ni2Al,, NiAl, and Ni3Al.l6 The 50 : 50 alloy usuallycontains two or three of these compounds, of which only the bst two areattacked by strong alkali.Raney nickel prepared from Ni2Al3 is 2-3times more active for hydrogenation of acetone than that formed fromNU,. Active Raney nickel can be made by treating the 50:50 alloy withwater a t 70--80°,17 and its activity for reduction of the keto-group can besuppressed by treatment with amino-acids and gelatine without impairingits activity for reduction of olefinic double bonds.ls The volume of carbonmonoxide adsorbed by Raney nickel depends critically on the leachingprocedure and on the Ni:Al ratio in the original all0y.lQ Some of the nobleJ. R. Anderson, B. G. Baker, and J. V. Sanders, J. Catalyds, 1962, 1, 443.lo L. S. Palatnik, M. Ya. Fuks, B. T. Boijo, and A. T. Pugachev, Piz. MetuZZ. il1 R. L. Moss and D. H. Thomas, Trans, Paraday SOC., 1964, 60, 1110.la R.Suhrmann, H. Heyne, and G. Wedler, 2. Elektrochem., 1962, 66, 725;lS P. Mars, J. J. F. Scholten, and P. Zwietering, ref. 6(b), p. 1245.l4 P. Mars, T. van der Mond, and J. J. F. Scholten, Ind. and Eng. Chem. (Prodwtl5 J.-M. Menard and Y. Trambouze, Bull. Sac. chim. Prance, 1963, 398; J.-M.l6 R. Sassoulas and Y. Trambouze, Bull. SOC. chim. Frame, 1964, 985.l7 J. H. P. Tyman, Chem. and Id., 1964, 404.Is H. Fukawa, Y. Izumi, S . Komatsu, and S. Akabori, Bull. Chem. SOC. Japan,l9 J. R. Huff, R. J. Jasinski, and R. Parthasarathy, I d . and Eng. Chem. (ProductMetallov., 1964, 17, 726.J . Catalysis, 1962, 1, 208.Res. and Development), 1962, 1, 161.Menard, Y. Trambouze, and M. Prettre, ibid., p. 401.1962, 35, 1703.Res.and Development), 1964, 3, 159BOND: CATALYSIS BY METALS 101Group VIII metals have been prepared in Raney form and their activity asfuel-cell catalysts has been examined.20 Also, a procedure for preparingRaney silver has been patented.*’Platinum black made from chloroplatinic acidand hydrogen is more active for decomposition of hydrogen peroxide andfor hydrogenation of hex-l-ene when ultrasonic vibration is used than whennormal mechanical agitation is used, providing the platinum concentrationis less than 0.1 %.22 The deactivation of electrodeposited platinum blackby thin layers of base metals (Cu, Ag, Pb, Cd, Zn) electrodeposited on tophas been examined with hydrogenation of ethyl cinnamate as the stepreaction; the results were interpreted in terms of the electronic structure ofthe base Platinum black sintered a t 400-600” in oxygen is moreactive for decomposition of hydrogen peroxide than when a temperature of200” is used, presumably as a result of surface oxide formation.24Considerable interest has been shown in the use of sodium and potassiumtetrahydridoborate for reducing metal salts to highly active metal catalysts.Such catalysts are variously described as being ‘‘ borides” or ‘‘ boron-promoted,” but their composition is not yet adequately defined.Nickel“boride,” made by reducing an aqueous or ethanolic solution of nickelacetate, is more active than Raney nickel for the reduction of oct-l-ene, andcauses less double-bond migration.25 The reduction of aqueous solutions ofthe chlorides of platinum,26,27 palladium,27 and rhodium27 with a boro-hydride also leads to highly active metal dispersions.Platinum- andpslladium-boron alloys have been prepared and their activity examined.28Sodium tetrahydridoborate has also been used successfully to produce finelydivided palladium-gold, platinum-gold, and platinum-iridium alloys,2s andplatinum-ruthenium alloys whose behaviour in the reaction of methanewith deuterium has been studied.30 The reduction of chloroplatinic acidwith silicon hydrides (e.g., tribenzylsilane) affords a very active platinumcatalyst . 31The Adams procedure has been adapted to prepare mixed oxides whichon reduction give catalysts more active or more selective than either oxideseparately. Rhodiurn-platinum oxides have been thoroughly examined 32and they reduce substituted benzenes with less hydrogenolysis than is causedOther unsupported metals.2o E.W. Justi and A. W. Winsel, J . Electrochem. SOC., 1961, 108, 1073.21 B.P. 951,990/1964.22 Li Wen-chou, A. N. Mal’tsev, and N. I. Kobomv, Russ. J . Phys. Chem., 1964,23 G. Lapluye, Bull. Xoc. chim. France, 1963, 2287.24 Yu. M. Tyurkin and L. G. Feoktistov, Kinetika i Katuliz, 1963, 4, 221.C. A. Brown and H. C . Brown, J . Amer. Chem. SOC., 1963, 85, 1003, 1005.26 C. A. Brown and H. C . Brown, J . Amer. Chem. SOC., 1962, 84, 1494, 2827.2 7 B. D. Polkovnikov, A. A. Balandin, and A. M. Taber, Doklady Akad. NaulcS.S.S.R., 1962, 145, 809; A. M. Taber, B. D. Polkovnikov, N. N. Mal’tseva, V. I.Mikheeva, and A.A. Balandin, ibid., 1963, 152, 119.28 B. D. Polkovnikov, A. A. Balandin, and A. M. Taber, Izvest. Akad. NaukS.S.S.R., Otdel. khim. Nauk, 1964, 267.2 9 E. L. Holt, Nature, 1964, 203, 857.30 D. W. McKee and F. J. Norton, J . Phys. Chem., 1964, 68, 481.31 R. W. Bott, C. Eaborn, E. R. A. Peeling, and D. E. Webster, Proc. Chem.8 2 5. Nishimura and H. Taguchi, Bull. Chem. SOC. Japan, 1963, 36, 353; see also38, 229.SOC., 1962, 337.preceding papers in this series102 GENERAL AND PHYSICAL CHEMISTRYby platinum alone. Platinum-ruthenium oxides, on reduction, are muchmore active for reduction of nitrobenzene to aniline than is platinum.33Although it was formerly believed that thesupport was an inert partner in supported metal catalysts, there is a growingbody of evidence to show that its role is more than simply that of a vehicleon which the metal can be thinly spread.The variation of the activity ofnickel supported on various doped oxides for decomposition of formicacid 34 is clear evidence of this, and it has been suggested that the supportinfluences the Fermi level of the meta1.35, 36 In a series of papers,37--39Maxted and his associates have investigated nickel, palladium, and platinumsupported on a variety of oxides (ZrO,, Tho,, Al,03, TiO,, Cr203, MgO,V,O,, and rare-ea.rth oxides), using the hydrogenation of ethyl oleate, cin-namic acid, and cyclohexene as test reactions. In the case of palladium,the loss of activity on sintering was found to increase with decreasing meanpore radius of the support.It is a matter of deep interest to know how a metal is dispersed on asupport.Information may be obtained by direct examination, e.g., byelectron microscopy, X-ray line-broadening or low-angle scattering whichcan give information on crystallite size, or by dynamic or static measure-ments of chemisorption of those gases (chiefly hydrogen and carbon mon-oxide) which do not interact with the support. The gas-adsorption procedureis applicable when the state of metal dispersion is too high to be revealedby other techniques.Platinum on alumina has commanded most interest by reason of itscommercial prominence. It has recently been shown that metal surfaceareas calculated from chemisorption of hydrogen and carbon monoxide arein excellent agreement ;4o the accompanying table quotes the mean crystalliteMetal crystallite sixes in supported metal catalystsThe agreement between the results obtained by the differentmethods is usually very satisfactory.The degree of dispersion found withlow metal concentrations on unsintered catalysts sometimes 41, 42 approachesthe atomic, although in such cases there is no means of telling whether themetal exists in isolated atoms, as " islands " one atom thick, or in small'' normal " crystallites in which for eight unit cells (d M 11 A) some SO%of the atoms are superfi~ial.~~ A procedure for using X-ray line-broadeninghas been described in detaiL43 Procedures for the dynamic measurementof metal areas by gas adsorption have been and kinetics ofsintering of platinum-alumina have been studied.34, 46s 4* The dehydro-cyclisation activity of platinum-alumina has been correlated with thepresence of a PtxV " complex " which is extractable with dilute hydrofluoricacid or a~ety1acetone;~g the " complex " may be a Pt02-A120, compound.50Novel supported catalysts. A technique for the evaporation of metals (Niand Ni + Cu) on to a support (corundum) has been described.51 Methodsfor the impregnation 52 or incorporation 53 of platinum in molecular sieveshave also been reported; the " incorporation " catalyst selectively hydro-genates n-alkenes in the presence of branched alkenes.53 The preparationand properties of silk-supported platinum and rhodium catalysts have beendescribed.54Isotopic Exchange Reactions.-Although hydrogen-deuterium exchangeand para-hydrogen conversion appear to have lost some of their formerattraction as catalytic probes, there has been a renewed interest in exchangereactions involving deuterium oxide and in the exchange of alkylbenzenes.A possibleexplanation for the apparent decrease in the volume of work reported onthese reactions is the growing realisation that, although formally simple,they are neverthelesa far from straightforward. The hydrogen-deuteriumexchange is not, of course, catalysed paramagnetically, while the para-hydrogen conversion is, and there is a welcome tendency to use both theseHydrogen-deuteriurn exchange and para-hydrogen conversion.reactions to distinguish between possible mechanisms, especially at lowtemperatures.&, 56 The complications to which these reactions are subjectare illustrated by the observations that the activity of nickel for thesereactions is less when it is cooled from the reduction temperature (350") tothe reaction temperature (-80") under hydrogen than when it is evacuatedand cooled under helium, but the effect is reversed for a nickel-copperalloy.55 The presence of ethylene residues on the nickel surface also catalysesthe reaction. The kinetics of the para-hydrogen conversion have beenexamined for films of chromium, iron, nickel (zero order at 20°), manganese(fractional positive, order at 20"), and zinc (first order at 95", probably para-magnetic mechani~m).~~ Over films of manganese, iron, cobalt, and nickelat - 183 " and cobalt at 20 O the order changes from zero or fractional negativeto fractional positive or fist with increasing pressure.The dissociativemechanism holds over nickel to quite low temperatures (- 196" 56 or - 105" 55)although the paramagnetic mechanism operates over this and other metalsand alloys at -252°.57 Nickel on alumina is about 100 times more activethan chromium oxide on alumina for para-hydrogen conversion at -196".58Hydrogen-deuterium exchange has been studied on high-vacuum evaporatedplatinum iilms at low temperatures with simultaneous measurements of resis-tance chances.59The exchange of aromatic compounds with deute&um and deuterium oxide.The metal-catalysed exchange of hydrogen atoms in organic molecules bytritium is an attractive alternative to radiation-induced labelling, particu-larly in regard to specificity, but much more needs to be known about fheeffect of molecular geometry on substitution rates before the method becomesgenerally applicable.Garnett and his associates, in a series of papers,eohave studied the catalysed deuteration of a number of organic molecules,chiefly using reduced platinum dioxide as catalyst, careful control of whichis essential if reproducible results are to be obtained. Aromatic hydrogenonly is exchanged. The effect of alkyl-substitution in the benzene ring onthe rate of deuteration is interpreted in terms of either associative ordissociative n-complex mechanisms (respectively A and B, p.105), and recentwork in which the equilibration of benzene and hexadeuteriobenzene wasstudied simultaneously with benzene-deuterium oxide exchange shows thatthe latter mechanism is predominant.62 The deuteration of p-xylene withdeuterium oxide has been studiedwithvarious metals(Pt, Pd, Ir, Ru, Rh, Co,and Ni) as catalysts;63 the last two metals cause exchange only in the methylgroups. Above go", platinum dioxide is readily reduced by benzene,64 andthe process is facilitated by previous irradiation of the oxide with ultraviolet56 W. K. Hall, F. E. Lutinski, and J. A. Hassd, Tram. Paruday Soc., 1964, 60,1823.66 D. D. Eley and D. Shooter, J . Catalysis, 1963, 2, 259.5 7 J. T. Kummer, J . Phys. Chern., 1962, 66, 1715.68 N. Wakao, J. M. Smith, and P.W. Selwood, J . Catalysis, 1962, 1, 62.59 H. Gentsch, 2. phys. Chem. (Frankfurt), 1962, 35, 69.6 0 J. L. Garnett and W. A. Sollich, J . Catalysis, 1963, 2, 339; references t o earlier61 J. L. Garnett and W. A. Sollich, Nature, 1964, 201, 902; J . Catalysis, 1963,2,350.J. L. Garnett and W. A. Sollich-Baumgartner, J . Phys. Chem., 1964, 88, 3177.K. Hirota and T. Veda, ref. 6(c), paper 11.2; J . Chern. SOC. Japan, 1963, 84, 882.134 J. L. Garnett and W. A. Sollich, J . Phys. Chem., 1964, 68, 436.papers are given thereBOND: CATALYSIS BY METALS 105light or y-radiati~n.~~ The activity of a number of metals reduced byhydrogen or sodium tetrahydridoborate for deuteration of pfldine andvarious azines has been reported.66 Poisoning phenomena have beeninvestigated.67The hydrogen atoms in alkylbenzenes can be classified according to theirease of exchange with deuterium over unsintered nickel films as follows :(A) those on carbon atoms a to the ring or in the ring positions not ortho toa substituent ; (B) those in ring positions ortho to a substituent ; and (C) those(B) -*.- .. *- -on carbon atoms #I or y to the ring.68 However, sintering at 200" 68 orpoisoning with carbon monoxide 69 selectively deactivates the catalyst forexchange of ring hydrogen. The exchange of p-xylene with deuterium overfilms of palladium, platinum, and tungsten has been examined.'OOther isotopic exchanges. In the exchange of methane with deuteriumover alloys of palladium-platinum and -rhodium made by reduction of themixed salt solutions by sodium tetrahydridoborate,7l stepwise exchange ispredominant although multiple exchange increases in importance withincreasing temperature.With similarly prepared platinum-rutheniumall~ys,~O activity is at a maximum in the 10-25% ruthenium range. Theexchange pattern of 1,1,3,3-tetramethylcyclohexane over palladium filmsprovides further evidence for the participation of n-bonded intermediates. 72The exchange of propene with deuterium oxide has been examined withnickel and palladium as catalysts,73 and the ammonia-deuterium reactionhas been further studied.74The Hydrogenation of Olefins and Acetylenes-The volume of work beingdone on these reactions continues to be prodigious, and in general only recentpapers are selected for mention here.There is much interest in the selective6 5 W. G. Brown, J. L. Garnett, and 0. W. VanHook, J . Phys. Chem., 1964,68,3064.6 6 G. E. Calf and J. L. Garnett, J . Catalysis, 1964, 3, 461.~3' R. A. Ashby and J. L. Garnett, Austral. J. Chem., 1963,16,549; C. G. Macdonald68 E. Crawford and C. Kemball, Trans. Faraday Soc., 1962, 58, 2452.69 M. J. Phillips, E. Crawford, and C. Kemball, Nature, 1963, 197, 487.70 R. J. Harper and C. Kemball, ref. 6(c), paper 1.76.71 D. W. McKee and F. J. Norton, J . Catalysis, 1964, 3, 252.7 2 J. J. Rooney, J. Catalysis, 1963, 2, 53.73K. Hirota, Y. Hironaka, and E. Hirota, Tetrahedron Letters, 1964, 1645; K.7 4 K. Miyahara, J . Res. Inst. Catalysis, Holckaido Univ., 1961, 9, 159; 1963, 11,and J.S. Shannon, Tetrahedron Letters, 1963, 1349.Hirota and Y. Hironaka, Bull. Chem. SOC. Japan, 1964, 37, 535.129; K. Miyahara and A. Ozaki, ibid., 1963, 11, 124106 GENERAL AND PHYSICAL CHEMISTRYhydrogenation of molecules containing more than one multiple C-C bond,and in the stereospecificity of the hydrogenation of substituted cyclic olefins.A comprehensive review of this field has been published.75That hardy annual of metal catalysis, the hydrogenationof ethylene, continues to be investigated. Reproducible rates can be obtainedon nickel films between 0" and 200" by careful purification of the reactants ;76the maximum rate occurs at 130" and the activation energy is 6.6 kcal.mole-1below this temperature. Sintering of nickel films between 25" and 400" iswithout affect on the kinetics and activation energy (measured between -40"and +40"),77 but it is a measure of the lack of agreement achieved by workersin this field that values of 9.1-10.3 kcal.mole-1 are reported.The hopethat studies of rate-dependence on alloy composition would lead directly tothe heart of metal catalysis seems doomed to disappointment; the activityof nickel-copper alloys varies markedly according to whether they arecooled from reduction temperature in helium or in hydr0gen,7~ and reproduci-bility of rates between investigations has not yet been achieved. Hopedeferred maketh the heart sick. More light comes from isotopic tracerstudies ; the analysis of the product distributions obtained from the reactionof ethylene with deuterium over platinum and iridium catalysts by a steady-state treatment shows unambiguously that the appearance of only smallamounts of deuterated ethylenes is due to the difficulty which ethylenemolecules experience in desorbing, and not to any reluctance of ethyl radicalsto revert to adsorbed ethylene.'g The reaction of hex-l-ene with deuteriumover reduced platinum dioxide shows similar behaviour .8OOlefin isomerisation (double-bond migration or cis-trans-isomerism) oftenoccurs concomitantly with olefin hydrogenation ; Russian workers (Freidlin,Litvin, Kazanski, and their associates) have been especially productive inthis field. Among the reactions studied are the hydroisomerisation of buteneisomers in the gas phase,799 82 of pentene isomers in the liquid phase,s3, g4and of hexene isomers (both positional and structural) in the gas 85 and theliquid pha~e.s6-~9 The racemisation of optically active olefins (e.g., 3,7-Mono-oleJim76 G.C. Bond and P. B. Wells, Adv. Catalysis, 1964, 15, in the press.76 K. Miyahara, J. Res. Inst. Catalysis, Hokkaido Univ., 1963, 11, 1.7 7 E. Crawford, M. W. Roberts, and C. Kemball, Trans. Paraday SOC., 1962, 58,7 8 W. K. Hall and J. A. Hassell, J. Phys. Chem., 1963, 67, 636.7 9 G. C. Bond, J. J. Phillipson, P. B. Wells, and J. M. Winterbottom, Trans.Faraday SOC., 1964, 60, 1847; see also J. H. Sinfelt, J. Phys. Chem., 1964, 68, 856;J. L. Carter, P. J. Lucchesi, J. H. Sinfelt, and D. J. C. Yates, ref. 6(c), paper 1.37.8 0 G. V. Smith and R.L. Burwell, J. Amer. Chem. SOC., 1962, 84, 926.8 1 G. C. Bond, G. Webb, P. B. Wells, and J. M. Winterbottom, J. Catalysia,'l962,8 2 J. J. Phillipson and P. B. Wells, Proc. Chem. SOC., 1964, 222.s3 G. C. Bond and J. S. Rank, ref. 6(c), paper 11.1.84 L. Kh. Freidlin, E. F. Litvin, and L. M. Krylova, Neftekhim., 1964, 4, 185.8 5 R. Maurel, M. Marcq, and J. E. Germain, Compt. rend., 1963, %7, 4196.86 L. Kh. Freidlin, Yu. Yu. Kaup, and E. F. Litvin., Izwest. Akad. Nauk S.S.S.R.,8 7 I. V. Gostunskaya, A. I. Leonova, N. B. Dobroserdova, and B. A. Kazanski,a8N. B. Dobroserdova, G. S. Bakhmet'eva, A. I. Leonova, I. V. Gostunskaya,89 I. V. Gostunskaya, A. I. Leonova, and B. A. Kazanski, Neftekhim., 1964, 4,1761.1, 74.Otdel. khim. Nauk, 1962, 1464.Neftekhim., 1963, 3, 498, and following paper.and B.A. Kazanski, Neftekhim., 1964, 4, 215.379BOND: CATALYSIS B Y METALS 107dimethyloct- l-ene) has been observed during their hydrogenati~n.~~ All theGroup VIII metals (except iron) have been examined. Cobalt is exception-ally active in catalysing isomerisation,82+ 86 and palladium only slightly lessso.81+ 83, e5, *7, 89 Rhodium is distinctly less active for this process at roomtemperature than cobalt or palladium,83, 84 while platinum and iridium causevery little isornerisation.8lS 83, 88 Interpretation of this pattern has beenattempted. 75, 81The addition of hydrogen to 1,2-disubstituted cycloalk-l-enes should giveonly the corresponding cis-l,2-dialkylcycloalkane if the addition is purelycis, and considerable discussion has centred round the pathway to thesignificant amounts of trans-isomers which are 0bserved.9~-g5 Siegel andhis associates believe 91, 92 (taking 1,2-dimefhylcyclohexene as an example)that the trans-isomer arises by isomerisation to 2,3-dimethylcyclohexene,followed by desorption and random re-adsorption.The Northwesternschool 8 0 ~ 9 4 postulates a " stereochemically symmetrical intermediate "which may be a dissociatively adsorbed olefin (see below); addition ofhydrogen to this species can lead to either isomer. The debate continues.M MeDissociatively adsorbed oleJin (l-adsorbed-2,3-dimethylcyclohex-l-erte).Acetylenes. The widespread use of metallic catalysts for removingtraces of acetylenes from olefin-containing gas streams has stimulatedinterest in the reasons underlying the high selectivity for removal ofacetylene often observed particularly with palladium.Selectivities shownby the Group VIII metals for olefin formation from acetylenes (not quitethe same thing) have been reviewed;'5, 81 these fall in the sequencePd > Rh > Ni w Fe w Co > Pt > Ru > 0 s > I r for gas-phase reactions,and similar partial sequences have been reported for the liquid-phasehydrogenation of the pentynes.w, g5 Freidlin has studied the liquid-phasehydrogenation of other acetylenic hydrocarbon^.^^ Addition of hydrogento dialkylacetylenes often gives high yields of the corresponding cis-olefin ;for example, but-2-yne reacts with deuterium over palladium-alumina togive 99 yo of cis-2,3-dideuteriobut-Z-ene at room temperature.97 MechanismsW.D. Huntsman, N. L. Madison, and S. I. Schlesinger, J. Catalysis, 1963, 2,S . Siegel and B. Dmuchovsky, J . Amer. Chem. SOC., 1962, 84, 3132; 1964, 86,9 2 S. Siegel and G. V. Smith, J . Amer. Chem. SOC., 1960, 82, 6087.Q g C. Lethuillier, D. Cornet, and F. G. Gault, Bull. SOC. chim. France, 1964, 1424.94 J. F. Sauvage, R. H. Baker, and A. S . Hussey, J . Amer. Chem. Soc., 1960, 82,96 L. Kh. Freidlin and Yu. Yu. Kaup, Doklady A k d . Nauk S.S.S.R., 1963, 152,96 L. Kh. Freidlin and Yu. Yu. Kaup, Izvest. Akad. Nauk S.S.S.R., Otdel. khim.97 E . F. Meyer and R. L. Burwell, J . Amer. Chem. SOC., 1963, 85, 2881, 2887; see498.2192.6090; 1961, 83, 3874.1383.Nauk, 1962, 1660; 1963, 166, 742, 1091; Neftekhim., 1962, 2, 154.also T. Kabe and I.Yasumori, J . Chem. SOC. Japan, 1964, 85, 410108 GENERAL AND PHYSICAL CHEMISTRYof formation of the by-products have been discussed.97,98 Wells hasreviewed this subject.99DioteJinS. These behave similarly to acetylenes in many respects, evenwhen the double bonds are not conjugated; thus, for example, Group VIIImetals show selectivities for olefin formation from allene and butadienesimilar to those given by acetylene.*l The products obtained from theliquid-phase hydrogenation of diolefins over nickel,lOO, lo1 cobalt,lO2 pal-ladium,83~ 101-103 platinum,83, 101, l o 3 9 lo4 and rhodium 83 catalysts have beenanalysed and mechanisms have been discussed. The cis-isomer of piperylene(penta-1,3-diene) yields the pentene isomers in amounts which differ sub-stantially from those given by the trans-isomer;83s lo1 this is indeed a happyhunting-ground for the mechanistically minded.Hydrogenation of Aromatic Rings.-Cyclohexane of high quality isrequired as a raw material in the production of nylon, and there is muchcommercial interest in its efficient manufacture from benzene.105 Kineticstudies of this hydrogenation have been reported in which nicke1,106--108cobalt,lo7 , lo9 nickel-cobalt palladium, platinum, and ruthenium ll1are used as catalysts.From the decrease in the activation energy with in-creasing methyl substitution (paralleling the decrease in ionisation potential),it appears that benzene may be adsorbed by a mbond to the surface.108Oxygenated solvents inhibit the hydrogenation of benzene.1°7 Much interesthas been shown in the factors affecting the ratio of cis- to trans-isomers ofdialkylcyclohexanes formed from the corresponding disubstituted benzene ;the systems studied include the xylenes 112, 113 and other derivatives (e.g.,cresols and t ~ l u i d i n e s ) .~ ~ ~ Siegel et aZ.l12 interpret their findings in terms ofa mechanism (similar to that outlined above for the hydrogenation ofdialkylcyclohexenes), requiring the desorption of dialkylcyclohexenes as inter-mediates. Their interpretation is much strengthened by the observation9 * J. J. Phillipson, P. B. Wells, and D. W. Gray, ref. 6(c), paper 11.3.99 P. B. Wells, Chem.and Id., 1964, 1742.lo0 L. Kh. Freidlin, E. F. Litvin, I. F. Zhukova, and B. A. Englin, Kinetika i101 L. Kh. Freidlin and E. F. Litvin, Neftekhim., 1963, 3, 326.lo2 L. Kh. Freidlin and E. F. Litvin, Neftekhim., 1964, 4, 374; L. Kh. Freidlin,103 L. Horner and I. Grohmann, Annalen, 1964, 670, 1.104 L. Kh. Freidlin and E. F. Litvin, Izvest. Akad. Nauk S.S.S.R., Otdel. khim.Nauk, 1963, 1307; I. F. Zhukova and N. A. Belikova, Neftekhim., 1964, 4, 381.105 See, for example, F. A. Dufau, F. Eschard, A. C. Haddad, and C. H. Thonon,Chem. Eng. Progr., 1964, 60, 43.106 S. Nagata, K. Hashimoto, I. Taniyama, H. Nishida, and S. Iwane, Chem.Eng. (Japan), 1963, 27, 558; 5. E. Germain, R. Maurel, Y. Bourgeois, andR. Sinn,J . Chim. phys., 1963, 60, 1219, 1227.107 Y.Orito and S. Imai, Reports Gov. Chem. Ind. Res. Inst., Tokyo, 1963, 58, 119.108 J. Volter, J. Catalysis, 1964, 3, 297.109 X. Rojek and A. Basinski, Roczniki Chem., 1963, 37, 1347.l10 Z. Sokalski and J. Podkokwa, Roczniki Chem., 1963, 37, 887.ll1 F. Hartog, J. H. Tebben, and C. A. M. Weterings, ref. 6(c), paper, 1.81.I12 S. Siegel, V. Ku, and W. Halpern, J . Catalysis, 1963, 2, 348; S. Siegel and V. Ku,R. D. Schuetz and L. R. Caswell, J. Org. Chem., 1962, 27, 486; P. N. Rylanderl 1 4 P . N. Rylander and D. R. Steele, Engelhard Ind. Tech. Bull., 1963, 3, 125;Kataliz, 1963, 4, 128.E. F. Litvin, and R. N. Shafran, ibid., p. 552.ref. 6(c), paper 1.80.and D. Steele, Engelhard Ind. Tech. Bull., 1962, 3, 91.1963, 4, 20BOND: CATALYSIS BY METALS 109of such intermediates, especially easy when rhodium-charcoal catalysts areused. From m-xylene, about 0.05% each of 2,4- and 1,3-dimethylcyclo-hexene is formed after 5 yo reduction and their concentration declines onlyslowly during the course of the experiment; from o-xylene, 007% of 1,2-dimethylcyclohexene is formed after 30% reduction and 0.05% of 2,3-dimethylcyclohexene after 5 yo reduction. Traces of deuteriocyclohexeneshave also been detected in the products of the vapour-phase reaction betweenbenzene and deuterium over ruthenium-charcoal at 60 ".lllThe relative rates of hydrogenation of benzene, toluene, and polymethyl-benzenes, alone and in binary mixtures over rhodium-alumina at 25" and1200 Ib./sq. in., in the absence of solvent, have been analysed to yield therelative strengths of adsorption of these molecules ;l15 the values relative tobenzene range from 0.70 for toluene to 0.0072 for hexamethylbenzene.Kinetics of hydrogenation of a number of polycyclic aromatic hydrocarbons(over platinum dioxide in glacial acetic acid) have been reported.ll6 Theobserved decreases in rate as the reactions proceed are attributed to inter-ference by one non-planar ring in the reaction between the remaining un-saturated rings and the surface.Other Reactions.-~'ischer-~o~sch synthesis. Work on the synthesis ofhydrocarbons by the reaction of carbon monoxide with hydrogen has con-tinued a t a diminished level since the realisation that the process can onlybe economic in the absence of cheap, naturally occurring fuels, and indeeda t the present only in South Africa is the process operated commercially.Interest continues to be shown, however, in the synthesis of normal paraffinsof very high molecular weight from carbon monoxide and hydrogen catalysedby ruthenium suspended in water or a hydrocarbon.l17 Molecular weightsup to lo5 are obtained when the reaction is conducted in nonane at 130" and1000 atrn.ll* Catalytic hydrocracking of higher hydrocarbons is responsiblefor only about 5% of the methane formed over nickel or cobalt catalysts upto about 200", and for only about 3% of that formed over iron catalysts.ll9' I Synthesis gas " prepared by gasification of coal contains sulphur com-pounds, and the effect of hydrogen sulphide on Fischer-Tropsch catalystshas therefore been examined.120 " Hiigg carbide " is more resistant to thisform of poisoning than is the reduced oxide, and &-Fe,N is even more resistant.The Temkin-Pyzhev equationhas been found valid for describing the rate of synthesis as a function ofreactant and product pressures over a triply promoted iron catalyst in therange 370495' and 150-310 atm.; a reactor operating under almostisothermal conditions was used.lZ1 Chimisorption of nitrogen on to anon-uniform surface was believed to be rate-determining, and a change inactivation energy between 330" and 370" was detected. The rate of synthesisover doubly promoted iron has been studied at sub-atmospheric pressuresfor a broad range of ammonia concentrations ;122 the Temkin-Pyzhevequation, of course, fails when the ammonia concentration is zero, underwhich conditions a simple bimolecular power rate law is adequate. Aniron-cobalt alloy containing 26% of cobalt is some three times more activeat 475" than a 6% cobalt alloy, but one containing 50% of cobalt is muchless active.123 Kinetics of the synthesis under plant conditions have beenreviewed,124 and the reactivity of chemisorbed nitrogen has been examined.125The kinetics of decomposition of ammonia over filings of several metalshave been measured, and the following activation energies recorded :l26 Cu ,44; Ni, 52; Co, 53; and Zr, 63 kcal.mole.-1. Rates were correlated withinteratomic distances and d- bond character. Charged species emitted froma platinum wire in the act of decomposing ammonia have been detectedmass-spectrometrically, NH4+ being formed at temperatures as slow as500 " .I27There is a welcome tendency towards the wider measure-ment of metal areas of supported metal catalysts, hence enabling speci$creaction rates to be determined ; this tendency is exemplified by three paperstreating the hydrogenolysis of ethane over platinum 128 and nickel 129, 13*catalysts. Heating nickel-silica in air to various temperatures gives, afterreduction, catalysts whose metal areas (measured by chemisorption of hydro-gen) range between about 4 and 13.5 m.Zg.-l. Rates of hydrogenolysis ofethane in a differential-flow reactor are proportiona,l to the metal areas, andorders and activation energies are invariant .l29 Specific activities of nickel onvarious supports are: SiO,, 15.5 x 10-5; Also3, 8.25 x Si0,-A1,O3,0.29 x 10-5 (moles of C2H, hr.-Im. -2 of Ni a t 191"); activation energiesand orders are again almost the same in each case. 130 However, platinum-silica and -alumina show similar rates and orders, but different activationenergies (respectively 54 and 31 kcal.mole-l).128 The case for a specificinteraction between metal and support is advanced, but evidently differentmetals respond differently to the same situation. This reaction has alsobeen examined with a ruthenium-silica ~ata1yst.l~~This reaction was formerly much usedas a means of assessing electronic factors in metal catalysis,3 but a growingawareness of its mechanistic complexity has caused it to be less used of late.In common with most catalytic reactions, the more deeply it is inquiredinto, the more complicated the mechanism seems to be. A valuable review 132summarises recent work. A useful aid in establishing mechanisms is thekinetic isotope effect.133 Rates of decomposition of H*CO,D, D*CO,H, andD*CO,D have recently been measured over copper, silver, gold and palladium,and the results have enabled some possible mechanisms to be excluded whilenot firmly establishing any other.134The principalreactions occurring in the catalytic re-forming of petroleum are skeletalisomerisation, dehydrogenation, and cyclisation ;135 the outlines of themechanisms involved are well understood. A number of studies of thereactions of pure hydrocarbons on silica- or alumina-supported metals havebeen reported ; these include cyclohexane dehydrogenation over nickel,136ruthenium,l37 and palladium and palladiurn-~ilver.~~8 The reactions ofmethylcyclopentane ,139 n- hept ane ,14 O alkylbenzenes,141 and other hydro -carbons l42 on platinum-alumina have been studied. The isomerisation ofany hexane isomer over platinum-alumina at 300" affords the other twoisomers in the same ratio as is given by the hydrogenolysis of methylcyclo-pentane, suggesting that a common (possibly cyclic m bonded) intermediateis involved.143Among the most interesting developments in dual-function catalysis isthe discovery that it is not necessary to have the two functions on the sameparticle.1" Weisz and his associates have shown 144 that platinum-silicaadmixed with silica-alumina gives isomerisation rates with n-heptane ashigh as those given by platinum on silica-alumina. The proposed interpreta-tion involves interparticle migration of reactive species (which in this systemwould be the heptenes), and classical diffusion theory shows that reasonablecyclisation rates would result from mixed particles of 1 ,u diameter if thepartial pressure of the migrating intermediate is only 10-7 atm. The mixedparticles can be in pellet form or preferably used in a fluidised bed. Thistechnique has obvious advantages in that it permits the rapid variation ofmetal and acid functions. Evidence suggesting interparticle migration hasbeen obtained from heat- and mass-transfer calculations,145 and cyclohexenehas been detected as a primary product in the dehydrogenation of cyclo-hexane over platinum-alumina at 520" when very high space velocitiesDehydrogenation of hydrocarbons and petroleum re-forming.The activity of the catalyst for the furtherdehydrogenation to benzene can be selectively poisoned by t-butyl mercaptanor by pyridine, and yields of cyclohexene of up to 18% are reported.Increase of platinum crystallite size in platinum-alumina caused bysintering has been quantitatively related to a loss of dehydrocyclisationactivity and an increase in isomerisation activity.147 Partial replacementof Ca2+ in calcium Y zeolite by a cationic platinum complex, [Pt(NH,),I2+,gives after reduction a catalyst resistant to poisoning by thiophen ; impregna-tion of the zeolite by hydrogen hexachloroplatinate leads to a readilypoisoned catalyst .l48Oxidation. Surprisingly little work is reported on metal-catalysedoxidations. Interest is still shown in the silver-catalysed oxidation ofethylene to ethylene oxide, with particular emphasis on means of improving~e1ectivity.l~~ The catalytic oxidation of ethylene and other olefins has beenthoroughly studied by using evaporated platinum and palladium hlms.l5oPlatinum films were active between 5" and loo", the products being carbondioxide and water only; however, some methyl t-butyl ketone was formedfrom t-butylethylene over palladium. Rhodium and tungsten flms wereless active. The reactions of oxygen with adsorbed carbon monoxide andof carbon monoxide with adsorbed oxygen on nickel and palladium filmshave been examined.lS1Much work has been reported on the electrochemical oxidation of hydro-carbons, carbon monoxide, and other oxygen-containing molecules inconnexion with their possible use in fuel cells, but it is impossible to reviewthis work here. Such, however, is the importance of catalysed reactionsproceeding on electrode surfaces that the term '' electrocatalysis " has beencoined to describe the phenomenon.l5l We may expect to hear much moreof it in the future.146 V. Haensel, G. R. Donaldson, and F. J. R i d , ref. 6(c), paper 1.9.147 H. J. Maat and L. MOSCOU, ref. 6(c), paper 11.5.148 J. A. Rabo, V. Schomaker, and P. E. Picked, ref. 6(c), paper 11.4.160 W. R. Patterson and C. Kemball, J . Catdyeis, 1963, 2, 465.1 5 1 W. T. Grubb, Nature, 1963, 198, 883.L. G. Nault, D. W. Bolme, and L. N. Johanson, Id. and Eng. Chem. (ProductRes. and Development), 1962, 1, 285

ISSN:0365-6217    

DOI:10.1039/AR9646100007

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

INORGANIC CHEMISTRY1. INTRODUCTIONBy A. K. Holliday and D. Nicholls(The Doman C h i a t v - y Laboratom'es, The U n k d t y of fiverpool.)THE yearly increase in the number of papers continues, and again muchof the work reported has been concerned with compounds containing organicgroups or ligands. The year has been marked by steady progress ratherthan by spectacular advances. Among the typical elements, the chemistryof the carboranes and other polyboron ring compounds continues to develop,as does the chemistry of organotin compounds; many new compounds con-taining two or more linked sulphur atoms have been prepared. Progressin organometallic chemistry has not been confmed to the synthesis andstructure determination ; in addition there has been considerable extensionof the well-known cases in which an organometallic compound is used toobtain an organic molecule that may be difficult, if not impossible, tosynthesise by other routes.Structural interest in cyclopentadiene-metaland related compounds is growing, particularly in those which do not havecylindrical symmetry and do not contain rings with equidistant carbonatoms. The chemistry of compounds containing metal-metal bonds hasattracted much interest, and a separate treatment of this topic has thereforebeen included in section 4.Advances in methods of structural elucidation have greatly increasedthe possibility of identifying and structurally charactensing reaction pro-ducts which are difficult or impossible to separate from the reaction mixture.Thus, combined structural and statistical studies of arsenic(II1) oxide andchloride mixtures have been used to obtain evidence for the existence andstructures of all possible (poly)arsenic(m) oxide halides, without separationor isolation, and similar methods have been applied for alkoxyarylborons,polyalkylsiloxanes, and polyhalogenophosphorus( 111) dia1kylamides.l Suchstudies, while not necessarily implying that isolation is an unnecessary pre-requisite for identification, are clearly of value when labile products, whichmay re-arrange during separation, are formed.Continued expansion in the number of publications devoted to reviewsappears to have produced no increase in general reviews, but many morespecialised reviews (which are referred to under the element or group con-cerned) have appeared.General reviews include those on reactions inelectric discharges,2 order-disorder phenomena in inorganic ~hemistry,~H. K. Hofmeister and J. R. van Wazer, J. Inorg. Nuclear Chenz., 1964, 26, 1201,1209; K. Moedritzer and J. R. van Wazer, J. Amer. Chem. SOC., 1964, 86, 802; J. R.van Wazer, K. Moedritzer, and D. W. Matula, ibid., p. 807; J. R. van Wazer andL. Maier, ibid., p. 811; M. D. Rausch, J. R. van Wazer, and K. Moedritzer, ibid.,p. 814.A. S. Kana'an and J. L. Margrave, Adv. Inorg. Chem. Radiochem., 1964, 6, 143.R. Collongues, Ann. Chim. (Prance), 1963, 8, 395114 INORGANIC CHEMISTRYfluorocarbon derivatives of metals? and a further part of a survey of in-organic heterocycles.5 Two elementary but interesting reviews havebeen concerned with thk ligand-field 6 and molecular-orbital 7 theories oftransition-metal complexes ; the review of molecular-orbital theory is timelyin view of the greater use now being made of such calculations in this field.A new journal 8 concerned with organometallic compounds appeared atthe end of 1963, and the first volume of a series on preparative inorganicreactions has been p~blished,~ as well as a further supplement lo (to Vol.VIII) of Mellor’s ‘‘ Comprehensive Treatise ”.4P.M. Treichel and F. G. A. Stone, Adv. Organmetallic Ch., 1964, 1, 143.TH. B. Gray, J . Chem. Educ., 1964, 41, 2.@ “ Preparative Inorganic Reactions ”, ed. W. L. Jolly, Vol. I, Interscience Publ.,10 “ Comprehensive Treatise on Inorganic and Theoretical Chemistry ”, Vol.VIII,H. Garcia-Fernandez, Bull. Soc. chim. France, 1964, 677.F. A. Cotton, J . Chem. Educ., 1964, 41, 466.J . Organmetallic Chem., 1963, 1.Inc., New York, 1964.Supplement 1 : Nitrogen, Part I. Longmans, London, 19642. THE TYPICAL ELEMENTSBy A. K . Holliday(The Donnan Chemistry Laboratm'm, The University of Liverpool.)Group 0.-Advances in the study of noble-gas compounds have not beenso spectacular as last year, but the field has been well reviewed in booksand articles.2 A krypton difluoride-antimony pentafluoride complex,KrF,,ZSbF,, similar to the previously reported XeF2,2SbF,, has been pre-pared, and is more stable than the parent krypton difl~oride.~ Aqueoushydrolysis of krypton tetrafluoride gives a low yield of an acid of uncertaincomposition, appropriately and temporarily called " cryptic acid," but thebarium salt appears to be BaKrO, and is stable up to 50°.4Passage of a glow discharge through a mixture of xenon, fluorine, andsilicon tetrafluoride gives a substance of approximate composition Xe,SiF,,and an analogous experiment with antimony pentafluoride gives XeSbF,which differs in properties from the XeF,,2SbF5 already menti~ned.~ I nneutral or acid solution, xenon difluoride appears to exist as undissociatedmolecules, forming no complexes with an excess of fluoride ion; in alkalinesolution, the +2 oxidation state is unstable?XeF, + 20H- --+ Xe + *O, + 2F- + K,OXenon tetrafluoride reacts with acetic acid, and with boron trifluoride, toform solid compounds of unknown composition ;7 xenon hexafluoride withboron trifluoride and arsenic pentafluoride gives white, solid 1 : 1 adducts.8The formation with sodium fluoride of an addition compound, Na,XeF,,which dissociates again below loo", permit,s xenon hexafluoride to beseparated from other fluorides, and its purification to give m.p.47.7 O rfi 0.2 O ;the corresponding compounds, Cs2XeF8 and Rb,XeF8, are both stable upto 400" and are therefore the most stable xenon compounds yet k n 0 ~ n . 9Hydrolysis of either the tetrafluoride or the hexafluoride yields the mole-cular species, XeO,, in aqueous solution. This has strongly oxidising pro-perties, but is otherwise stable; above pH 10.5, HXe0,- ions are formed, andin strongly basic solution disproportionation to give xenon and xenon( VIII)l G.J. Moody and J. D. R. Thomas, " Noble Gas:: and their Compounds ",Pergamon Press, Oxford, 1964; Noble Gas Compounds , ed. H. H. Hyman, Uni-versity of Chicago Press, Chicago, 1963.2A. Feltz, 2. Chem., 1964, 4, 41; G. Gnauck, ibid., p. 186; R. Hoppe, Angew.Chem., 1964, '76, 455; H. H. Hyman, Science, 1964, 145, 773; A. B. Neiding, UspekhiKhim., 1963, 32, 501 (224)*; J. Serre, Bull. SOC. chim. France, 1964, 671.A. G. Streng and A. V. Grosse, Science, 1964, 143, 242.E. H. Appelman and J. G. Malm, J . Arner. Chem. SOC., 1964, 86, 2297.E. Schumacher and M. Schaefer, Helw. Chim. Acta, 1964, 47, 150.H. Selig, Science, 1964, 144, 537.I. Sheft, T. M. Spittler, and F.H. Martin, Science, 1964,145, 701; R. D. Peacock,8H. Selig and R. D. Peacock, J. Amer. Chem. SOC., 1964, 86, 3895.SA. F. Clifford and G. R. Zeilenga, Science, 1964, 143, 1431:H. Selig, and I Sheft, Proc. Chem. SOC., 1964, 285.* Throughout the inorganic sections, numbers in parentheses at the end of references to Russian periodicalsindicate the corresponding page in the English or U.S. translation116 INORGANIC CHEMISTRYionic species occurs. The latter exist as perxenate, Xe0,4-, ions, but inless basic solution species, HXe063- and H2Xe0,2-, are formed, and inacid solution rapid evolution of oxygen and reversion to the +6 oxidationstate occurs.1o The perxenates are powerful oxidising agents [e.g., oxidising&(a) to Mn(vn)]; the structures of sodium perxenate octa- and hexa-hydrate, and of potassium perxenate nonahydrate, have been found tocontain regular Xe06,- octahedra with extensive interconnecting hydrogenbonding.ll Reaction of a perxenate with sulphuric acid gives the xenon(=)oxide, XeO,, and the infrared spectrum suggests a tetrahedral structureanalogous t o that of OsO, or I04-.12 A comparison of the Mossbauerspectrum of XeF, and that obtained from the ,&decay product of K1291C14,H,0(where r291 ---+ 12@Xe) gives evidence for the existence and planar configur-ation of XeC1,.13 The nature of the bonding in the xenon fluorides hasbeen discussed in terms of the various models already used; the significanceof a central atom of large size and relatively low ionisation energy unitedwith ligands of small size and high electron affinity is stressed.14Group 1.-Reaction of ethyl-lithium with either iodomethane or dimethyl-meruury can produce a mixed ethylmethyl-lithium compound ; reductionof the ethyl content to <25% gives some of the tetramer, (MeLi),, withfour lithium atoms at the corners of a tetrahedron and a methyl groupabove the centre of each face, forming four-centre bonds with the threeadjacent lithium atoms.l5 High-frequency titration of a lithium akylwith diethyl ether shows the stoicheiometry :(R2Li2)n + nEt,O ---+ n[(R2Li2)OEf2]suggesting that two electrons are required to satisfy the deficiency in eachdimer unit.16 However, dielectric constant and freezing-point measurementson ethyl-lithium-triethylamine mixtures suggest that, at low concentrationof base, co-ordination to an intact alkyl-lithium hexamer occurs, with dis-sociation to a dimer, (RLi),(base),, as base concentration increases.17 Thehighly reactive and electrophilic trichloromethyl-lithium has been preparedby addition of bromotrichloromethane to an ethereal solution of methyl-lithium.18 Phase-rule studies have shown the existence of a hydratedlithium polyiodide, formulated as 2Li(H,O),fI,2-.l9 An electron spinreaonance spectral study of the reaction of atomic sodium with ice at 77'9:11 J.A. Ibers, W. C. Hamilton, and D. R. MacKenzie, Inorg. Chem., 1964, 3, 1412;A. Zalkin, J. D. Forester, and D. H. Templeton, ibid., p. 1417; A. Zalkin, J. D. Forester,D. H. Templeton, S.M. Williamson, and C. W. Koch, J . Amer. Chem. SOC., 1964, 86,3569.12 J. L. Huston, M. H. Studier, and E. N. Sloth, Science, 1964, 143, 1162; H. Selig,H. H. Claassen, C. L. Chernick, J. G. Malm, and J. L. Huston, ibid., p. 1322.lS G. J. Perlow and M. R. Perlow, J . Chem. Phys., 1964, 41, 1157.l4 C. A. Coulson, J . Chem. SOC., 1964, 1442; J. Bilham and J. W. Linnett, Nature,l c E. Weiss, Chem. Ber., 1964, 97, 3241; E. Weisa and E. A. C. Lucken, J. Organo-l6 F. A. Settle, M. Haggerty, and J. F. Eastham, J . Amer. Chem. SOC., 1964, 86,1 7 T. L. Brown, R. L. Gerteis, D. A. Bayfus, and J. A. Ladd, J . Amer. Chem.18 W. T. Miller, Jr., and D. M. Whalen, J . Amer. Chem. SOC., 1964, 86, 2089.1s G. H. Cheeseman and E. K. NU=, J . Chem. SOC., 1964, 2265.E. H.Appelman and J. G. Malm, J . Amer. Chem. Soc., 1964, 86, 2141.1964, 201, 1323.metaEEic Chem., 1964, 2, 197.2076.SOC., 1964, 86, 2135HOLLIDAY: THE TYPICAL ELEMENTS 117indicates that the blue colour is due to a trapped electron in a tetrahedralenvironment of four protons from neighbouring water molecules;20 theabsorption spectra, solubilities, and conductances of alkali metals (M) inethylenediamine have been interpreted in terms of three species-solvatedelectron, covalent metal h e r , and (solvated molecule-ion M2+ + trappedelectron).21 Formulation of " alkali carbonyls " as acetylenediolates (atlow temperatures) has been confirmed; the C-0 and C-C distances inRbO*CkC*ORb are 1-27 and 1-20 A, respectively.22 Reaction of caesiurnsuperoxide with an oxygen-ozone mixture yields czesium ozonide, CsO,,which can be extracted with liquid amm0nia.~3 The chemistry of organo-sodium and -potassium compounds has been reviewed.24Group IL-The alkylberyllium hydride (1) is obtained as one productwhen trimethylamine is added to an ethereal solution containing methyl,beryllium, and hydride in the ratio 4:3:2; the Be-H-.Be bridges resistsplitting by donor molecule^.^^ Reaction of diethylberyllium, or of itstrimethylamine adduct, with methylhydrazines gives a variety of productse.g., Be(MeNNH,), and polymers (EtBe*MeN*NH2),.26 The structure ofdi( cyclopentadieny1)beryllium has two plane-parallel, staggered rings andis interpreted in terms of ionic bonding.27 Reaction of beryllium nitratewith pentane-2,4-dione in acetic anhydride gives simultaneous chelationand nitration of the chelate a t the 3-position, and reduction then yieldsdi- (3-aminopentane-2 ,ddiono) beryllium.28 Adducts of normal berylliumacetate with amines, and of beryllium halides with ethers, have been pre-pared; the etherates BeX2,2Et20 (X = C1, Br) lose 1 mol. of alkyl halidewhen heated and form the polymeric alkoxide halides, (XBe-OEt),.29 Thestructure [Be40(C0,),16- has been con&med for the " carbonatoberyllates "both in the solid state and in solution.30 The existence of fluoroberyllates,(RO*BeF,)2- (R = alkyl or H) is doubtful, but polymeric compounds ofempirical formulae K,[BeF,O] and K4[Be[Be,F60] have been prepared bydecomposition of oxalatofluoroberyllium compounds.s1 Magnesium hydride2o J.E. Bennett, B. Mile, and A. Thomas, Nature, 1964, 201, 919.21R. R. Dewald and J. L. Dye, J . Phys., Chem., 1964, 68, 121, 128, 135.22 W. Buchner and E. Weiss, Helv. Chim. Acta, 1964, 4'7, 1416; E. Weiss andW. Buchner, Z . anorg. Chem., 1964, 330, 251; cf. Ann. Reports, 1963, 60, 180.23 I. I. Vol'nov and V. V. Matveev, Izvest. Akad. Nauk S.S.S.R., Otdel. khim.NuuE, 1963, 1136 (1040).24 M. Schlosser, Angew. Chem., 1964, '76, 124, 258.2 5 N. A. Bell and G. E. Coates, Proc. Chem. SOC., 1964, 59.26 N. R. Fetter, Canad. J . Chem., 1964, 42, 861.27 A. Allmeningen, 0. Bastiansen, and A. Haaland, J . Chern. Phys., 1964, 40, 3434.28 R. M. Klein and J. C. Bailar, Jr., Inorg. Chem., 1963, 2, 1187, 1190.29 A.K. Tyulenev, A. I. Grigor'ev, and A. V. Novoselova, Z h w . neorg. Khim.,1963, 8, 251 (127); N. Ya. Turova and A. V. Novoselova, ibid., p. 525 (273); N. Ya.Turova, N. S. Sitdykova, A. V. Novoselova, and K. N. Semenenko, ibid., p. 528 (275);K. N. Semenenko and N. Ya. Turova, ibid., p. 2093 (1093).30 J. Faucherre and F. Fromage, Bull. SOC. chim. France, 1964, 1244.31 L. Kolditz and K. Bauer, 2. anorg. Chem., 1963, 325, 196118 INORGANIC CHEMISTRYhalides have been prepared by reduction of Grignard reagents with hydrogenunder pressure; reaction of, e.g., MgHCl with aluminium chloride gives thehydride, AlH2Cl.32In dimethylmagnesium, the metal atoms are connected by pairs ofmethyl bridges, with an approximately tetrahedral arrangement of fourmethyl groups around each magnesium at0m.~3 E'urther methods for thepreparation of alkylmagnesium alkoxides are reported ; reaction of n-butyl-magnesium isopropoxide with propan-2-01 gives magnesium isopropoxidein an initially rubber-like, metastable form.34 Studies of the systemLiH-MH, (M = Ca, Sr, Ba) have led to identification of a ternary perovskitephase, LiMH3.3jBooks have appeared dealing with boron hydridesand organoboron c0mpounds.3~ Crystalline cc-rhombohedra1 (red) boronhas been obtained by decomposition of boron tri-iodide on tantalum wireat about 1000°.37 Diborane has been obtained by high-pressure hydro-genation of boric oxide in presence of aluminium and aluminium chloride,S8by low-pressure hydrogenation of boron monoxide (prepared from boroncarbide),39 and (pure) by reaction of orthophosphoric acid with potassiumb or oh y dride .40Distillable borohydrides of some lanthanides are reported ;41 the ionBH3*OH- has been identified spectroscopically as a likely intermediate inthe hydrolysis of sodium b0rohydride.4~ Improved methods for the pre-paration of ammonia-borine have been gi~en,4~ and diaminoborines can beobtained from reaction of the appropriate diarnine monohydrochloride withsodium borohydride.44 Compounds of the type [H,B(base),]+X- havebeen prepared; the base can be an amine or a tertiary phosphine or arsine([H,B(NR,),+ compounds are very stable to hydrolytic or oxidative attack} ,while X- can be (e.9.) halide-, 4(B12H122-), PF,-, or N,-.45 A re-investiga-tion of the reaction of boron trichloride with diborane suggests that the pro-ducts, B,H,Cl and BHCl,, are stable only in an equilibrium mixture,46 andGroup III.-Boron.8PT.N. Dymova and N. G. Eliseeva, Zhur. neorg. Khim., 1963, 1674 (820).as E. Weiss, J . Organornet. Chem., 1964, 2, 314.34D. Bryce-Smith and B. J. Wakefield, Proc. Chern. SOC., 1963, 376; J . Chem.Soc., 1964, 2483; cf. Ann. Reports, 1963, 60, 181.35 C. E. Messer, J. C. Eastman, R. G. Mers, and A. J. Maeland, Inorg. Chem.,1964, 3, 776.86 W. N. Lipscomb, " Boron Hydrides ", Benjamin, New Yo$, 1963; H. Steinberg," Organoboron Chemistry: Vol. I. B-0 and B-S Compounds , Interscience Publ.,Inc., New York, 1964.37 E. Amberger and W. Dietze, 2. anorg. Chem., 1964, 332, 131.38 T.A. Ford, G. H. Kalb, A. L. McClelland, and E. L. Muetterties, Inorg. Chem.,39 L. Barton and D. Nicholls, Proc. Chem. SOC., 1964, 243.40 13, J. Duke, J. R. Gilbert, and I. A. Reed, J. Chem. SOC., 1964, 540.4 1 K. Rossmanjth, Monatsh., 1964, 95, 1424.42 J. A. Gardiner and J. W. Collat, J. Arner. Clzem. SOC., 1964, 86, 3166.4a V. P. Sorokin, B. L. Vesnina, and N. S. Klimova, Zhw. neorg. Khim., 1963,8, 66 (32); S. G. Shore and K. W. Boddeker, Inorg. Chem., 1964, 3, 914.4 4 J. Goubeau and H. Schneider, Anizalen, 1964, 675, 1.O5 H. Noth, H. Beyer, and H.-J. Vetter, Clzern. Ber., 1964, 97, 110; N. E. Millerand E. L. Muctterties, J. Amer. Chem. SOC., 1964, 86, 1033; N. E. Miller, B. L. Chamber-land, and E. I;. Muetterties, Inorg. Chem., 1964, 3, 1064.46 J.V. Kerrigan, Inorg. Chem., 1964, 3, 908; cf. Ann. Reports, 1963, 60, 183.1964, 3, 1032HOLLIDAY: THE TYPICAL ELEMENTS 119the IH and 1lB nuclear magnetic resonance spectra of bromodiborane confirmthe view that the bromine atom is terminal and not Furtherstudies of tetrabarane carbonyl have been made; it may be prepared fromtetraborane-I0 or pentaborane-11, and reaction with ethylene “ fixes ” thecarbon monoxide as (C,H,),B,H,(CO), but the structure of the parentcarbonyl is still ~ncertain.~, In ether solutions of tetraborane-10, cleavageto form, initially, (ether),BH,+ and B,H,- ions occurs; the anion is stablein presence of BH,- ions, but otherwise loses a hydride ion and forms anether-B 3H7 adduct .49Halogenoalkylation of pentaborane-9 yields two new derivatives, di-( 1 -pentaboryl)methane, ( B5H8),CH2, and (dichlorobory1)-l-pentaboryl methane,B5H,*CH,*BC1,.50 Methanolysis of the 1 : 1 adduct of pentaborane-9 withNNN’N’-tetramethylethylenedarnine (TMED) yields B4H,,TMED,S1 andreaction of the pentaborane-9-trimethylamine adduct with diborane pro-ceeds by incorporation of a NH, group in the adduct before liberationof Me,N-BH,.52 Ethylpentaborane-11 is formed from pentaborane-11either by exchange reactions with ethyldiboranes or by reaction withethylene. 53 Hexaborane- 10 (obtained on hydrolysis of magnesium boride)and hexaborane-12 (obtained by other boron hydride interconversions)have been separated in improved yields by gas chr~matography,~~ and thenew hydride, BsH12, with a B, unit as an icosahedral fragment, has beenobtained by passage of an electric discharge through a mixture of diboraneand pentaborane-9.5 5 Octachlorononaborane-9, B,C18H, has been pre-pared by pyrolysis of H2B,,C1,,,H20; it is readily reduced in aqueoussolution to the anion, BgC1,H2-.5s The nonaboron nonachloride, BsClg,prepared by thermal decomposition of diboron tetrachloride, may be thecorresponding nonachlorononaborane.57The chemistry of decaborane-14 and its derivatives has been reviewed,58and the thermal decomposition of 2-ethyldecaborane has been studied.59The first stable, optically active boron compound in which the molecularasymmetry resides on the boron, 2,7(8)-Me,NoB,,H,.C0, has been syn-thesised. 6o Further substituted decaboranes, e.g., (MeCN),B,,H,,Br and47 D.F. Gaines and R. Schaeffer, J. Phys. Chem., 1964, 68, 955.48 J. R. Spielman and A. B. Burg, Inorg. Chem., 1963, 2, 1139.49 R. W. Parry, R. W. Rudolph, and D. F. Shriver, Inorg. Chrn., 1964, 3, 1479;R. Schaeffer, T. Tebbe, and C. Phillips, Inorg. Chem., 1964, 3, 1475.50 E. R. Altwicker, G. E. Ryschkewitsch, A. B. Garrett, and H. H. Sisler, Inorg.Chest&., 1964, 3,. 454.51 N. E. Miller, H. C. Miller, and E. L. Muetterties, Inorg. Chem., 1964, 3,866.5 2 T. Onak, R. P. Drake, and I. W. Searcy, Chem. and I d . , 1964, 1865.53 R. G. Maguire, I. J. Solomon, and M. J. Klein, Inorg. Chem., 1963, 2, 1133;5 4 P. L. Timms and C. 8. G. Phillips, Inorg. Chem., 1964, 3, 297; C. A. Lutz, D. A.55 R.E. Enrione, F. P. Boer, and W. N. Lipscomb, J. Amer. Chern. Xoc., 1964,6 6 J. A. Forstner, T. E. Haas, and E. L. Muetterties, Inorg. Chem., 1964, 3,57 A. G. Massey and D. S. Vrch, Nature, 1964, 204, 877.58 M. F. Hawthorne, Adv. Inorg. Chem. Radiochem, 1963, 5, 308.59 F. W. Emery, P. L. Harold, and A. J. Owen, J . Chem SOC., 1964, 426.6 o W. R. Hertler, J . Amer. Chem. Soc., 1964, 86, 2950.I. J. Solomon, M. J. Klein, R. G. Maguire, and K. Hatton, ibid., p. 1136.Phillips, and D. BZ. Ritter, ibid., p. 1191.86, 1451.155120 INORGANIC CHEMISTRY(Et2S)2Bl,,HllBr, have been prepared,G1 and a decaborane triammoniate,prepared by direct addition in benzene, is formulated62 asThe ion, B,,H,,-, is formed as an intermediate by attack of borohydrideion on decaborane-14; it loses hydrogen to give Remarkableprogress has been made in the synthesis of anions of this type from diborane,by reactions such as2NaBH4 + 5B2H6-Na2B12H12 + 13Hsin which the anion B3H,- seems to be an important intermediate.64 Theions, B,2H1,2- and B1J3102-, show notable kinetic stability and have aderivative chemistry comparable with that of aromatic hydrocarbons ; thus,as well as forming salts such as [Cr(NH3)6][B12Hl,]3,7H20,65 they canundergo halogenation,66 aminationY67 alkylation by oleh addition ,6*dimofisation and ~arbonylation,~~ and oxidation ;70 in the last case, couplingcan occur thus (L = substituent):With L = H, under suitable oxidation conditions, the ion B2,H182- isformed, and has been reported (1962) to exist in two isomeric forms; it nowappears that one form is, in fact, the anion 7 1 of the double salt[Et3~1S[B20%) *-, (B20HlD) 5-1The hydride, B2,HN, reported last year, has been shown to consist of twoB1oH14 cages joined at the open faces with removal of all hydrogen atomsfrom bridges and from the four joining boron at0ms.7~ The structures ofthe boron hydrides have been reviewed.73The appearance of a large group of papers on carboranes in late 1963necessitated a system of nomenclature; one system uses the name of theappropriate polyborane prefixed by '' clovo " to indicate a non-hydrogen-bridged boron cage, and an additional prefix to indicate the position andnumber of carbon atoms " replacing " cage boron atoms; thus, C2BloH12NR,+[BlOHl ,*=, ,=,I -.EttN.%&a&- --+ B2,Hl6L2 + 2H+ + 48-61T.L. Heying and C. Naar-Colin, Inorg. Chem., 1964, 3, 283.62 J. Williams, R. L. Williams, and J. C. Wright, J. Chem. SOC., 1963, 5816.63 R. Schaeffer and T. Tebbe, Inorg. Chem., 1964, 3, 1638.6 4 H. C. Miller, N. E. Miller, and E. L. Muetterties, J. Amer. Chem. SOL, 1963,85, 3885; I. A. Ellis, D. F. Gaines, and R. Schaeffer, ibid., p. 3885; H. C. Miller, N. E.Miller, and E. L. Muetterties, Inorg. Chem., 1964, 3, 1456.66 E. L. Muetterties, 5. H. Balthis, Y. T. Chia, W. H. Knoth, and H. C. Miller,Inorg. Chem., 1964, 3, 444.66 W. H. Knoth, H. C. Miller, J. C. Sauer, J. H. Balthis, Y. T. Chia, and E. L.Muetterties, Inorg. Chem., 1963, 3, 159.6 7 W. R. Hertler and M. S. Raasch, J.Amer. Chem. SOC., 1964, 86, 3661; W. R.HerUer, Inorg. Chem., 1964, 3, 1195.68 W. H. Knoth, J. C. Sauer, D. C. England, W. R. Hertler, and E. L. Muetterties,J . Amer. Chem. SOC., 1964, 86, 3973.139 W. H. Knoth, J. C. Sauer, H. C. Miller, and E. L. Muetterties, J. Amer. Chem.Soc., 1964, 86, 115.7 0 B. L. Chamberland and E. I;. Muetterties, Inorg. Chem., 1964, 3, 1450; cf. Ann.Reports, 1962, 59, 131.71M. F. Hawthorne, R. L. Pilling, P. F. Stokely, and P. M. Garrett, J. Amer.Chem. SOC., 1963, 85, 3704.7 2 R . D. Dobrott, L. B. Friedman, and W. N. Lipscomb, J. Chem. Phys., 1964,40, 866.78 G. W. Campbell, Jr., Progr. Boron Chem., 1964, 1, 167HOLLIDAY: THE TYPICAL ELEMENTS 121is a dicarbaclovododecaborane-12.74 The alternative name " barene " iaused by Russian workers.75 Most of the papers relate to the carboraneaobtained by reactions of decaborane with acetylene^;^^ these have thecage structure (2) and thermal interconversions have given two otherisomers of the parent 1,2-dicarbaclovododecaborane-12 (" ortho "), zlix.,the 1,7 (" meta " or " neocarborane ") and the 1,12 (" para ").77 Forbrevity, the formula (3a) may be used to describe the 1,2 form, becauseMelSiBlOH,,'O'c/ c - \/ s i c-c \\O/BIOHIO/O\c'PC,/' -CIP/ c-c \\o/these carboranes are characterised by a rather unreactive BloHlo cage andreactive R,R' groups.Thus, while complete chlorination to give perchloro-and perchloroneocarboranes, C,B,Cl,, is possible, 7 6 3 7 * the B,,H,, part ofthe structure remains unattacked when R and/or R' are replaced by Li,75, 79,VaR.Adams, Inorg. Chem., 1963, 2, 1087.75 L. I. Zakharkin, Tetrahedron Letters, 1964, 2255; L. I. Zakharkin, V. I. Stanko,and Yu. A. Chapovsky, Izvest. Akad. Nauk S.S.S.R., Ser. Ichim., 1964, 582.7 6 T. L. Heying, J. W. Ager, Jr., S. L. Clark, D. T. Mangold, H. L. Goldstein,M. Hillman, R. J. Polak, and J. W. Szymanski, Inorg. Chem., 1963, 2, 1089; M. M.Fein, T. Bobinski, N. Mayes, N. Schwartz, and M. S . Cohen, ibid., p. 1111.7'D. Graftstein and J. Dvorak, Inorg. Chem., 1963, 2, 1128; H. Schroeder andG. D. Vickers, ibid., p. 1317; S. Papetti and T. L. Heying, J . Amer. Chem. SOC., 1964,86, 2295.78 H. Schroeder, T. L. Heying, and J. R. Reiner, Inorg. Chem., 1963, 2, 1092;H. Schroeder, J.R. Reiner, R. P. Alexander, and T. L. Heying, ibid., 1964, 3, 1464. '* T. L. Heying, J. W. Ager, Jr., 8. L. Clark, R. P. Alexander, S. Papetti, J. A.Reid, and S . I. Trotz, Inorg. Chern., 1963, 2, 1097122 INORGANIC CHEMISTRYNO,so CH2*MgBr,81 and HCiC. 82 These substitutions permit, in turn,formation of bis- 82 and poly-carboranes (3b),s3 carboranylalkyl ethers(e.g., 3c),84 and silylene- 85 and phosphino-carboranes (e.g., 3d, 3e).S6 Reactionof 1,2-dicarbaclovododecaborane-12 with methanolic potassium hydroxideproduces the ion, [C,B,H,,]-, and with acid this yields the dicarbaundeca-borane-13, C,B,H13; the latter on pyrolysis gives a new carborane,C2B@ll.s7 Structural examination of the carborane, C,B,,H,Cls, indicatesa nearly icosahedral arrangement for the C2B1, cage,ss and the carboraneC2B5H, has been shown to have the structure (4).S9 Heating diethylborineMe 15)with acetylene gives the alkylated 1,5-dicarbaclovopentaborane-5 (5),90 andother alkylated carboranes have been prepared from alkyborines, themechanism being considered to involve formation of R,B* radicals (whichcan be trapped as coloured adducts with a The changes occurringwhere organoboron compounds are heated have been reviewed.92 The useof tetra-alkyltin(1v) as a means of preparing dialkylborines, R,BX, has beendem~nstrated,~~ and the low-temperature oxidation of trimethylboron hasbeen re-investigated.9* Reaction of tetra-allryldiborane with methylcyanide gives, e.g. , the dialkyl( ethylideneamino)borine, (Me*CH:N*BMe,),,two isomeric forms of which have been isolated.95 Earlier work on theJ.M. Kauffman, J. Green, M. S. Cohen, M. M. Fein, and E. L. Cottrill, J . Amer.Chem. Soc., 1964, 86, 4210.M. M. Fein, D. Grafstein, J. E. Paustian, J. Bobinski, B. M. Lichstein, N. Mayes,N. N. Schwartz, and M. S . Cohen, Inorg. Chem., 1963, 2, 1115.J. A. Dupont and M. F. Hawthorne, J . Amer. Chem. Soc., 1964, 86, 1643.83 J. Green, K. Mayes, and M. S . Cohen, J . Polymer Sci. Part A , General Papers,1964, 2, 3113; J. Green, N. Mayes, A. P. Kotloby, and M. 8. Cohen, ibid., p. 3135. ** D. Grafstein, J. Bobinski, J. Dvorak, J. E. Paustian, H. F. Smith, S. Karlan,C. Vogel, and M. M. Fein, Inorg. Chem., 1963, 2, 1125.86 S. Papetti and T. L. Heying, Inorg. Chem., 1963, 2, 1105; S.Papetti, B. B.Schaeffer, H. J. Troscianiec, and T. L. Heying, ibid., 1964, 3, 1444; S. Papetti andT. L. Heying, ibid., p. 1448.R. A. Wiesboeck and M. F. Hawthorne, J . Amer. Chem. SOC., 1964, 86, 1642;F. Tebbe, P. M. Garrett, and M. F. Hawthorne, ibid., p. 4222.86R. P. Alexander and H. Schroeder, Inorg. Chem., 1963, 2, 1107.88 J. A. Potenza and W. N. Lipscomb, J . Amer. Chem. SOC., 1964, 86, 1874.8 g R. A. Beaudet and R. L. Poynter, J . Arner. Chem. SOC., 1964, 86, 1258.91 R. Koster and G. Benedikt, Angew. Chem., 1964,76,650; R. Koster, G. Benedikt,92 R. Koster, Angew. Chem., 1963, 75, 1079.93 W. Gerrard, E. F. Mooney, and R. G. Rees, J . Chern. Sec., 1964, 740.9 p L. Parts and J. T. Miller, Jr., Inorg. Chem., 1964, 3, 1483.95 J .E. Lloyd and K. Wade, J . Chem. SOC., 1964, 1649.R. Koster and G. W. Rotemund, Tetrahedron Letters, 1964, 1667.and H. W. Schrotter, ibid., p. 649HOLLIDAY: THE TYPICAL ELEMENTS 123mechanism of the addition of nitric oxide to trialkylborine has been sub-stantially c0nfirmed.~6 The properties of some coloured bipyridylyl-diphenylboronium salts, e.g., [Ph,( bipy)B]Cl, have been investigated ; someof these are insoluble in water.97 Reaction of phenylboron dichloride withalkali metals gives polymers (PhB), (n = 9-12); these take up ammoniato give polymers, [(PhB)2NH3],.9* Reaction of sodium acetylides, NaCiCR(R = H, alkyl, or aryl) with trialkoxy- or trihalogeno-borines yield the veryunstable trialkynylborines, (RCiC),B, but these can be stabilised by donormolecules ;QQ however, reaction of, e.g., LiiCPh with diphenylboron chloridegives the stable PhCiC*BPh2.lo0 Reaction of diborane with acetylene in1,2-dimethoxyethane yields polymers containing-[CH,I,*~.[CH,~,*B.[CH,~- 1units which 1vit.h boron trihalides yield X2B*CH2*CH,-BX2 (X = F orThe papers read at a conference on boron-nitrogen chemistry havebeen published in book form,lo2 and developments in the chemistry ofaminoboranes have been reviewed.lO3 The highest occupied orbitals inaminoborine, BH,*NH, and borazine are computed to be cr-type; contraryto the formal representation of the B-N bond as +N-B-, the nitrogen isthe more negative.lW An examination of the C-N stretching frequency inadducts of the type MeCN,BX, shows that this is insensitive t,o variationsin X or in the force constant of the B-N bond.lO5 The first triborylamine,tri-( 1,3,2-benzodioxaborol-2-yl)amine, has been prepared ; its stability isattributed to chelation which prevents rearrangement or overcrowding atthe boron atom.106 Earlier work on aminophosphinoborines has beenextended, and bisdimethylamino-compounds such as (Me,N),B*PEt,, havebeen prepared.lO7 The dimethylaminoboron dihalides Me2N*BX2 (X = F,C1, Br, or I) have been prepared by improved methods and their infraredspectra studied ; the fluorine compound exhibits a monomer-dimer equili-brium but all the others are exclusively monomeric in the gas phase.lo8Some new B-vinylated and N-vinylated boron-nitrogen compounds, e.g.,MePhC:CH*NH*BR,) have been prepared ; the reactions of lithium azidewith dialkylaminoboron halides, (R2N),-xBCl, (R = Me or Et ; x = 1 or 2)C1) .lolB6 S . T . Brois, Tetrahedron Letters, 1964, 345; cf. Ann. Reports, 1962, 59,B7 L. Banford and G. E. Coates, J . Chern. SOC., 1964, 3564.BB E. C. Ashby and W. E. Foster, J . Org. Chem., 1964, 29, 3225.143.W. Kuchen and R.-D. Brinkmann, 2. anorg. Chem., 1963, 325, 225.loo M. F. Lappert and B. Prokai, J . Organomet. Chem., 1964, 1, 384.lol G. F. Clark and A. K. Holliday, J . 0,rgccnomet. Chem., 1964, 2, 100.lo2 " Boron-Nitrogen Chemistry ", ed. R. F. Gould, Amer. Chem. Soc., Washington,lo3 K. Niedenzu, Angew. Chern., 1964, 76, 168.lo4R. Hoffmann, J . Chem. Phys., 1964, 40, 2474.Io6 I. R. Beattie and T.Gilson, J . Chem. SOC., 1964, 2292.loeM. F. Lappert and G. Srivastava, Proc. Chem. SOC., 1964, 120.lo' H. Noth and W. Schriigle, Chern. Ber., 1964, 97, 2218; 2374; cf. Ann. Reports,Io8 A. J. Banister, N. N. Greenwood, B. P. Straughan, and J. Walker, J . Chern.1964.1962, 59, 134.Soc., 1964, 995.124 INORGANIC CHEMISTRYgive amidoborazides, (R2N)ezB(N3)z, which lose nitrogen when heated.109Investigations of the reactions of bistrimethylsilylamine and its alkali-metalsalts with boron derivatives have shown the formation of cyclic compoundssuch as (R,Si*d*BCl-), and [ (Me3Si)2N*B*N*SiMeJ2.110 The borazines(borazoles) have been reviewed,lll and numerous substituted borazines arereported, including N-halogenoalkyl- ,112 various (B,N-)methyl- and ethyl- ,113BBB-tribr~mo-ll~, B-~yclopentadienyl-,~15 NNN-trialkyl(or aryl)-BBB-trihy&oxy-,116 and various N-alkyl-B-cyano-b0razines,~17 as well as poly-borazyl compounds with ring-boron atoms linked directly,ll* through-NR- groups,11g or through - 0 - .l 2 O Further properties of the two isomersof 1,3,5-trimethylcycloborazane are reported,121 and 1,1,3,3-tetramethyl-diborazane, H,B*NMe,*BH,*NHMe,, has been obtained as a by-product inthe preparation of ( H2B*NMe2),.12Z New boron-nitrogen heterocycles havebeen obtained by reaction of substituted hydrazines with aminoborylaminesto give, e.g., compound (6), and with alkylbisdimethylaminoborines to give,I 1Re.g., compound (7) ;l23 the same borines, by transamination with am-diamines,give heterocycles of type (S).124 Several new phosphinoborines with bothlinear and cyclic structures have been r e ~ 0 r t e d .l ~ ~ The infrared spectrumof gaseous boroxine suggests a planar D3h structure similar to that of bora-log K. Niedenzu, P. Fritz, and J. W. Dawson, Inorg. Chem., 1964, 3, 626, 778;P. I. Paetzold and G. Maier, Angew. Chem., 1964, 76, 343.110 P. Geymeyer, E. G. Rochom, and U. Wannagat, Angew. Chern., 1964, 76, 499;C. R. Russ and A. G. MacDiarmid, ibid., p. 500; H. Jenne and K. Niedenzu, Inorg.Chem., 1964, 3, 68.ll1 E. K. Mellon, Jr., and J. J. Lagowski, Adv. Inorg. Chem. Radiochem., 1963,5, 259.113 P. Powell, J. A. Semlyen, R. E. Blofeld, and C. S. G. Phillips, J . Chem. SOC.,114 R. F. Riley and C. T. Schack, Inorg.Chem., 1964, 3, 1651.115 V. Gutmann, A. Meller, and E. Schaschel, J . Organmet. Chem., 1964, 2,116 R. K. Bartlett, H. S. Turner, R. J. Warne, and M. A. Young, Chem. and Ind.,117 V. Gutmann, A. Meller, and E. Schaschel, Monatsh., 1964, 95, 1188.118 V. Gutmann, A. Meller, and R. Schlegel, Monatsh., 1964, 95, 314.ll9 V. Gutmann, A. Meller, and R. Schlegel, Monatsh., 1963, 94, 1071.lao R. H. Toeniskoetter and K. A. Killip, J . Avner. Chem. Soc., 1964, 86, 690.lal D. F. Gaines and R. Schaeffer, J . Arner. Chem. SOC., 1963, 85, 3592; cf. Ann.Reports, 1963, 60, 185.122 G. A. Hahn and R. Schaeffer, J . Amer. Chern. SOC., 1964, 86, 1603.la3 K. Niedenzu, P. Fritz, and H. Jenne, Angew. Chern., 1964, 76, 535; H. Nothand W. Regnet, 2. Naturforsch., 1963, 18b, 1138.12* K.Niedenzu, P. Fritz, and J. W. Dawson, Inorg. Chem., 1964, 3, 1077.laa M. H. Goodrow, R. I. Wagner, and R. D. Stewart, Inorg. Chem., 1964, 3, 1212;W. Gee, R. A. Shaw, and B. C . Smith, J . Chern. SOC., 1964, 4180; A. D. Tevebaugh,Inorg. Chein., 1964, 3, 302.A. J. LefRer, Inorg. Chem., 1964, 3, 145.1964, 280.287.1964, 1026HOLLIDAY: THE TYPICAL ELEMENTS 125zine; 126 a new method for the synthesis of tetra-alkyldiboroxides involvesreaction of sulphur dioxide with an aminoborine, e.g.ZBu,B*NMe, + SO, -+ Bu,B-O*BBu, + OS(NMe,),Reactions of diborane with alkanethiols give products of the type (RS),B,(RSBH,),, and with dithiols give compounds H,B*S*CH,*CH,*S*BH, and(CH,S),BH; reduction of (RS),B compounds gives products (RS),BH, andthese with secondary amines yield (alkylthio)dialkylaminoborines,RS-BH*NR,.128 The cyclic 1,2,4-trithia-3,5-diborolan has been preparedfrom alkylboron dihalides and hydrogen disulphide.129 The chemistry ofboronic and borinic acids has been reviewed.130The relative acceptor powers of boron halides and the BH3 group withrespect to trimethylamine as donor have been assessed by proton nuclearmagnetic resonance methods; the order BBr, > BCl, > BH, > BF, isfound.lal Some aspects of boron co-ordination chemistry have been re-viewed.ls2 Difluoroborine, HBF,, has been prepared ; it slowly disproportion-ates at room temperature and adds ethylene to give C2H,-BF,.133 The 1 :Iaddition compound of boron trifluoride with chlorine trifluoride is formu-lated as [ClF2][BF4] on conductivity and spectroscopic evidence,134 and theproducts of the reactions of boron trifluoride with the three oxides, N203,N205, and N204 contain as predominant species NOBF,, NO,BF,, and amixture of these two, respectively.l35 The much discussed structure of" boron trifluoride dihydrats " has been resolved by formulation as a mole-cular addition compound, F,B,OH,, with the second water molecule linkingthese species together by hydrogen bonds.136 1lB nuclear magnetic resonancestudies have established the existence of the mixed halide BBrClI in amixture of BCl,, BBr,, and B13.13' Vinyldibromoborine has been pre-pared by reaction of boron tribromide with tetravinyltin in the presenceof mercury; B-vinylated bisaminoborines are formed on reaction witha m i n e ~ .l ~ ~ Some boron azides have been prepared by reaction of theappropriate halide with an alkali-metal azide, e.g., Cl,BN, and Ph,BN3;heating the pyridine adduct of the latter compound gives the borazine,(PhB-NPh)3.13g The chemistry of compounds with B-B bonds has beenlZ6 S. K. Wason and R. F. Porter J . Phys. Cherra., 1964, 68, 1443.lZ7 H. Noth and P. Schweizer, Chem. Ber., 1964, 97, 1464.E. L. Muertterties, N. E. Miller, K. J. Packer, and H. C. Miller, Inorg. Clhem.,1964,3,870; B. Z. Egan, S. G. Shore, and J. E. Bonnell, ibid., p. 1024; T. A. Shchegoleva,E. M. Shashkova, and B. M. Mikhailov, Izvest. Akad. Nauk S.S.S.R., Otdel. khim.Nauk, 1963, 494 (443); B. M. Mikhailov, V. A. Dorokhov, and T.A. Shchegoleva,ibid., p. 498 (446); B. M. Mikhailov, T. A. Shchegoleva, and V. D. Sheludyakov, ib.icl.,p. 816 (738).l z 9 M . Schmidt and W. Siebert, Angew. Chem., 1964, 76, 687.lSo K. Torssell, Progr. Boron Chem., 1964, 1, 369.ls1 J. M. Miller and M. Onyszchuk, Canad. J . Chem., 1964, 42, 1518.132 T. D. Coyle and F. G. A. Stone, Progr. Boron Chem., 1964, 1, 83.lS3 T. D. Coyle, J. J. Ritter, and T. C . Farrar, Proc. Chern. Xoc., 1964, 25.la* H. Selig and J. Shamir, Inorg. Chem., 1964, 3, 294.136 J. C. Evans, H. W. Rinn, S. J. Kuhn, and G. A. Olah, Iraorg. Chem., 1964,136 W. B. Bang and G . B. Carpenter, Acta Cryst., 1964, 17, 742.lS7 P. N. Gates, E. F. Mooney, and D. C. Smith, J . Chem. SOC., 1964, 3511.13aP. Fritz, K. Niedenzu, and J.W. Dawson, Inorg. Chem., 1964, 3, 626,lS9 P. I. Pmtzold? 2. onorg. Chem., 1963, 326, 47, 53, 58, 64.3, 857126 INORGANIC CHEMISTRYreviewed,140 and the reactions of diboron tetrafluoride and the polymers( BF)n with some oxides and organometallic compounds are reported.l41An electron-diffraction study has confirmed the staggered conformation ofdiboron tetrachloride;142 reaction of an excess of the latter with acetyleneyields the 1,2-tetraliisdichloroborylethane ( C1,B),CH*CH(BC1,),.143 Mass-spectral studies suggest the formation of trichloro(dichloroboryl)silane,Cl,B*SiCI,, in the preparation of diboron tetrachloride in an electric dis-charge.144 Compounds of type B,(NMe,),-.X,, (X = C1 or Br) have beenprepared by reactions of BX, or RBX,,R,BX with B2(NMe,)4;145 the lastcompound adds HY molecules (Y = C1, Br, or CN), to give the bisdi-methylamine adducts, HNMe,*BY,*BY,*HNMe2.146Aluminium.The fist direct synthesis of an amine alane has beenachieved by heating aluminium and hydrogen in the presence of triethylene-diamine (TED) to give TED,A1H,.14' Polyiminoalanes (polymers withA1-N backbones; M , 750-2500) have been obtained by reactions of tri-alkylamine alanes with, e.g., amines or methyl cyanide,148 phenylalanesPh,AlH and PhAlH, by reaction of Ph,Al with AlH3,149 and the compound(9) by reaction of lithium aluminium hydride with trimethylsiloxyaluminiumch10ride.l~~ Complex formation by organoalurninium compounds has beenH'A,/c'MeJSi-0 'O-siMe,' A F(9) CI' 'Hreviewed;l51 an order of stability N > 0 > S is suggested for moleculesdonating through these atoms to triethylaluminium.152 Further complexesof trimethylaluminium with amines and polyamines have been obtained, andstructures involving either 4- or 5-co-ordinated aluminium have been pro-posed ;l53 tetramethylhydrazine forms a 1 : 1 adduct with triethylaluminiumin which both nitrogen atoms are equivalent and aluminium is probably5-c0-0rdinated.l~~ Structural studies of LiAlEt, suggest a tetrahedral AlEt4-ion but with weak covalent interaction involving lithium.155 Tri-t- butyl-lCo R.J. Brotherton, Progr. Boron Chem., 1964, 1, 1 .1 4 1 A. K. Holliday and F. B. Taylor, J . Chem. SOC., 1964, 2731.I42 K. Hedberg and R. Ryan, J . Chem. Phys., 1964, 41, 2214.143 C.Chambers, A. K. Holliday, and S . Walker, Proc. Chem. SOC., 1964, 286.1 4 4 A. G. Massey and D. S. Urch, Proc. Chem. SOC., 1964, 284.145H. Noth, H. Schick, and W. Meister, J . Organornet. Chem., 1964, 1, 401; cf.14' E. C. Ashby, J . Amer. Chem. SOC., 1964, 86, 1882.148R. Ehrlich, A. R. Young, B. M. Lichstein, and D. D. Perry, Inorg. Chem.,149 J. R. Surtees, Chem. and Id., 1964, 1260.l 8 O H. Schmidbaur and F. Schindler, Chem. Ber., 1964, 97, 952.151 H. Lehmkuhl, Angew. Chem., 1963, 75, 1090.152 H. E. Swift, C. P. Poole, Jr., and J. F. Itzel, Jr., J . P h p . Chem., 1964, 68, 2509.153 T. Mole, Chem. and I d . , 1964, 281; N. R. Fetter and D. W. Moore, C a d .154 D. F. Clemens, W. S. Brey, Jr., and H. H. Sisler, Inorg. Chem., 1963, 2, 1281.155 K.Mach, J . Organornet. Chem., 1964, 2, 410; R. L. Gerteis, R. E. Dickerson,Ann. Reports, 1963, 60, 185.S. C. Malhotra, Inorg. Chern., 1964, 3, 862.1964, 3, 628.J . Chem., 1964, 42, 885.and T. L. Brown, Inorg. Chem., 1964, 3, 872HOLLIDAY: THE TYPICAL ELEMENTS 127aluminium has been obtained as the diethyl ether complex,156 and acetylidesMIA1(C:CR), have been prepared by reaction of the appropriate acetylenewith the alkali-metal aluminium hydride.157 Reaction of potassium thio-cyanate and aluminium chloride in acetonitrile gives the complex,K 3[ d( SCN)], . *’ *The chemistry of gallium has beenreviewed.159 A determination of the crystal structure has confirmed thatthe adduct Me3N,GaH3 is monomeric.160 A spectroscopic study of thestructure of trimethylgallium is consistent with a planar non-associatedmolecule formation of the iso-, cis-, and trans-tripropenylgallium com-pounds (isolated as trimethylamine adducts), from dipropenylmercury andgallium, occurs with retention of configuration.ls2 Alkylgallium chlorideshave been prepared from gallium trichloride and tetramethylsilane (or thesiloxane Me3Si*O*SiMe3).la3 Reactions of the trialkyls Me3M (M = Al, Ga,or In) with some carboxylic, phosphinic, thiophosphinic, and sulphuric acidsgive &membered rings each containing two W e , groups.ls* The reactionsof some gallium allroxides, prepared from gallium trichloride and sodiumalkoxide, have been studied.lG5 For the compound InC,H,, an “open-faced half-sandwich ” structure with symmetry closely approximating toCSv and essentially covalent binding is proposed.ls6 Some adducts of thetetrachloroindate( III) anion InC1,2- with urea and thiourea have beenprepared,l67 and solid indium(m) iodide has been shown to be dimeric.168Solvent-extraction studies afford no evidence for x > 4 in [TICl,](z-S)-anions.lsQ A Grignard synthesis of triethylthallium has been achieved intetrahydrofuran,l70 and some complexes of thallium trichloride with pyridineand quinoline have been studied.171 Thallium(1) dithionite has been pre-pared.172Electrochemical methods have been used to formgraphite compounds from a variety of acids, e.g., H,SO,, H,Se04, HClO,,and HN03.173 The reaction of active nitrogen with graphite at high temper-ature gives mainly cyanogen.174 Surface oxides of carbon have been166 I.Paul and T. D. Smith, J . Chem. SOC., 1964, 2770.157 L. I. Zakharkin and V. V. Gavrilenko, Izvest. Akad. Nauk S.S.S.R., Odtel. khim.168 0. Schmitz-Dumont and B. Ross, Angew. Chem., 1964, 76, 647.169 N. N. Greenwood, Adv. Inorg. Chem. Radiochem., 1963, 5, 91.160 D. F. Shriver and C. E. Nordman, Inorg. Chem., 1963, 2, 1298.161 G. E. Coates and A. J. Downs, J . Chem. SOC., 1964, 3353.162 D. Moy, 6. P. Oliver, and M. T. Emerson, J . Amer. Chem. SOC., 1964, 86, 371.lsa H. Schmidbaur and W. Findeiss, Angew. Chem., 1964, 76, 752, 753.164 G. E. Coates and R. N. Mukherjee, J . Chem. SOC., 1964, 1295.166 R. C. Mehrotra and R. K. Mehrotra, Current Sci., 1964, 33, 241.lB6 S. Shibata, L.S. Bartell, and R. M. Gavin, Jr., J . Chem. Phys., 1964, 41, 717.16’D. J. Tuck and E. J. Woodhouse, Chem. and Id., 1964, 1363.16* J. D. Forrester, A. Zalkin, and D. H. Templeton, Inorg. Chem., 1964, 8, 63.16D G. Nord and J. Ulstrup, Ada Chem. Scand., 1964, 18, 307.170 0. Yu. Okhlobystin, K. A. Bilevitch, and L. I. Zakharkin, J . Organmet. Chem.,171 F. Ya Kul’ba, V. E. Mironov, V. I. Sazhina, and T. G. Ogibenina, Zhur. nemg.P. W. Schenk and W. Muller, Chem. Ber., 1964, 97, 2404.M. J. Bottomley, G. S. Parry, A. R. Ubbelohde, and D. A. Young, J . Chem.Gallium, .indium, and thallium.Group IV.-Curbon.Nauk, 1963, 1146 (1053).1964, 2, 281.Khim., 1963, 8, 911 (468).SOC., 1963, 5674.174 H. W. Goldstein, J . Phy8. Chenz., 1964, 68, 39128 INORQANIC CHEMISTRYreviewed;175 the polymeric carbon suboxide prepared at 100" has approxim-ately six suboxide units fused into a heterocyclic structure with five carbonatoms and one oxygen in the ring and a carbonyl group adjacent, to theoxygen.17* The peroxocarbonates Na,C,O,,zH,O and NaHCO,,H,O havebeen obtained by the action of carbon dioxide on sodium hydroxide-hydrogen peroxide mixtures.177 Reaction of CH,& or CX, (X = Br, I, orC10,) with o-phenylenebisdimethylarsine (diars) gives the new 4-co-ordinateGarbon complexes, [H,C diar~]~+[X-], and [C(diars),14+[X-],, as stable white~ 0 l i d s .1 7 8A review has appeared on the acceptor properties of the quadripositiveelements Si, Ge, Sn, Pb,17@ and several papers relate to these elements (M)collectively. Acetylides, e.g., Ph*CiC.MR, and R,M*CiC*CiC*MR,, have beenobtained from alkali-metal acetylides and the R,MX (X = halogen) com-pounds,l80 and X in these is also replacable by cis- and tram-propenyl (exceptPb),181 azide,ls2 R'0*0-,lB3 and Me3Si*O-.ls4 Reaction of dihydric phenolswith R,MCl, (M = Si or Sn) gives very stable 5- and 7-membered hetero-c y c l e ~ . ~ ~ ~ Hydroxyfluoro-anions containing germanium and tin, but notsilicon, e.g., [GeF,*OHI2-, [SnF,( OH)J2-, have been obtained, and thermalcondensation gives species such as [Ge2Fl,0]4- and [SnF,0J2-.186High-purity silicon has been prepared by high-temperaturereduction of chlorosilanes and hydrogen.187 The two isomers n- and iso-tetrasilane, prepared in an electric discharge, have been isolated andidentified.ls8 Mixed silicon-germanium hydrides have been preparedfrom mixtures of the lower oxides by addition of hydrofluoric acid,1ss frommetalSi-Ge " alloys " and acid,lQO and by metathetic reactions;lD' andtrisilyl compounds, (SiH,),X (X = P, As, Sb, or CH) have been obtainedby, e.g., reaction of SiH,Br and KPH,.lg2 Cyclic organosilicon compoundshave been reviewed,lg3 and the compounds Si(SiMe3),,lg4 Me(Me,Si),MeSilicon.1 7 6 H.-P.Boem, E. Diehl, W. Heck, and R. Sappok, Angew. Chem., 1964, 76, 742.176 A. R. Blake, W. T. Eeles, and P. P. Jennings, Trans. Furaday SOC., 1964, 60,177 T. P. Firsova, A. N. Molodkina, T. G. Morozova, and I. V. Aksenova, Zhur.178R. N. Collinge, R. S. Nyholm, and M.L. Tobe, Nature, 1964, 201, 1322.179 I. R. Beattie, Quart. Rev., 1963, 17, 382.l81D. Seyferth and L. G. Vaughan, J . Organomet. Chem., 1963, 1, 138.182 J. S. Thayer and R. West, Inorg. Chem., 1964, 3, 889.lS8 A. Rieche and J. Dahlmann, Annalen, 1964, 675, 19.185 H. J. Emeldus and J. J. Zuckerman, J . Organomet. Chem., 1964, 1, 328.18'JL. Kolditz and H. Preiss, 2. anorg. Chern., 1963, 325, 245, 252, 263.387E. Sirtl and K. Rensohel, 2. anorg. Chem., 1964, 332, 113.188 S. D. Gokhale and W. L. Jolly, Inorg. Chem., 1964, 3, 946.le9P. L. Timms and C. S. G. Phillips, Irwrg. Chem., 1964, 3, 606.1f"JP. Royen and C. Rockthschel, Angew. Chem., 1964, 76, 302; P. L. Tinmu,191R. Varma and A. P. Cox, Angew. Chem., 1964, 76, 649.lop E. Amberger and H. D.Boeters, Chem. Ber., 1964, 79, 1999.108 K. A. Andrianov, I. Haiduc, and L. M. Khananashvili, Uspekhi Khim., 1963,32, 539 (243); H. Gilman and G. L. Schwebke, Adv. Organomet. Chem., 1964, 1, 90.194 H. Gilman and C. L. Smith, J . Amer. Chem. SOC., 1964, 86, 1454.691; A. R. Blake and A. F. Hyde, ibid., p. 1775.neorg. Khim., 1963, 8, 278 (140).H. Hartmann and K. Komorniczyk, Naturwit~?., 1964, 51, 214; H. Hartmann,H. Wagner, B. Karbstein, M. K. el A'ssar, and W. Reiss, ibid., p. 215.H. Schmidbaur and H. Hussek, J . Organomet. Chem., 1964, 1, 235, 244,257.C. C. Simpson, asd C. S. G. Phillips, J . Chem. SOC., 1964, 1467HOLLIDAY: THE TYPICAL ELEMENTS 129(n = 2-7),195 Ph,SiLi,lS6 and the carbene analogue MeSiMe (as an inter-mediate)197 have been obtained by the reaction of the appropriatealkyl( ary1)halogenosilanes and alkali metals.Contrary t o an earlier ob-servation,lg8 lithiomethyltrimethylsilane is, like other lithium alkyls, associ-ated in benzene s0lution.1~9 Trimethylsilyl derivatives of some mineralsilicates retain the silicate structure of the latter and may be used to studythe distribution of silicate structures in aqueous solutions of, e.g., sodiumsilicates.Zo0 A review of silicon-nitrogen chemistry has appeared ;zO1 thezero dipole moment of trisilylamine in the gas phase confirms the planarstructure.202 Although the dimethylaminosilanes, SiH4-,(NMe,), (n = 2 or3) are stable in vucuo, the Si-N bond is easily cleaved by many reagents.203The reactionsMe,Si*NHR + Me,Si*NRNa + Me,Si*NR, + NaXhave been used to prepare new alkylaminosilanes,204 and others that havebeen prepared include (Me,Si),NX [X = H, IF, C1, Br, I, NCO, SiR(NH,),,or SiF,*N( SiR,),].205 The sodium silylamide NaN( SiMe,), reacts with cyan-ates or thiocyanates of silicon to give the di-imide, (Me,SiN),C,206 and withhalides [MX, (M = Cr, Mn, Ni, or Cu) to give compounds M[N(SiMe,),],.207The deep blue liquids obtained by oxidation of metallated silylarylhydrazinesNa RXstpeneare shown spectroscopically to be diazenes R,Si*N:NAr and not hydrazylradicals.208 Reaction of silyl azides with antimony pentachloride gives thetetrachloroantimony azide C14SbN,,209 and silylamines undergoing reactionlesM.Kumada and M. Ishikawa, J . Organmet. Chem., 1963, 1, 153.lee G.Marr and D. E. Webster, J . Organmet. Chem., 1961, 2, 93.IB7 0. M. Nefedow and M. N. Manakow, Angew. Chem., 1964, 76, 270; P. S. SkelllB8 J. W. Connolly and G. Urry, Inory. Chem., 1963, 2, 645.lee G. E. Hartwell and T. L. Brown, Inorg. Chem., 1964, 3, 1656; R. H. BaneyaolU. Wannagat, Adv. Inorg. Chem. Radiochem., 1964, 6, 225.ao2 R. Varrna, A. G. MacDiarmid, and J. G. Miller, J . Chem. Phys., 1963, 39, 3157.*OS B. J. Aylett and L. K. Peterson, J. Chem. SOC., 1964, 3429.204 E. W. Abel and G. R. Willey, J . Chem. SOC., 1964, 1528.205 U. Wannagat, K. Behmel, and H. Biirger, Chem. Ber., 1964, 97, 2029; U. Wan-nagat and H. Biirger, Angew. Chem., 1964, 76, 497; U. Wannagat, H. Biirger, P. Gey-mayer, and G. Torper, Monatsh., 1964, 95, 39; U.Wannagat and G. Schreiner, ibid.,p. 46; U. Wannagat and H. Biirger, 2. anorg. Chem., 1964, 326, 309.H. Biirger and U. Wannagat, Monatsh., 1964, 95, 1099.U. Wannagat and C. Kriiger, 2. anorg. Chem., 1964, 326, 288, 304; C. Kriigerand E. J. Goldstein, J . Amer. Chem. SOC., 1964, 86, 1442.and R. T. Krager, ibid., p. 1657.C. W. Lentz, Inorg. Chem., 1964, 3, 574.ao6 U. Wannagat, J. Pump, and H. Biirger, Monatsh., 1963, 94, 1013.and U. Wannagat, ibid., p. 296.aoB N. Wiberg and K. H. Schmid, Angew. Chem., 1964, 76, 380130 INORGANIC CHEMISTRYwith halogen compounds of phosphorus and sulphur have been used to affordcompounds containing P-N and S-N bonds.210 Some new N-substitutedcyclotrisilazanes,211 as well as spiro-compounds such as (10)212 and ( l l ) 2 1 3have been prepared.Many new cyclosiloxazanes have also been reported,e.g., the mixed heterocycle ( 12).214 The alkali-metal silanolates, MIO-SiM,(M = Rb or Cs) have been prepared, and also the ‘‘ double ” silanolateK[Li( O*SiMe,),] ;2l5 reaction of the sodium silanolate with ferric chlorideyields the paramagnetic yellow-green dimer [(Me3Si*0)3Fe]2, which with anexcess of silanolate gives a salt Na[(Me,Si*O),Fe].216 Electron-diffractionstudies of disiloxane, (SiH,),O, and disilyl sulphide, (SiH,),S, indicate shortSi-0 bonds and a very large SiOSi angle but a normal SiSSi angle, suggestingn-interaction of the oxygen unshared pairs with the silicon &orbitals ;,l7this is supported by the weak donor power of the oxygen when comparedwith that in compounds containing C-0-Si and C-0-C bond systems.21sFurther cyclic dimers of the type [Me,Si*O*AlX,], and the correspondingcompounds of germanium, tin, and lead have been de~cribed.2~~ Reactionsof siloxanes with boron trichloride and silicon tetrachloride lead to fissionof some Si-0 bonds ; e.g., ( SiH3*SiH,),0 yields SiH3*SiH,C1, and hexamethyl-cyclotrisiloxane gives Cl,Si(O*SiMe,),Cl (n = 3 or 6).220 A derivative of anew heterocycle, octamethylcyclotetradm- 1 ,kdithian, has been preparedby reaction of dichlorotetramethylsilane with hydrogen sulphide.,,l Aninfrared-spectroscopic study of silicon tetrahalide adducts suggests formu-lation of Si14,4py (py = pyridine) as ~is-[SiI,py,]~+21-.2~~ Silicon dihalidepolymers (Six,), (X = F or I) have been obtained by pyrolysis of the Si,X,compounds; SiF, monomer is stable below Several papers 224*lo E.W. Abel and D. A. Armitage, J. Chem. SOC., 1964, 3122; G. C. Demitras,211 E. W. Abel and R. P. Bush, J. Inorg. Nuclear Chem., 1964, 26, 1685; L. W.212K. Lienhard and E. G. Rochow, 2. anorg. Chem., 1964, 331, 307, 316.21sC. H. Yoder and J. J. Zuckerman, Imrg. Chem., 1964, 8, 1329.J. G. Murray and R. K. GrifEth, J. Org. Chem., 1964, 29, 1215; C. Kriiger and215 H. Schmidbaur and S. Waldmann, Angew. Chem., 1964,76, 753; H. Schmidbaur,*16 H. Schmidbaur, Chem. Ber., 1964, 97, 836, 842; cf. Ann. Reports, 1963, 80, 191.%17 A. Ahenningen, 0. Bastiansen, V. Ewing, K. Hedberg, and M. Traetteberg,Acta Chem. Scam?., 1963, 17, 2455; A.Almenningen, K. Hedberg, and B. Seip, ibid.,p. 2264.21sM. G. Woronkow and A. G. Deitsch, J. prakt. Chem., 1963, 22, 214.219 H. Schmidbaur, J. Organomet. Chem., 1963, 1, 28; H. Schmidbaur, H. Hussek,and F. Schindler, Chem. Ber., 1964, 97, 255; H. Schmidbaur, H.3. Arnold, andF. Beinhofer, ibid., p. 449; H. Schmidbaur, i b a . , p. 459.22oC. H. Van Dyke and A. G. MacDiarmid, Inorg. Chem., 1964, 3, 747; K. A.Andrianov and V. V. Severnyi, Izvest. Akad. Nauk S.S.S.R., Otdel khim. Nauk, 1963,82 (72); J . Organomet. Chem., 1964, 1, 268.221 U. Wannagat and 0. Brandsthtter, Monatsh., 1963, 94, 1090.2 2 2 I. R. Beattie, T. Gilson, M. Webster, and G. P. McQuillen, J. Chem. SOC., 1964,238.22a M. Schmeisser and K.-P. Ehlers, Angeu). Chem., 1964, 76, 781; M.Schmeisserand K. Friederich, ibid., p. 782.224 G. Urry, J . Inorg. Nuclear Chem., 1964, 26, 409; A. Kaczmarczyk and G. Urry,ibid., p. 415; A. Kaczmarczyk, M. Millard, J. W. NUSS, and G. Urry, ibid., p. 421;A. Kaczmarczyk, J. W. NUSS, and G. Urry, ibid., p. 427; J. W. Nuss and G. Urry,ibid., p. 435.R. A. Kent, and A. G. MacDiarmid, Chem. and Ind., 1964, 1712.Breed and R. L. Elliott, Inorg. Chem., 1964, 3, 1622.E. G. Rochow, Inorg. Chem., 1963, 2, 1295.J. A. Perez-Garcia, and H.-S. Arnold, 2. anorg. Chem., 1964, 328, 105HOLLIDAY: THE TYPICAL ELEMENTS 131have described the preparation and properties of perchloropolysilanes, e.g. ,Si5Cl12, Si6Cl14; some of these are stabilised as amine complexes.Germccnium. Vapour pressures of pure germane have been determined,225and the barrier to internal rotation in the ethane-like digermane molecule isestimated as 1490 5 200 cal./mole.226 Reaction of digermane with iodinehas given an iodide, Ge2H,I, the first substituted digermane retaining Ge-Hbonds.227 In contrast to disilyl ether, (SiH,),O (see under silicon, above),digermyl ether (and the sulphide) have sharp GeOGe and GeSGe angles,indicating little tendency for ( p +d)n-bonding by oxygen or sulphur withgermanium( I V ) .~ ~ * Some methylgermanium azides, e.g. , Me,Ge(N,), andMe,GeN,, have been prepared by metathetic reactions ; hydrolysis givescompounds, (Me,GeO), and (Me,Ge),O, res~ectively.2~9 The amines,(Me,Ge),NH and (Me,Ge) ,N, have also been Benzyl deriva-tives of germanium of the type (CH2Ph),GeM4-, have been prepared byusing the lithium compounds (CH2Ph) ,GeLi and (CH,Ph)2GeLi,.231 A6-membered ring containing alternate Me2Ge and NMe groups has beenobtained by reaction of methylamine with dichl~rodimethylgermane.~~~Confirmation of the germanium tetrahalides as stronger electron-pair ac-ceptors than the silicon tetrahalides has been obtained by a study of theirpyridine and isoquinoline addu~ts.~,3 Reaction of germanium(@ iodidewith acetylene gives a 1 : 1 adduct with a di-iodogermiren structure ; replace-ment of the iodine atoms by alkyl groups gives polymers (-GeR2*CH:CH-),.2341 : l Addition of germanium(=) iodide to alkyl iodides also occurs, to giveRGeI,, and mixed alkyls can then be prepared from thk2,5The large number of papers on this element demonstrates thecurrent interest in its chemistry.A preliminary study of the Mossbauerspectra of some inorganic tin compounds has permitted correlation of theresonant absorption frequency with the electronic structures of both oxidationstates and with the ionicity of the bonding 0rbitals.23~ Tin(u) being definedas using only two electrons in any type of bonding, it is concluded that (withthe possible exception of the difluoride) there is no simple ionic compoundin this oxidation state, and that covalent compounds are either 3-co-ordinatewith bond angles -90" (e.g., SnCl,,H,O and SnS) or 6-co-ordinate (e.g.,SnTe and cubic SnSe).237 (Compounds " R,Sn " are discussed below.)Tin(I1) phosphite has been prepared as a very stable anhydrous solid fromphosphorous acid and tin(@ and some new EDTA-tin(@ chelates2 2 5 G.G. Devyatykh and I. A. Frolov, Zhur. neorg. Khim., 1963, 8, 265 (133).228 J. E. Griffiths and G. E. Walrafen, J . Chem. Phys., 1964, 40, 321.227 K. M. Mackay and P. J. Roebuck, J . Chem. SOC., 1964, 1195.228 T. D. Goldfarb and S. Sujishi, J . Amer. Chem. SOC., 1964, 86, 1679.228 I. Ruidisch and M. Schmidt, J . Organornet. Chem., 1964, 1, 493.230 I. Ruidisch and M. Schmidt, Angew. Chem., 1964, 76, 229.031 R. J. Cross and F. Glockling, J . Chem. SOC., 1964, 4125.232 I. Ruidisch and M. Schmidt, Angew. Chem., 1964, 76, 686.23s J. M. Miller and M. Onyszchuk, Proc. Chem. SOC., 1964, 290.234 M. E. Vol'pin, V. G. Dulova, and D. N. Kursanov, Izvest.Akad. Nauk S.S.S.R.,Otdel khim. Nuzlk, 1963, 727 (649); L. A. Leites, V. G. Dulova, and M. E. Vol'pin,ibid., p. 731 (653).2s5 M. Lesbre, P. Mazerolles, and G. Manuel, Compt. rend., 1963, 257, 2303.238 M. Cordey-Hayes, J . Inorg. Nuclear Chem., 1964, 26, 915.a37 R. E. Rundle and D. H. Olson, Inorg. Chern., 1964, 3, 596.Tin.J. D. Donaldson, W. Moser, and W. B. Simpson, J . Chem. SOC., 1964, 323132 INORGANIC CHEMISTRYhave been reported.23g Solid phases, MIS*, and MTSn,F, (M = Na, K,or NH,) have been identified in SnF,-MIF-H,O systern~.~~O Further evi-dence that ‘‘ R,Sn ” compounds are oligomeric or polymeric tin(rv) deriv-atives has been published; the 6-membered ring form of (Ph,Sn), has beenconfirmed, other methods of making (Ph,Sn),, (Ph*CH,*Sn),, and Ph,Sn,have been found,241 and a nonameric cyclic ‘‘ diethyltin ” 242 and a tetrameric“di-t-butyltin ” 243 have been isolated.Reaction of trialkyltin(1v) N-phenyl-formamide with triarylstannanes has been used to prepare mixed alkylaryl-polytin compounds, [R,Sn*SnR’,]SnR”3 (R = alkyl or ary1),244 and similarcompounds can be obtained from reactions of R,SnH, + R’3SnEtz.245Reaction of stannous chloride with lithium triphenylstannate gives a product(Ph3Sn),Sn,246 and the compound, Ph2SnLi2, has been prepared.,,‘ Newcompounds containing R,Sn or R,Sn groups are reported in great variety;most of these have been synthesised by metathetic reactions using, e.g.,R,SnM1 or R,SnHal; amino-derivatives of tin have also been used, e.g.:R,Sn*NMe, + HA --+ R,SnA + Me,NH(e.g., A = OH, OR, PR,, h R , , C,H,, CjCR 248cf.R4-nSn(NEt2)n + nBu,AlH + R&3nHla + nBu,Al-NEt, 24Qand additions to the hydrides R,SnH or R,SnH, of, e.g., azobenzene to giveorganotin hydra~ines,,~~ and isocyanates to give R,Sn*NR*CH0,251 arereported. The general topic of organotin hydride addition to organiccompounds has been the subject of a revie~,~52 and the mechanism of olefinaddition has been further discussed.253 Other new compounds containingR,Sn or R2Sn groups include Me,N*B(SnEt,), 254 and R,SnX2,AlX,(X = Hal) ;255 Et,Sn*CiC*CH:CH,,256 Bu3Sn*NCS,257 and Me,Sn(NO,), 258-the last, like Me,Sn(C10,),,259 behaves as a 1 : 2 electrolyte in aqueous solution ;239 H. G. Langer, J . Imrg. Nuclear Chem., 1964, 26, 767.240 J.D. Donaldson and J. D. O’Donoghue, J . Chem. SOC., 1964, 271.241 D. H. Olson and R. E. Rundle, Inorg. Chem., 1963, 2, 1310; W. P. Neumannand K. Konig, Annalen, 1964,677,1,12; W. P. Neumann, K. Konig, and G. Burkhardt,ibid., p. 18; W. P. Neumann and K. Konig, Angew. Chem., 1964, 76, 892.242 W. P. Neumann and J. Pedain, Annalen, 1964, 672, 34.24sW. V. Farrar and H. A. Skinner, J . Organomet. Chem., 1964, 1, 434.244 H. M. J. C. Creemers, J. G. Noltes, and G. J. M. van der Kerk, Rec. Traw.246 W. P. Neumann and B. Schneider, Angew. Chern., 1964, 76, 891.2a6H. Gilman and F. K. Cartledge, Chem. and Ind., 1964, 1231.247 H. Schumann, K. F. Thorn, and M. Schmidt, J . Organmet. Chem., 1964, 2, 97.248 K. Jones and M. F. Lappert, Proc. Chem.SOC., 1964, 22; E. Amberger, M.-R.249 M.-R. Kula, J. Lorberth, and E. Amberger, Chem. Ber., 1964, 97, 2087.250 J. G. Noltes, Rec. Trav. chim., 1964, 83, 575.251 J. G. Noltes and M. J. Janssen, J . Organomet. Chem., 1964, 1, 346.252 H. G. Kuivila, Adv. Organomet. Chem., 1964, 1, 47.2 5 3 C. Barretson, H. C. Clark, and J. T. Kwon, Chem. and Ind., 1964, 458.a64 H. Noth and K.-H. Hermannsdorfer, Angew. Chem., 1964, 76, 377.255 W. P. Neumann, R. Schick, and R. Koster, Angew. Chem., 1964, 76, 380.256V. S. Zavgorodduii and A. A. Petrov, Zhur. obshchei Khim., 1963, 33, 2791257 R. A. Cummins and P. Dunn, Azcstral. J . Chem., 1964, 17, 411.258 C. C. Addison, W. B. Simpson, and A. Walker, J . Chem. SOC., 1964, 2360.269M. M. McGrady and R.S. Tobias, Inorg. Chern., 1964, 3, 1157.chirn., 1964, 83, 1284.Kula, and J. Lorberth, Alzgew. Chem., 1964, 76, 145.( 27 18)HOLLIDAY: THE TYPICAL ELEMENTS 133(Me,Sn),N (prepared by using Me,SnHal and Li,N or LiNH,),260 R,Sn*MPh,(M = P, As, or Sb),261 R,Sn*PPh*SnR,, and cyclic (Ph2Sn*P*SnPh,),;262Me,Sn*OH, dimeric in solution with OH bridges giving 5-co-ordinate tin,2@and distannoxane derivatives XR,Sn*O*SnR,*OH (X = halogen), alsodimeric in solution with the suggested structure (13);264 many organotincarboxylates, with bridging or chelating carboxylate groups,265 and organotin-bidentate ligand compounds (ligand = oxine, 2,2'-bipyridyl, or 1 , l O phen-anthroline), where the co-ordination number of the tin is usually 6;266stannosiloxanes (Ph,Si.O),SnR, ;267 and (Ph3Sn),S.268 Reaction of hexa-phenyldistannane with glacial acetic acid gives the stable acetate, Sn2( OAc),,R\ ,R ? IRHO-Sn - 0 - Sn -Xf +X- Sn -0-Sn -OHR"R R' 'R (13)for which tin-acetate-tin bridges are pr0posed.26~ The tendency of un-symmetrically substituted organotin( rv) oxides to disproportionate in solutionis attributed to the removal of the symmetrical diorganotin oxide by preci-pitation.270Reaction of tin( IT) chloride with tetrabutylgermanium, or of tetrabutyltinand germanium(Iv) chloride, gives exchange of only one butyl group.27fThe product of reaction of tin(Iv) chloride and acetylacetone (acac) inbenzene depends upon the temperature; in hot benzene replacement to givethe monomeric SnC12(acac), occurs, while in the cold, addition givesSnC14,Hacac (formulated as [(Ha~ac),SnCl,][SnC1~]).~7~ The existence of1 : 1 molecular addition compounds of tin(Iv) chloride in solution has beenand spectroscopic studies of the 1 : 1 adducts of Me,MCl (M = Snor Pb) with some amides and sulphoxides indicate trigonal pyramidalstructures with the ligand trans to the chlorine atom.274 Some SnHal,L,260 W.L. Lehn, J . Amer. Chem. SOC., 1964, 86, 305; K. Sisido and S. Kozima,J . Org. C'hem., 1964, 29, 907.1. G. M. Campbell, G. W. A. Fowles, and L. A. Nixon, J . Chem. SOC., 1964,3026; H. Schumann, H. Kopf, and M. Schmidt, J . Organomet. Chem., 1964, 2, 169;2. amrg. Chem., 1964, 331, 200.362 I. G. M. Campbell, G. W. A. Fowles, and L. A. Nixon, J . Chem. Soc., 1964,1389; H.Schumann, H. Kopf, and M. Schmidt, Chem. Ber., 1964, 97, 2395.2asR. Okawara and K. Yasuda, J . Organomet. Chem., 1964, 1, 356.264R. Okawara and M. Wada, J . Organomet. Chem., 1963, 1, 81.r65R. A. Cummins and P. Dunn, Austral. J . Chem., 1964, 17, 185; R. Okawaraand 3%. Ohara, J . Organomet. Chem., 1964,1, 360; M. Wada, M. Shindo, and R. Okawasa,&d., 1964, I , 95; H. H. Anderson, Imrg. Chem., 1964, 3, 912.Za6 L. Roncucci, G. Faraglia, and R. Barbieri, J . Organomet. Chem., 1964, 1, 427;T. Tanaka, M. Komura, Y. Kawasaki, and R. Okawara, ibid., p. 484.267 C. Thies and J. B. Kinsinger, Inorg. Chem., 1964, 3, 551.268 E. J. Kupchik and P. J. Calabretta, Inorg. Chem., 1964, 3, 905.269 E. Wiberg and H. Behringer, 2. anorg. Chem., 1964, 329, 290.270 W.J. Considine, J. J. Ventura, B. G. Kushlefsky, and A. Ross, J . Organomet.271 J. G. A. Luijten and F. Rijkens, Rec. Trav. chim., 1964, 83, 857.27aR. C. Mehrotra and V. D. Gupta, J . Indian Chem. SOC., 1963, 40, 911.J. Laane and T. L. Brown, Inorg. Chem., 1964, 3, 148.N. A. Matwiyoff and R. S. Drago, Inora. Chem., 1964, 3, 337.Chem., 1964, 1, 299134 INORGANIC CHEMISTRY(L = ligand) complexes have also been studied; in solution, SnF4,2EtOHforms an equilibrium mixture of the cis and trans octahedral forms;275 andSnCl,,ZAmide (where Amide includes dimethylformamide and acetanilide)complexes are monomeric with metal-oxygen b0nds.27~ In general, SnCl,,L,complexes assume the cis-configuration (e.g., with L = Me2CO), but moresterically hindered ligands (e.g., Me3N and Me,O) give trans-is~mers.~~~ Thethermal stability of the hexachlorostannates, M1,SnC16, is in the orderM = NH, > CS > Rb > K.278A useful review of organolead chemistry over the period 1953-1963 has been A study of the structure of the Pb94- ion sug-gests a similarity to the isoelectromic Big5 f.280 Investigation of the light-scattering of lead(I1) species in aqueous perchlorate shows the presence ofunhydrolysed and uncomplexed species of charge 2+ in a slight excess ofperchloric acid, but as [OH-] increases, species such as [Pb4(OH)4(C104),]2+are formed.281 An extensive study has been made of compounds (Ph,M),M'(M = Pb or Sn; M' = Sh or Ge) with the " neopentane " configuration; itseems likely that the " red cliphenyl-lead " noted by Krause is (Ph,Pb),Pb 2a2(cf.refs. 241, 246). Cyclopentadienyl compounds of type R,,PbX,, whereX = C,H5 or C,H,Me, have been prepared and their infrared and nuclearmagnetic resonance spectra recorded ;283 and the acetylides R,Pb*[CiC];R'and R,Pb*[CiC];PbR, (n = 2 or 3) have been obtained as colourless crystalsby reaction of the appropriate R3PbHal with an alkali-metal a ~ e t y l i d e . ~ ~ ~The triphenyl-lead compounds, Ph,Pb.CN and Ph,Pb*SCN,285 and the firstorganolead-phosphorus compound, Ph,Pb*Ph ,PH (less stable than thecorresponding compounds of the other Group IV elements)286 have beenprepared ; in the cleavage of alkyldiplumbanes, R6Pb2, by hydrogen chloride,Pb-C bonds break before the Pb-Pb bond.287 Complexes,have been prepared by reaction of either lead(I1) or lead(1v) acetate withtrialkanolamines in chloroform or water.Sa8 Fusion of anhydrous potassiumhydroxide with lead dioxide has given two new plumbates, K2Pb03and K2Pb307, isostructural with the corresponding tin andLead.{Pw"OH)3121(0Ac)a (R = [CH2ln),276 R.0. Ragsdale and B. B. Stewart, Proc. Chem. SOC., 1964, 194.27sR. C. Aggarwal and P. P. Singh, 2. anorg. Chem., 1964, 332, 103.277 I. R. Beattie and L. Rule, J. Chem. Soc., 1964, 3267.I. S. Morozov and Li Ch'ih-fa, Zhur. neorg. Khim., 1963, 8, 651 (330).279 L. C. Willemsens, " Organolead Chemistry ", International Lead Zinc Research280 D. Britton, Inorg. Chem., 1964, 3, 365; cf. Ann. Reports, 1962, 59, 147.281 F.C. Hentz, Jr., and S. Y. Tyree, Jr., Inorg. Chem., 1964, 3, 844.282 L. C. Willemsens and 0. J. M. van der Kerlr, J. Organomct. Chem., 1964, 2, 260;W. Dreuth, M. T. Janssen, G. J. M. van der Kerk, and J. G. Vliegenthart, ibid., p. 265;L. C. Willemsens and G. J. M. van der Kerlr, {bid., p. 271 ; W. Dreuth, L. C. Willemsens,and G. J. M. van der ICerk, ibid., p. 279.Organisation, New York, 1964.28s H. P. Fritz and K.-E. Schwarzhans, Chem. Ber., 1964, 97, 1390.2 8 r H . Hartmann and K. Komorniczyk, Natztwiss., 1964, 51, 214.286 H. J. Emeldus and P. R. Evans, J. Chem. Soc., 1964, 510.2~ H. Schumann, P. Schwabe, and M. Schmidt, J . Organomet. Chem, 1964, 1, 366.287 H. J. Emel6us and P. R. Evans, J. Chem. SOC., 1964, 511.288 R. C. Olberg and M. Stammler, J.Inorg. Nuclear Chem., 1964, 26, 565.289 C. Fouassier, M. Tournoux, and P. Hagenmuller, J. Inorg. Nuclear Chem., 1964,26, 1811HOLLIDAY: THE TYPICAL ELEMENTS 135lead(1v) oxide chloride, PbOCl,, has been obtained by the reaction,290PbC1, + C1,O -+ PbOC1, + 2C1,.Group V. Nitrogen. A wave-mechanical calculation predicts that theammonium radical should be stable by 4 . 0 0 7 a.u ; a substituted ammoniumamalgam Me,N*Hg has been prepared electrolytically.2s1 An infraredspectroscopic study of solid di-imide, (NH),, prepared by passage of amicrowave discharge through hydrazine, suggests a planar cis-str~cture.~~~Reviews concerned with alkali and alkaline-earth amides 293 and withinorganic azides 29* have appeared, and the azides Ph,M(N3), and Ph3MN3(M = Si, Ge, Pb, or Sn) have been obtained; their high stability is correlatedwith d,-p, bonding; and while Ph,SiN, gives on pyrolysis a cyclic dimer(Ph,Si*NPh), and a 1 : 1 complex with Ph,P, the corresponding tin and leadcompounds are pyrolysed to form Ph,Sn(Pb) and nitrogen, and form nophosphine ad duct^.^^^ Cyanogen fluoride (b.p.-46") has been isolated bypyrolysis of cyanuric fluoride at 1300 O under reduced pressure,296and cyanogenazide by the reactionNaN, + CIN 4 N,CN + NaClAddition of triphenylphosphine gives the '' phosphinimide", Ph,P:NCN,and nitrogen.297 Ammonium dicyanamide has been prepared by twometh0ds,2~8 and structural examination of some metal cyanamides suggeststhat those of thallium(I), silver(I), and lead(r1) are essentially covalent andthat Na,CN2 is ionic.299 Fluorination of cyanogen or cyanogen chloridewit,h metal fluorides gives 'specific products, e.g., mercuric fluoride yieldsSome reactions of N-bromobistrifluoromethylamine, (CF,),NBr, havebeen studied ; nitric oxide yields the nitrosoamine, (CF3),N*N0, and carbonmonoxide gives a product (CF,),N*COBr.301 Pure nitrous acid has beenprepared by low-temperature ion-exchange of sodium nitrite in aqueousglycol diinethyl ether,302 and the peroxynitrite ion, O*NO,-, has been formedin the oxidation products of chloramine or hydro~ylamine.~03 Nitrylfluoride is obtained in 90% yield by passage of nitrogen dioxide over a stirredbed of cobalt triflu~ride,~ at 300°, and nitryl bromide exists in equilibriumwith bromine and NO,-N2O4 in a mixture of these reagents.305 Some 1 : 1MeCNHg"(CF3)212.3 O0290 K.Dehnicke, Natwwiss., 1964, 51, 536.291 D. M. Bishop, J . Chem. Phys., 1964, 40, 432; G. Brauer and G. Dusing, 2. anorg.292 E. J. Blau and B. F. Hochheimer, J . Chem. Phys., 1964, 41, 1174.298 R. Juza, Angew. Chem., 1964, 76, 290.294 P. Gray, Quart. Rev., 1963, 17, 441.295 W. T. Reichle, Inorg. Chenz., 1964, 3, 402; J. S. Thayer and R. West, ibid.,296 F. S. Fawcett and R. D. Lipscomb, J . Amer. Chem. SOC., 1964, 86, 2576.297 F. D. Marsh and M. F. Hermes, J . Amer. Chem. SOC., 1964, 86, 4506.298 J. W. Sprague, J. G. Grasselli, and W. M. Ritchey, J . Phys. Chem., 1964,68,431.299 M. J. Sole and A. D. Yoffe, Proc. Roy. Soc., 1964, A , 277, 498, 523.Chena., 1964, 328, 154.p.406.H. J. Emeldus and G. L. Hurst, J . Chem. SOC., 1964, 396,H. J. Emeldus and B. W. Tattershall, 2. unorg. Chem., 1964, 327, 147.C. S. Scanley, J . Amer. Chem. SOC., 1963, 85, 3888.H. Martin, W. Seidel, H.-G. Cnotka, and W. Hellmayr, 2. unorg. Chem., 1964,8os G. Yagil and M. Anbar, J . Inorg. Nuclear Chem., 1964, 26, 453.so* R. A. Davis and D. A. Rausch, Inorg. Chem., 1963, 2, 1300.331, 333136 INORGANIC CHEMISTRYand 1 :2 addition compounds of nitrosamines, R,N*N:O, with metallic andnon-metallic halides are rep0rted.~06 Inorganic nitrogen fluorides havebeen reviewed;,07 direct fluorination of urea yields products which, onstorage, evolve difluoroamine, HNF, ; this forms weak adducts with ethers,yields chlorodifluoramine with hydrogen ~hloride,~O~ and gives *NF, radicalson anodic oxidation, which can be recovered either as N,F, or as RNF, bysimultaneous generation of *R radicals.309 Nitrogen trifluoride, containingno other N-F compounds, has been synthesised from its elements by usingan electric discharge at liquid-nitrogen temperature ;310 it has also beenformed by electrolysis of nitrous oxide in anhydrous hydrogen fl~oride,~11and (in small amounts) by fluorination of some nitrides.312 trans-Difluoro-diazine, N,F,, has been obtained by reaction of fluorine with sodium azide;the first product of the reaction is N,F (not isolated) and this loses nitrogenon warming.313 Better methods for the preparation of thiazyl fluoride,NSF, and the trifluoride, NSF,, have been given; when kept in a glassvessel the liquid fluoride forms N,S,F3.314 Some nitrogen-fluorine com-pounds forming adducts with Lewis acids (e.g., BF, or BCl,) have been placedin order of base strength, vix.,EtNF, > MeNF, > HNF, > N2F, > CF,*NF, 3 NF,;there is no evidence for co-ordination other than by N+B bonds in theadducts.,15 The reaction of perfluorohydrazine with sulphur dioxide givesthe compound, FSO,*NF, ; the corresponding imido-compound, (FSO,)&F,is obtained by fluorination of imidodisulphuryl fl~oride.~ls Many 1 : 1 adductsof trimethylamine oxide with typical metal halides (e.g., BBr,, AlCl,, andInCl,) have been prepared.317Nuclear magnetic resonance spectra for a series of GroupV compounds with 5-co-ordination, e.g., Et,NPF,, C,F,-PF,, and PhAsF,,suggest that trigonal-bipyramid geometry prevails, with the more electro-negative ligands preferring the axial positions.318 Triphosphines and arsinesand mixed hydrides of phosphorus, arsenic, nitrogen, and germanium havebeen obtained by hydrolysis of compressed mixtures of phosphides, nitrides,etc., and the phosphines, Si,H,*PH, and (SiH,),PH, have been identified.319Phosphorus.306 D.Klamann and W. Koser, Angew. Chem., 1963, 75, 1104; A. Schmidpeter,307 A. V. Pankratov, Uspelchi Khim., 1963, 32, 336 (157).308E. A. Lawton and J. Q. Weber, J . Arner. Chem. SOC., 1963, 85, 3595.309 G. A. Ward and C. M. Wright, J . Amer. Chem. Soc., 1964, 88, 4333.310 W. Maya, Inorg. Chem., 1964, 3, 1063.311 H.H. Rogers, S. Evans, and J. H. Johnson, J . Electrochem. Soc., 1964, 111, 704.313 W. C. Schumb and R. F. O'Malley, Inorg. Chem., 1964, 3, 922.s13 H. W. Roesky, 0. Glemser, and D. Borinann, Angew. Chem., 1964, 78, 713.u4 Oskar Glemser, H. Meyer, and A. Haas, C h . Ber., 1964, 97, 1704; cf. Ann.315A. D. Craig, Inorg. Chem., 1964, 3, 1628.als M. Lustig, C. L. Burngardner, F. A. Johnson, and J. K. Ruff, Inorg. Chem.,317 M. J. Frazer, W. Gerrard, and J. A. Spillman, J . Inorg. Nuclear Chem., 1964,518 E. L. Muetbrties, W. Mahler, K. J. Packer, and R. Schmutzler, Inorg. Ohem.,819 R. Royen, C. Rocktiischel, and W. Mach, Angew. Chem., 1964, 78, 860; S. D.Chern. Ber., 1963, 98, 3275.Reports, 1962, 59, 149.1964, 3, 1165.26, 1472.1964, 3, 1298.Gokhale and W.L. Jolly, Inorg. Chem., 1964, 3, 1141HOLLIDAY: THE TYPICAL ELEMENTS 137A mass-spectral study of the decomposition of disphosphine, P,H,, inthe vapour phase, suggests that PzH3 is the first product, and this breaks upto give phosphine and a solid (P2H),.320 The structure and reactivity oforganophosphorus compounds have been revie~ed.~Zl Reactions of phenyl-lithium with the diphosphines R2P*PR, (R = alkyl or aryl) give PhR2Pand P-substituted lithium phosphides.322 Methyldibromophosphine hasbeen studied as an alternative to the dichloro-compound in synthesis; avariety of compounds MePR, (R = alkyl, aryl, SiR,, R,N, CN, NCO, orNCS) has been 0btained.~2~ Pentaphenylphosphorus, unlike the square-pyramidal Ph,Sb, has a trigonal-pyramidal structure.324 Two isomericpolyphosphines, (PhP),, were reported last year; it now seems likely thatthe pentamer and the hexamer exist in the solid state, with cyclic structures.325Compounds containing P-P bonds are readily synthesised by using tri-n-butylphosphine in chlorine atom-abstraction rea~tions,~26 e.g.,4Bu,P + 4PhPC1, + 4Ru,PCI, + (PhP),Further methods of preparing mixed alkyl(perfluoroalky1)phosphineshave been given,327 and the perfluoroalkylphosphes, MeHP*P(CF,),,MeP[P(CF,),],, and P,(CF,),, have been prepared; P,(CF3), decomposes togive P,(CF,), and cyclic (PCF,), (n = 4 or 5).32s The oxidation of triphenyl-phosphine to its oxide by hydrogen peroxide has been shown to proceedthrough the adduct (Ph3PO),H2O2, in which the two Ph3P0 groups are heldtogether through the hydrogen bonds of the bridge H,02329.Reaction ofalkali metal phosphides, MIPHR (R = alkyl or aryl), with carbon dioxidegives, finally, the esters RP(CO,R),, which are stable and can be distilled.330Interest in phosphorus-nitrogen compounds continues. Mono- andbis-diphenylphosphinoalkylamines have been prepared and studied ; the biscompounds can be converted into the corresponding dioxides or disulphides,and they form 1 : 1 adducts with alkyl iodides and 1 : 1 complexes with saltsof nickel(=) and Reaction with chloramine gives thecorresponding onium chlorides, e.g., [H2N(R,N)PhP]C1.332 Phosphorus(m)fluoride and dimethylamine react to give the aminodifluorophosphine,Me2N-PF2; this reacts with acids HX (X = C1 or I) to give PF,X, or withboron trifluoride to form an unstable 1 : 1 adduct, and replaces carbon mon-oxide in some metal carbonyls to give, e.g., Ni(CO)2(Me,N*PF,)2.333 The320 Y.Wada and R. W. Kiser, Inorg. Chem., 1964, 3, 174.3zlR. F. Hudson, Adv. Inorg. Chem. Radiochem., 1963, 5, 347.s22 K. Issleib and F. Krech, 2. unorg. Chem., 1964, 328, 21; K. Issleib and K. Krech,323 L. Maier, Helv. Chim. Acta, 1963, 46, 2667.s24 P. J. Wheatley, J. Chm. SOC., 1964, 2206.32s J. J. Daly and L. Maier, Nature, 1964,203, 1167; cf. Ann. Reports, 1963, 60, 196.s26 S. E. Frazier, R. P. Nielsen, and H. H. Sisler, I w g . Chem., 1964, 3, 292.a27 B. J. Pullman and B. 0. West, Austral. J . Chem., 1964, 17, 30.sas A. B. Burg and K. K. Joshi, J . Amer.Chem. Soc., 1964, 86, 353; A. B. Burgs2B D. B. Copley, F. Fairbrother, J. R. Miller, and A. Thompson, Proc. Chem. SOC.,s30 K. Issleib and H. Weichmann, Chem. Ber., 1964, 97, 721.331G. Ewart, A. P. Lane, J. McKechnie, and D. S. Payne, J . Chem. SOC., 1964,ss2 W. A. Hart and H. H. Sisler, Inorg. Chem., 1964, 3, 617.3s3 R. G. Cavell, J . Chem.Soc., 1964, 1992; R. Schmutxler, Inorg. Chem., 1964,3,310.ibid., p. 69.and J. F. Nixon, ibid., p. 356.1964, 300.1543138 INORGANIC CHEMISTRYcorresponding reaction with phosphorus( v) fluoride yields first the amidePF4*NMe2 and then (with an excess of amine) PF3(NMe2),;3% the phenylcompound, PhPF *me,, has been prepared by fluorination of PhPCloNMe,with arsenic or antimony trifluoride or by reaction of PhPF4 with the arnino-silane, Me,Si*NMe,, and undergoes slow conversion 3s5 into[ PhPF (We,) ,]+[PhPF5] -Reactions of trisalkylaminophosphorus(v) compounds, (Me,N),PX (X = 0or S) with POCl, or PSCl, give (Me,N),PXCl; and similar compounds,e.g., (MeN),PO*N, have also been prepared; the latter with P(NMe,), yields(Me,N),P.( O)*N-P(NMe,),.33s Diaminodiphosphines R,N*PR’*PR‘.NR, havebeen obtained by reaction of R,NPR’Cl with sodium; reaction with brominebreaks the P-P bond, but sulphur adds on to give, e.g.,Et2N*R’P(S)*P(S)R’*NEt2.337Further studies have been made of the compounds containing the cations[Cl,P:N*(PCl,N),*PCl,]+ and [Cl,P:N*PCl,]+, reported last year, and newderivatives have been pre~ared.~~s The reaction of methylammoniumchloride and phosphorus(v) chloride in presence of a trace of water givesP4(NMe),C1,, for which the structure (14), with 5-co-ordinate phosphorus,is suggested.339 The chemistry of phosphonitrilic derivatives and relatedRN-PCI~-NNR CI(1 4) (15)compounds has been reviewed,340 and some further methods of preparingthese compounds are reported ; thus, diphenylphosphinic azide, Ph,PO*N,,prepared by reaction of lithium azide with the chloride Ph,POCl, decomposesto give the diphenylphosphonitrilic trimer, and gives, with diphenylchloro-phosphine, linear derivatives Ph,PO*(N:PPh,),C1.341 Reaction of[Ph2P(NH2)*N-P(NH,)Ph2]CIwith R,PCl, gives heteroaubstituted cyclic trimers and tetramers,342 andpolyphosphonitriles are obtained by heating the phosphoryl chlorides of334 D.H. Brown, G. W. Fraser, and D. W. A. Sharp, Chem. an& Ind., 1964, 367;R. Schmutzler, Inorg. Chem., 1964, 3, 410, 415, 421.R. Schmutzler, Angew. Chem., 1964, 76, 570, 893; J . Amr. Chem. Soc., 1964,86, 4500.336 H.-J. Vetter, 2. Naturforsch., 1964, lQb, 72, 168.337 W. Seidel and K. Issleib, 2. anorg. Chem., 1963, 325, 113.33a M. Becke-Goehring and W. Lehr, 2. anorg. Chem., 1963, 825, 287; 1964, 827,128; M. Becke-Goehring, W. G-ehrmann, and W. Goetze, 2. anorg. Chem., 1963,326,127.339 M. Becke-Goehring and L. Leichner, Angew. Chern., 1964, 76, 686.340 N. L. Paddock, Quart. Rev., 1964, 18, 168.K. L. Paciorek, Inorg. Chem., 1964, 3, 96; K. L. Paciorek and R. Kratzer, ibid.,342 D. L. Herring and C. M. Douglas, Inorg.Chem., 1964, 3, 428.p. 594HOLLIDAY: THE TYPICAL ELEMENTS 139linear phosph~nitriles.~~~ Optimum conditions for making the cyclic trimershave been defined and used to prepare the cis- and trans-(NPPhCl), isomers,344and the isomerism (positional and &-trans) of cyclic dimethylaminotri-phosphonitriles has been el~cidated.~~5 One of the geometrical isomers oftetrameric phenylphosphonitrilic chloride has been identified ( 15) (theseparation of three of these isomers was reported last year).346 Two pairsof isomers have been characterised for cyclic diaminodichlorodiphenyltri-phosphonitriles.347 New derivatives of the cyclic P-N compounds includethat obtained from the trimer by reaction with catechol (which chelatesat each phosphorus atom) ;34* alkoxy- and aryloxy-trimers and tetramers(with possible rearrangement to give oxophosphazanes) trifluoroethoxy-derivatives [PN( OR,)& ;350 replacement of > PCl-NH, by 2 PC1-NCO 351and by >PC1-N:PPh3 ;352 aziridinyl derivatives ; 353 and the N-alkylphospho-nitrilium salts, e.g., [N3P,Me,R]+I-, obtained by addition of the allcyl iodide,RI.354 Polymers with the unit (16) have been obtained by transamidationof organophosphine oxides with diamines H,N*X-NH, ;355 metal complexes(17) are formed by reaction of the appropria'te metal chloride with theimido-derivative, N[Ph2P*NH,],C1 (X = NH; M = Cu, Zn, Ni, or Cd) andsimilar compounds with X = 0 or S have been prepared;356 some metalcomplexes of phosphino-1 , 3, 5-triazines are also reported.357A true sodium hexametaphosphate , NadP,018], has been obtained byfractional precipitation from a mixture of polymetaph~sphates.~~~ Self-dissociation equilibria in liquid phosphoric acid have been studied; there isextensive dissociation to give H4PO4' and H2P04- ions and, while watera43 A.Ya. Yakubovich, N. I. Shvetsov, I. V. Lebedeva, and V. S. Yakubovich,s44 B. Grushkin, M. G. Sanchez, and R. G. Rice, Inorg. Chem., 1964, 3, 623.346 C. T. Ford, F. E. Dickson, and I. I. Bezman, Inorg. Chem., 1964, 3, 177.846 B. Grushkin, J. L. McClanahan, and R. G. Rice, J . Amer. Chem. Soc., 1964,347 K. Hills and R. A. Shaw, J . Chem. SOC., 1964, 130.a48 H. R. Allcock, J . Amer. Chena. SOC., 1963, 85, 4051; 1964, 86, 2591.s49 B. W. Fitzsimmons and R. A.Shaw, J . Chem. SOC., 1964, 1735; B. W. Fitz-simmons, C. Hewlett, and R. A. Shaw, J . Chem. SOC., 1964, 4459.s60M. V. Lenton, B. Lewis, and C. A. Pearce, Chem. and Id., 1964, 1387.361 G. Tesi and R. Zimmer-Galler, Chem. and I d . , 1964, 1916.362 R. Keat, M. C. Miller, and R. A. Shaw, Proc. Chem. SOC., 1964, 137.364 G. Allen, J. Dyson, and N. L. Paddock, Chem. and Ind., 1964, 1832.866 L. Parts, M. L. Nielsen, and J. T. Miller, Jr., Inorg. Chem., 1964, 3, 1261.366 A. Schmidpeter, R. Bohm, and H. Groeger, Angew. Chem., 1964, 76, 860.367 W. Hewertson, R. A. Shaw, and B. C. Smith, J . Chem. Soc., 1964, 1020.366 E. Thilo and U. Schiilke, Angew. Chem., 1963, 75, 1176.Zhur. neorg. Khim., 1963, 8, 534 (279).86, 4204; cf. Ann. Reports, 1963, 60, 197.G.Ottmann, H. Agahigian, H. Hooks, G. D. Vickers, E. Kober, and R. Ratz,Inorg. Chem., 1964, 8, 753140 INORGANIC CHEMISTRYacts as a base, sulphuric and perchloric acid act as strong monoprotic a~ids.35~Two peroxides of phosphorus appear to exist ; one (unidentified) coloured andstable only at low temperatures, changes into the other, colourless P4OI1,on warming.360 Potassium dihydrogen peroxophosphate has been pre-pared and ~haracterised,,~l and peroxomonophosphoric acid has beenisolated by anion-exchange ~hrornatography.~~2 Pentaethoxyphosphorushas been obtained by reaction of diethyl peroxide with triethyl pho~phite.~~,The acetoxytrifluoroalkylphosphines, (CF,),P*OAc and CF,*P( OAc),, havebeen obtained by reaction of silver acetate and the appropriate chlorophos-phine.364 Slow hydrolysis of Cl,C*PCl, yields the solid, trimeric, and mono-basic acid, Cl,C*P( OH),, which is formulated as [CCl,-HPO*OH],.365 Furtherwork on thiophosphinic acid derivatives is reported, and selenium compounds,e.g., Na[Et2P(S)Se],2H2O have been obtained ;s66 the latter with metal ionsM2+ (e.g., Zn2+) forms complexesr se 1Alkoxyphosphorus-sulphur compounds, e.g., (EtO),PS*SH have been ob-tained by reaction of ethanol with P4S7, and reaction of bromine with thelatter gives P,S,Br4 which, with ethanol yields P,S,(OEt),, formulated as aderivative of the acid (HO),(S)P*S,*P(S)( Two new thioiodides ofphosphorus, PSI, and P214S2, both decompose to give P4S7, PI,, and iodine.368Reaction of phosphorus( 111) iodide with aluminium iodide gives the adductBPI,,AlI,, to which is assigned a probably trigonal-pyramidal structurewith 5 - co- ordinate aluminium ., The hydridotetrafluoro( trifluoromethyl) -phosphate anion, CF,=PF,H-, has been identified.,‘ONew preparations of trialkylarsinesand stibines are described, involving the reaction of an aluminium trialkylwith the oxide M,O, (M = As or Sb).371 In a tertiary arsine, RR’R”As,at least two of the substituents must be aryl groups to permit cleavage bypotassium in dioxan to give, e.g., KAsRR’.372 Further perfluoroalkylarseniccompounds have been prepared, including PhAs(CF,), and the thioarsine,Arsenic, antimony, and bismuth.a6QR. A. Munson, J . Phys. Chem., 1964, 88, 3374.s60 P. W. Schenk and K.Domain, 2. anorg. Chem., 1963, 326, 139; P. W. Schenk~361 G. Mamantov, J. H. Burns, J. R. Hall, and D. B. Lake, Inorg. Chem., 1964,362 R. B. Heslop and J. W. Lethbridge, J . Chromatog., 1964, 13, 199.363 D. B. Denney and H. M. Relles, J . Amer. Chem. SOC., 1964, 86, 3897.364L. K. Peterson and A. B. Burg, J . Amer. Chem. SOC., 1964, 86, 2587.a66 J. F. Nixon, J. Chem. Soc., 1964, 2471.866 W. Kuchen and B. Knop, Angew. Chem., 1964, 76, 476.367 H. Petschik and E. Steger, Angew. Chem., 1964, 76, 344; R. Klement, H.-D.368 M. Baudler, G. Fricke, and K. Fichtner, 2. anorg. Chem., 1964, 327, 124; A. H.369M. Baudler and G. Wetter, 2. anorg. Chem., 1964, 329, 3.370R. G. Cave11 and J. F. Nixon, Proc. Chem. SOC., 1964, 229.8 7 1 W. Stamm and A. Breindel, Angew.Chem., 1964, 76, 99.372 A. Tzschach and W. Lamge, 2. anorg. Chem., 1964, 330, 317.and H. Vietzke, ibid., p. 152.3, 1043.Hahne, H. Schneider, and A. Wild, Chem. Ber., 1964, 97, 1716.Cowley and S. T. Cohen, I w g . Chem., 1964, 3, 780HOLLIDAY: THE TYPICAL ELEMENTS 141M~,AS*SCF,.~~~ Many new compounds with As-N bonds have been re-ported, and the general methods for preparing (R,M),N compounds (M = Asor Sb) have been discussed and used, e.g.374(Me,Si),NH + 3 C k M e , + (Me,As)3N + 2Me3SiC1 + HClThe corresponding Et,As.NEt, and (Me,As),NMe compounds have also beenprepared, and reaction of the latter with lithium gives LieMeNAsMe,, andwith NN-dimethylethylenediamine the compoundMe,As*NMe*CH,*CH,*NMe*AsMe,. 875The cyclic tetra-arsenic heximides, As,(m),, with the structure (18) havebeen obtained by reaction of arsenic(m) iodide or chloride with primaryAsRN'/ 'NR s ' Me- IIAs AsHMe Me*' .S' \MeI N R IAs,! ,AsI i N R /(1 8)amines, or by transamination of As(NMe,),; but amination of the latterwith ButNH, gives (Bu~NH*AsNBu~),,~~~ and use of a secondary aminegives the type of 4-membered ring structure previously whileaddition of bromine gives [(Me2N),AsBr]Br.37s A study of the structureof " cacodyl disulphide ", (Me,As),S,, suggests the formulation (19) withone trigonal-pyramidal arsenic( m) and a tetrahedral arsenic( v) atom, andpossible change-transfer from the arsenic(m) lone pair to the arsenic(v)4~Z-orbitals.~~~ Some organoperoxides, R3M(O*OR'), (M = As or Sb) andR,SbX-OaOR' (X = Br or OR), have been prepared.3s0 A study of thereactions of arsenite ion with anions containing more than one sulphur atomsuggests that the arsenite is strongly nucleophilic, as compared with sul-phite, e.g.:as1s2Os2- + &03'-+ so,,- + S h 0 , ' -S20S2- + (x - + 2SO,,- + (x: - 2)As03S3- + HASO,,-Cryo- and ebullio-scopic studies of solutions of arsenic(m) oxide in arsenichalides indicate solvolysis and polymerisation equilibria, e.g. :382and (AsOX)~lAsX, + AsOX*AsX, + AsX, + (AsOX)~A~X,As,O, + 8AsX3 + GAsOX*AsX,873 W. R. Cullen and N. K. Hota, Canad. J . Chem., 1964, 42, 1123; W. R. Cullen,s 7 4 0. J. Scherer and M. Schmidt, Angew. Chem., 1964, 76, 144; 0. J. Scherer876 0. J. Scherer and M. Schmidt, Angew. Chem., 1964, 76, 787; A.Tzschach and876 D. Hass, 2. anorg. Chem., 1963, 325, 139; 326, 192; H.-J. Vetter, H. Noth,377 H.-J. Vetter, H. Noth, and U. Hayduk, 2. anorg. Chem., 1964, 331, 35; cf. Ann.378 H.-J. Vetter and H. Noth, 2. anorg. Chem., 1964, 330, 233.379 N. Camerman and J. Trotter, J . Chem. SOC., 1964, 219.3ao A. Reiche, J. Dahlmann, and D. List, Annalen, 1964, 678, 167.881 M. Schmidt and R. R. Wiigerle, Chem. Ber., 1963, 96, 3293.~2 E. Thilo and P. Flogel, 2. anorg. Chem., 1964, 329, 244.P. S. Dhaliwal, and W. B. Fox, Inorg. Chem., 1964, 3, 1332.J. F. Schmidt, and M. Schmidt, 2. Naturforsch., 1964, 19b, 447.W. Lange, 2. anorg. Chem., 1964, 326, 280.and W. Jahn, ibid., 1964, 328, 144.Reports, 1962, 59, 199; 1963, 60, 147142 INORGANIC CHEMISTRYand AsF2C1 and AsFC1, have been identified by 19F nuclear magnetic reson-ance and mass-spectral studies of the AsF,-AsCI, sy~tem.3~ Solutions ofthe adducts bipy,MX, (X = C1 or Br; bipy = 2,Y-bipyridyl; M = As, Sb, orBi) in nitrobenzene indicate dissociation in the orderBr > C1 and As > Sb > Bi.884Reactions of the trichlorides, MCl,, with triphenyltinlithium give thecolourless solids (Ph,Sn) 3M.385The unstable diphenylstibine has been prepared by reaction of diphenyl-chlorostibine with lithium aluminium h ~ d r i d e , ~ ~ ~ and the square-pyramidalstructure of pentaphenylantimony has been established (cf.ref. 324).387Several compounds, R,SbX, (R = Me or Et; X = Hal, NO,, OH, or S0,/2)have been prepared, and most have a trigonal-pyramidal structure ;Me,Sb(NO,), contains the Me,Sb2+ cation, and the oxides (R,SbX),O(X = C10,- or Cl-) contain the [(Me,Sb),0I2+ cation.388 Similar com-pounds R,SbY (Y = S or Se) have also been prepared; with R = Me the(possibly cyclic) dimer Me,SbSe, is formed.s8g Antimony( 111) fluoride hasbeen found to fluorinate alkylchlorosilanes and silanols, but will not cleaveSi-0-Si bonds reaction of antimony(v) fluoride with sulphur trioxidegives an adduct formulated as SbF,(SO,F), polymerised in the liquid statethrough fluorosulphate bridges.391 Reaction of antimony(1rr) chloride withlithium dimethylamide gives the easily hydrolysable liquid, (Me,N),Sb.392Several adducts of antimony(v) chloride with donor molecules such asMeN,, HCN, ClCN, when treated with hydrogen chloride, are then formu-lated as hexachloroantimonates(v) ; e.g., methyl azide give~3~3[H,C:NH,][ SbCl,].Some polymeric alkylamino-antimony and -bismuth iodides, e.g., (ISbNR)have been obtained by heating the primary amine adducts of thetri-i~dides.~~* The stability and diamagnetism of the Big5+ ion have beencorrelated with a bond system involving 22 p-electrons in 11 bonding mole-cular orbitals (cf.refs. 280).395 A new bismuth sulphide, BiS,, has been~btained,"~ and a better method for the preparation of the trisulphide isSome hexathiocyanatobismuthates, M:I[Bi(SCN),] (M = Fe,Co, Ni, or Zn), have been prepared by reaction of bismuth nitrate and the383 J. K. Ruff and G. Paulett, I w g . Chem., 1964, 3, 998.384 W.R. Roper and C. J. Wilkins, Inorg. Chem., 1964, 3, 500.385H. Schumann and M. Schmidt, Angew. Chem., 1964, 76, 344.3s'JA. X. Nesmeyanov, A. E. BoriSov, and N. V. Novikova, Izvest. Aka&. Nauk387 P. J. Wheatby, J . Chern. Soc., 1964, 3718.388 G. G. Long, G. 0. Doak, and L. D. Freedman, J . Amer. Chem. SOC., 1964,86,209.889 R. A. Zingaro and A. Merijanian, J . Organmet. Chem., 1964, 1, 369.3 9 o R . Muller and C. Dathe, 2. anorg. Chem., 1964, 330, 195; cf. Ann. Reports,391 R. J. Gillespie and R. A. Rothenbury, Canad. J . Chem., 1964, 42, 416.sg2 K. Moedritzer, Inorg. Chern., 1964, 3, 609.393 J. Goubeau, E. Allenstein, and A. Schmidt, Chem. Ber., 1964, 97, 884; E. Allen-stein and A. Schmidt, ibid., pp. 1286, 1863.394 D. Haw, 2. Chem., 1964, 4, 31, 186.395 J.D. Corbott and R. E. Rundle, Inorg. Chem., 1964, 3, 1408.396 M. S. Silverman, Inorg. Chem., 1964, 3, 1041.39' A. C. Glatz and V. F. Meikleham, J . Electrochem. SOC., 1963, 110, 1231.S.S.S.R., Otdel khim. Nauk, 1963, 194 (178).1962, 59, 147HOLLIDAY: THE TYPICAL ELEMENTS 143metal nitrate in presence of ammonium thiocyanate ; hydrolysis givesbismuthyl t h i ~ c y a n a t e . ~ ~ ~Evidence for the existence of 0, at low temper-atures has been obtained from magnetic-susceptibility data.399 Whencarbon tetrachloride is saturated with ozone and water, white crystals oflimiting composition 2 0 ,,CCl,, 17H,O separate.400 Gaseous hydroxideshave been reviewed.401 Some new dioxygenyl compounds have beenobtained by reaction of dioxygen difluoride with boron trifluoride and someGroup V pentafluorides ; formulation of oxygenyl tetrafluoroborate as 02BF4is confirmed by its reaction with dinitrogen tetroxide to give N0,*BF4 andnitrogen; the 02MF, (M = As or Sb) compounds are stable up to 100" inan inert atmosphere.402 Structural problems associated with S-0 and Se-0bonding have been reviewed,*03 and evidence that in Me,PO and Me,SOthe P-0 and S-0 bonds are double has been given.404 Reactions of oxygendifluoride have been studied; nitrogen bases yield the acid fluoride of thebase and nitrous oxide, and pyrosulphuryl fluoride, FS0,-O*SO,F, can beformed from oxides ofSulphur.A review of the solid allotropes of sulphur has appeared.406Raman spectral studies of molten thiocyanates suggest that in ionic meltsB-CEN is the predominant Several studies of compounds con-taining the C-s,-C bond system have been published; in Cl,C*S,*CCl, thetwo S-S bond lengths are equal and imply some double-bond character,while the staggered configuration of the sulphur chain is attributed tointeractions between the chlorine atoms and the central sulphur atom.408In the dicyanotrisulphane, NC-S,*CN, the CN groups are cis to the linearsulphur chain, and reaction with bromine breaks the latter, giving finallythe cyclic cyanuric derivative (-N*C-SBr) ,.do9 Reaction of perfluoro-hydrazine with the bistrifluororomethyl disulphide, F,C*S,*CF,, gives theunstable F3C-S*NF,.41c Lithium triphenyltin sulphide, LiPh,SnS, preparedby reaction of sulphur with LiPh,Sn, can be used in metathetic reactions;e.g., with Ph3PbC1 the product is Ph,Sn*S*PbPh,.411 The reaction of MIVR,(M = Si, Ge, or Sn; R = Bu or Ph) compounds with sulphur, previouslyobserved for Ph,Sn, has been generalised, and is considered to proceed byGroup VI.Oxygen.I39* A. CygEbnski, Zeszyty Nauk Politech. lodz., 1964, 41, 45.399 L. N. Mulay and L. L. Keys, J . Amer. Chem. SOC., 1964, 86, 4489.400 G. McTurk and J. G. Waller, Nature, 1964, 202, 1107.401 0. Glemser and H. G. Wendlandt, Adu. Inorg. Chem. Radiochem., 1963, 5,215.40z I. J. Solomon, R. I. Brabets, R. K. Uenishi, J. N. Keith, and J. M. McDonough,Inorg. Chem., 1964, 3, 457; A. R. Young 11, T. Hirata, and S. I. Morrow, J . Amer.Chem. SOC., 1964, 86, 20.403 R.Paetzold, 2. Chem., 1964, 4, 321.404 P. Haake, W. B. Miller, and D. A. Tyssee, J . Amer. Chem. SOC., 1964, 88, 3577.405 R. A. Rhein and G. H. Cady, Inorg. Chem., 1964, 3, 1644; G. Franz and F.Neumayr, Inorg. Chem., 1964, 3, 921.406 B. Meyer, Chem. Rev., 1964, 64, 429.407 C. B. Baddiel and G. J. Janz, Tram. Faraday SOC., 1964, 60, 2009.40a H. J. Berthold, 2. anorg. Chem., 1963, 325, 237.409 F. Feher and K.-H. Linke, 2. anurg. Chem., 1064, 327, 151; Chem. Ber., 1964,410 E. C. Stump, Jr., and C. D. Padgett, Inorg. Chem., 1964, 3, 610.411 H. Schumann, K. F. Thorn, and M. Schmidt, J . Organmet. Chem., 1963, 1, 167.97, 2413144 INORGANIC CHEMISTRYcarbanion rupture of S-S b0nds.4~~ Sulphoxylic acid, H2S02, has been postu-lated as an intermediate product of hydrolysis of trithiazyl chloride, thefinal products being thiosulphate and trithionate.413 Compounds of thetype, R*C6H4*SN:S:NS*C6H4R (R = H, Cl, Br, or OMe) have been pre-pared by reaction of Grignard reagents with tetrasulphur tetranitride,41*and reaction of the latter with phenyldichlorophosphine givesPhPC1,:N-PC1Ph:S.Sulphur-nitrogen bonds can also be broken by reaction of boron trichloridewith, e.g., MeS-NMe,, to give Me2N-BC12 and C1SMe.41s Further work onthionyl imide, OS:NH, prepared from thionyl chloride and ammonia, indi-cates that it is monomeric in the gas phase and reacts with water to giveS4N4 and NH4HS04.41' A new S-N heterocycle (20) is obtained by reactionof NN-dimethylurea with the chloride of imidodisulphuric acid; it is aMe N#C\ NMe MevCO j S e , .COMeMe*CO 'se/ 'COMeI :c cstrong acid, and some salts have been prepared.418 The reactions of element-ary sulphur with nitrites, phosphites, and arsenites have been studied;nitrite (in dimethylformamide) reacts to give an unstable thionitrite (whichdecomposes to nitrous oxide and thiosulphate), phosphite does not react,and arsenite breaks the S, ring to give, finally, thioarsenite (cf.ref. 381).41aFurther methods of preparing disulphur monoxide have been re-ported,420,421 and alkali-metal derivatives of dimethyl sulphoxide have beenprepared by direct reacti~n.*~Z Dimethyl sulphoxide behaves as a strongbase, dialkylsulphanes are weak bases, and diarylsulphanes are non-electro-lytes in sulphuric acid as solvent;423 Raman spectral stildies suggest a lowdegree of dissociation of H2S,0, in this solvent, and that H,S,Olo is thehighest oleurn existing in it as such.424 Many free thio-acids have beenobtained and stabilised by chilling solutions in organic solvents ;425 reactionof one of these, thiosulphuric acid, with thionyl and sulphuryl chloride, gives412 M.Schmidt and H. Schumann, 8. anorg. Chem., 1963,325, 130; cf. Ann. Reporcs,413 Oskar Glemser, S. Austin, and F. Gerhart, 1964, 97, 1262.414 J. Weiss and H. Piechaczek, 8. Naturforsch., 1963, 18b, 1139.416 E. Fluck and R. M. Reinisch, 2. anorg. Chem., 1964, 328, 165, 172.u6 H. Noth and G. Mikulaschek, Chem. Ber., 1964, 97, 709.417 P. W. Schenk, E. Krone, and H. Kartono-Soeratinam, Monatsh., 1964, 95, 710.*la H.Thielemann, H.-A. Schlotter, and M. Becke-Goehring, 2. anorg. Chem., 1964,529, 235.419M. Schmidt and R. Wiigerle, 8. anorg. Chern., 1964, 530, 48.420 P. W. Schenck and R. Steudel, Angew. Chem., 1964, 76, 97; P. W. Schenck,R. Steudel, and M. Topert, 8. Natzsrforsch., 1964, 19b, 535; S. R. Satyanarayana andA. R. V. Murthy, 2. anorg. Chem., 1964, 330, 245.1963, 60, 194.421 M. Schmidt and D. Eichseldorfer, 8. anorg. Chem., 1964, 330, 130.422 A. Ledwith and N. McFarlane, Proc. Chem. SOC., 1964, 108.42g S. K. Hall and E. A. Robinson, Canad. J . Chem., 1964, 42, 1113.424 G. A. Walrafen, J . Chem. Phye., 1964, 40, 2326; cf. Ann. Reports, 1962, 59, 149.426 M. Schmidt and M. Wieber, 8. anorg. Chem., 1963, 326, 170, 174, 182HOLLIDAY: THE TYPICAL ELEMENTS 145derivatives of di- and tri-sulphanedisulphonic acids, respectively, e.g.,H0,S*S*(SO)-S*S03H, and the properties of some potassium sulphanedisul-phonates have been extensively investigated.426 Thiodiphosphoric acidsS,(PO,H,), (x = 3-10) have been prepared as unstable oils by reactionof monothiophosphoric acid with chlorosulphanes, S,Cl, (x = 1-8) ; thebarium salts are stable and the free acids react with other acids such as HCN,thus :427Sz(P03H,), + (x - 1)HCN + 2H,O + ZH3P0, + H2S + (z - 1)HSCNReaction of sulphuryl chloride in benzene with hydrogen sulphide gives S20and other products ; with liquid hydrogen sulphide, sulphanes and chloro-sulphanes are f0rmed.42~ Some reactions of sulphuryl di-isocyanate,O,S(NCO),, have been studied; reaction with dimethyl sulphoxide gives thecompound, Me,S:N(SO,)N: SMe2.428 Further discussion of the isomerismof disulphur difluoride suggests that both positional and geometrical isomer-ism is possible, with a pyramidal S=SF2 and (possibly) cis and trans (non-planar) FS=SF.429 Sulphur hexafluoride, usually considered to be un-reactive, is rapidly and completely decomposed by sodium at 20" in a glycolether to give sodium sulphide and sodium fluorideY430 and easily by hydrogeniodide at 30" to give hydrogen sulphide, hydrogen fluoride, and iodine.alPentafluorosulphur chloride, SF5Cl, has been prepared in high yield byreaction of sulphur tetrafluoride and chlorine in presence of czesium fluoride(CsSF, being a likely intermediate); it undergoes reactions with nitriles togive SF,*N< derivatives ; e.g., CF,*CN gives SF,*N: CC1*CF,.432 Caesiurrifluoride is also used in the preparation of Dhe oxyfluoride, SF,*OF, fromthionyl fluoride and fluorine.433 Further reactions of fluorosulphur peroxideshave been reported, e.g., reactions with perfluoro-olefins ;*:4 reaction of sul-phur dioxide with the compound SF5*O-SF,*O-O*SF, gives the new product,SF,~O~S02*O*SF4*O*SF5.435 The new compounds, CF,*O*SF5, (CF,*O),SF,,and CF,*O*SF,*NF,, have also been prepared and characterised.&G Thecyclic a( trans)-sulphanuric chloride, when treated with potassium fluoride incarbon tetrachloride at 145", gives a mixture of the stable, cyclic cis- andtrans-sulphanuric fluoride^.^' Conductivity and transport measurementsof fluorosulphates dissolved in fltnrosulphuric acid suggest the self-ionisation,426 M.Schmidt and T. Sand, Chem. Ber., 1964, 97, 282; J . Inorg. Nuclear Chem.,427 M. Schmidt, A. Fassler, and F. I. Rankl, Chem. Ber., 1964, 97, 1075, 1082.428 R. Appel and H. Rittersbacher, Chem. Ber., 1964, 97, 849, 852.4a0 F. Seel and R. Budenz, Chimia (Switz.), 1963, 17, 355; F. Seel and D. Golitz,2. anorg. Chem., 1364, 327, 32; F. Seel, R. Budenz, and D. Werner, Chem. Ber., 1964,97, 1369; R. L. Kuozkowski, J. Amer. Chem. SOC., 1964, 88, 3617.1964, 26, 1165, 1173, 1179, 1185, 1189.G. C. Domitras and A. G. MacDiarmid, Inorg. Chem., 1964, 3, 1198.D. K. Padina and A. R. V . Murthy, Inorg. Chem., 1964, 3, 1653.4ae C.W. Tullock, D. D. Coffman, and E. L. Muetterties, J . Amer. Chem. SOC.,488 J . K. Ruff and M. Lustig, Inorg. Chem., 1964, 3, 1422.484 C. T. RatcliiTe and J. M. Shreeve, Inorg. Chem., 1964, 3, 631; J. R. Case and436 L. C. Duncan and G. H. Cady, Inorg. Chem., 1964, 3, 850, 1045.487 F. See1 Qnd G. Simon, 2. Naturforsch., 1964, lob, 354; cf. Ann. Reports, 1962,1964, 86, 357.G. Pass, J. Qhm. Soc., 1964, 946.G. Pass, J . Chem. SOC., 1963, 6047.59, 148146 INORGANIC CHEMISTRY2HS03F + H,SOF+ + so3F-,438 and exchange experiments with disulphurdichloride as a solvent suggest ready dissociation only with a strong chloride-accept or solute .439Oxidation of potassium selenocyanate withiodine pentafluoride gives first selenocyanogen, (SeCN),, and this decom-poses to give selenium selenocyanate Se(SeCN), and selenium cyanide ; thereis no evidence for the corresponding TeCN- ion.440 Selenides and telluridesof the type, (R3M),Se (M = Si, Ge, or Sn) have been prepared by usingcompounds Li[R3MSe] ;441 and the phosphine telluride Bun3P*Te has beenobtained by direct reacti0n.~4~ Reaction of dimethyl selenate with am-monia yields the unstable selenic diamide, SeO,(NH,),, which is convertedinto NH,NSeO, at -50°.443 Solutions of sublimed selenium trioxide inliquid sulphur dioxide may be used for selenation; e.g., Me3SiC1 givesMe3Si*Se0,C1 (but Me3SnC1 gives only Me3SnC1-SeO,).Alkanethiols withselenium trioxide give the “ half-esters ” of thioselenic acid, i.e., O,Se*SHR,and reaction with hydrogen peroxide gives peroxomonoselenic acid H,SeO, ;the corresponding peroxoselenious acid, H,Se(1v)0, is more stable thanH,S( I V ) ~ , which rearranges to form H,S( VI)O,.~U Peroxomonotelluric acidcan be obtained by reaction of hydrogen peroxide with potassium t e l l ~ r a t e .~ ~ ~The structures of acetylacetonate derivatives of sulphur, selenium, andtellurium have been investigated ; reaction of selenium tetrachloride withacetylacetone gives the diselenacylobutane derivative (21) ,446 The adduct,SeCl,,Zpy, has been shown to be [SeCl,py2]+C1-.447 Reaction of an alkali-metal (K, Rb, or Cs) fluoride with tellurium dioxide and selenium tetra-fluoride gives the pentafluorotellurates(Iv), MTeF5,448 and reaction of bariumtellurate and fluorosulphuric acid gives pentafluoro-orthotelluric acid,HOTeF 5, which undergoes rapid hydrolysis to telluric and hydrofluoricacid.449 The supposed uronium pentachlorotellurate( IV) is now consideredto be ammonium hexachlorotellurate( IV) .450Group VII.-Reviews of inorganic and organic hypofluorit es,451 oxidesand oxyfluorides of the halogen^,"^, and perchloric acid 453 have appeared.Selenium and tellurium,438 J.Barr, R. J. Gillespie, and R. C. Thompson, Inorg. Chem., 1964, 3, 1149.43g R. R. Wiggle and T. H. Norris, Inorg. Chem., 1964, 3, 539.440 E. E. Aynsley, N. N. Greenwood, and M. J. Sprague, J . Chem. SOC., 1964, 704;441 H. Schumann, K. F. Thom, and M. Schmidt, J . Orgunomet. Chem., 1964, 2, 361;442 R. A. Zingaro, J . Orgunomet. Chenz., 1963, 1, 200.443 K.DostB and L. Zborilova, 2. Chem., 1964, 4, 352.444 M. Schmidt and I. Wilhelm, Chem. Ber., 1964, 97, 872, 876; 2. anorg. Chem.,1964, 330, 324; M. Schmidt and P. Bornmann, 2. anorg. Chem., 1964, 330, 328; 331, 92.445 M. Schmidt and P. Bornmann, 2. Nuturforsch., 1964, lgb, 73.448 D. H. Dewar, J. E. Fergusson, P. R. Hentschel, C. J . Wilkins, andP. P. Williams,J . Chem. SOC., 1964, 688.447 A. W. Cordes and T. V. Hughes, Inorg. Chem., 1964, 3, 1640.448 A. J. Edwards, M. A. Mouty, R. D. Peacock, and A. J. Suddens, J . Chem. SOC.,44@A. Engelbrecht and F. Sladky, Angew. Chem., 1964, 76, 379.450 I. R. Beattie, H. Chudzynska, R. Hulme, and (in part) E. E. Aynsley, Chem.4 5 1 C. J. Hoffman, Chern. Rev., 1964, 64, 91.452 M. Schmeisser and K.Brandle, Adv. Inorg. Chem. Radiochem.. 1963, 5, 42.45sA. A. Zinov’ev, Uspekhi Khim., 1963, 32, 590 (268).N. N. Greenwood, R. Little, and 35. J. Sprague, ibid., p. 1292.I. Ruidisch and M. Schmidt, ibid., 1963, 1, 160.1964, 4087.and Id., 1963, 1842; cf. Ann. Reports, 1963, 60, 202HOLLIDAY: THE TYPICAL ELEMENTS 147The reaction Me,NF(s) + HF(g) -+ Me,NHF(s) has been used to obtain avalue of -37 kcal./mole for the energy of the hydrogen bond in the HF2-and crystalline salts R,N+HXY- containing the hydrogen dihalideions HBrC1-, HClI-, and HI2- are reported; the strength of the bond inthe HX molecule produced determines the course of their decompo~ition.~~The fluorides CIF, and BrF, have been investigated as possible solvents;reactions with alkali-metal fluorides MIF give MClF, and MBrF, salts,respectively ; and the crystalline solid, NOClF,, has also been obtained.456Reaction of boron trichloride with refractory metal oxides, e.g., Fe203, athigh temperatures (-1000') has been suggested as a means of preparinganhydrous chlorides,&' and methods for the preparation of anhydrous hydro-gen bromide 45* and of pure hydrobromic and hydriodic acid 459 have beendescribed.A number of amine-interhalogen adducts D,IX, and D,,IX,(D = acridine, isoquinoline, or pyridine; X = C1 or Br; n = 1 or 3) havebeenICI, > IC1 > IBr;studies of triethylamine-iodine mixtures in n-heptane suggest existence ofa complex [Et3N),1]+I-.461 Reactions between iodine pentoxide and iodinein the solvents H2S04, H,S,07, and H2Se0, have given the compounds1203,so3, I,03,4S03,H,0, and I,03,Se03; these yield 120, on slowhydrolysis.462 Further studies relating to iodine cations and oxycationssuggest that iodic acid in sulphuric acid exists as solvated or polymericforms of I0,,HS04, and 1 :3 HI03-I, mixtures as I0,HS04, which behavesas a weak electrolyte.463 There is evidence that the " bi-iodate " KH(I03)2exists only in the solid state or in very concentrated solution;464 heatingof orthoperiodic acid gives a product with 1207 : 1,05 = 1 : 1 ,465 and formationof the paramagnetic Na,I( w)04 is suggested by thermal decomposition ofdisodium periodate.466 Thermal decomposition of czsium di-iodoastatate( I),CsAtI,, gives all the astatine in the gaseous fraction, as expected for apolyhalide de~omposition.4~7 The chemistry of astatine has beenre~iewed.~esand acceptor strength decreases in the order454 S.A. HarreU and D. H. MeDaniel, J . Amer. Cheirt. SOC., 1964, 86, 4497.455 J. A. Salthouse and T. C. Waddington, J . Chem. SOC., 1964, 4664; K. M. Harmon456 E. D. Whitney, R. 0. MacLaren, C. E. Fogle, and T. J. Hurley, J . Amer. Ckem.457 B. Attwood and R. A. J. Shelton, J . Inorg. Nuclear Chem., 1964, 26, 1758.458A. D. B. Sloan, Chem. and I d . , 1963, 574.469 H. Irving and P. D. Wilson, Chem. and I,&., 1964, 653.460 R. D. Whitaker, J . Inorg. Nuclear Chem., 1964, 26, 1405.461 C. D. Schmulbach and D. M. Hart, J . Anaer. Chem. SOC., 1964, 86, 2347.462 G. Daehlie and A. Kjekshus, Acta Chem.Scand., 1964, 18, 144.469 R. J. Gillespie and J. B. Senior, Inorg. Chem., 1964, 3, 440, 972.484 J. F. Harvey, J. P. Redfern, and J. E. Salmon, J . Inorg. Nuclear Chem., 1964,465 L. Pacesova and Z. Hauptman, 2. anorg. Chem., 1963, 325, 325.466 M. Dratovskii, Zhur. neorg. Khim., 1963, 8, 2434 (1276).467 G. A. Brinkman, J. T. Veenboer, and A. H. W. Aten, Jr., Radiochim. Acta468A. H. W. Aten, Jr., Adu. Inorg. Chem. Radiochem., 1964, 6, 207.and P. A. Gebauer, Inorg. Chem., 1963, 2, 1319.SOC., 1964, 86, 2583, 4340.26, 1328.1963, 2, 483. THE TRANSITION ELEMENTSBy D. Nicholls(The Donnan Chemistry Laboratories, The University of Liverpool)THE year's progress in transition-metal chemistry will be reviewed in theusual way; within each group, compounds will be mentioned in order ofincreasing oxidation number of the central metal atom.General reviewsthat have appeared during 1964 have been concerned with the stabilisationof oxidation states of the transition metaIs,l the spectra of transition-metalions in crystalsY2 peroxy-compounds of the transition metals,, and theMossbauer effect in chemistry.4Scandium and the Lanthanides.-The reactions of the rare-earth metalswith sulphur at around 800" have been studied and polysulphides of terbium,holmium, and erbium have been prepared for the &st time.s Europiumdicarbide, EuC,, obtained by the reaction of the oxide with carbon at 1450"or from the metal and carbon at 1050", is a black solid hydrolysing rapidlyin moist air to give acetylene.s The magnetic susceptibilities of neodymiumchlorides and iodides have been determined over a wide temperature range;they confirm the 4f4 configuration of the cation in the two neodymium(@halides as well as the presence of the expected low-lying excited state.'The chemistry of the hydroxides and hydroxide chlorides of the scandiumgroup and the lanthanides has been reviewed.8 Double fluorides, NaMF,,have been prepared for the tervalent lanthanides, plutonium, and americi~m.~Several types of complex of lanthanide chlorides and thiocyanates with1 ,IO-phenanthroline (phen) have been isolated. All the lanthanides exceptpromethium form [M(phen) 3]( SCN), complexes which dissociate in solution;the chlorides form only bis-( 1 ,lo-phenanthroline) complexes and mostof these are solvated, e.g., [M(phen),(H2O)C1]C1,.1O The unstable peroxideacetate, Ce2( 02)3(C2H302)2, is precipitated from aqueous solutions containingacetic acid, sodium acetate, cerium(m) nitrate, and hydrogen peroxide.llThe Actinides.-The neutral complex, U(bipy), (bipy= 2,2'-bipyridyl),slowly loses bipyridyl in vacuo above 135"; it has a room-temperaturemagnetic moment between 2-52 and 2.81 B.M.12 Uranium monophosphide,UP, is satisfactorily prepared from h e l y divided uranium and phosphinea t 385"; it is stable to oxidation and hydrolysis at room temperature.131 R.S. Nyholm and M. L. Tobe, Adv. Inorg. Chem. Radiochem., 1963, 5, 1.a J. Ferguson, Rev. Pure Appl. Chem. (Awtralia), 1964, 14, 1.8 J. A. Connor and E. A.V. Ebsworth, Adv. Inorg. Chem. Radiochem., 1964,6,280.4 C . C. Addison and N. Logan, Adv. Inorg. Chem. Radiochem., 1964, 6, 72.S. A. Ring and M. Tecotzky, Inorg. Chem., 1964, 3, 182.R. E. Gebelt and H. A. Eick, Inorg. Chem., 1964, 3, 335.R. A. Sallach and J. D. Corbett, Inorg. Chem., 1964, 3, 993.C. Keller and H. Schmutz, 2. Naturforsch., 1964, 18b, 1080.* N. V. Aksel'rud, Uspekhi Khim., 1963, 32, 800 (353).*1oF. A. Hart and F. P. Laming, J . Inorg. Nuclear Chem., 1964, 26, 579.11C. G. Warren, J . Inorg. Nuclear Chm., 1964, 26, 1391.l2 S. Herzog and H. Oberender, 2. Chem., 1963, 3, 429.13 Y. Baskin and P. D. Shdek, J . Inorg. Nuclear. Chem., 1964, 26, 1679.* For Russian journals, figures in parentheses are page numbers of the British or American translation8NICHOLLS : THE TRANSITION ELEMENTS 149Eachthorium atom has eight iodine neighbours a t the corners of an irregularpolyhedron (which is approximately a square antiprism) ; these polyhedrashare edges and triangular faces to form layers which are only weakly bondedto each other.14 Thorium(rv) chloride forms a complex, ThCl4,4DMA (withNN-dimethylacetamide) from which the corresponding nitrate, thiocyanate,and perchlorate complexes have been prepared.15 The thermal decomposi-tion of U02F2(N2H4HF),,16H20 at 200" in wacuo results in reduction of theuranium to UF4,N2H4HF,H,0 ; at 400" pure uranium(m) fluoride is obtained.lsStudies of the NH4F-UF4-H,0 system have shown that emerald-green(NH4),UF, is the solid phase in equilibrium with aqueous solutions containing24.2A5-1 yo of ammonium fluoride.The lower complexes (NH4)2UF, and7NH4F,6UF4 are obtained from solutions containing less than 24-2y0 ofammonium fluoride; the former complex is polymorphic, exhibiting fourcrystalline modifications near room temperature.1' Solutions of uranium(rv)chloride in ethanol undergosolvolysis inthepresenceof 2,2'-bipyridyl and 1,lO-phenanthroline ; the hexachlorouranates(w), (bipyH),UCl, and (phenH),UCl,,and the addition compounds, UCl,(OEt)(bipy), and UCl,(OEt)(phen),, havebeen isolated.18 Oxidation of the chloride (R3PH),Uc1,, with air gives thetetrachlorodioxouranates( IV), ( R3PH)2U02C14, but oxidation with chlorinegives uranium(1v) chloride bis(phosphine oxide) addition a'.e. :(R,PH),UCI, + 2C1, + 2H,0~UC1,,2R3P0 + 6HClThe attempted preparation of uranium(1v) thiocyanate from uranium(w)chloride and potassium thiocyanate has resulted in the isolation of grey-green K,U(NCS),.The magnetic properties of this compound and of someother uranium(m) complexes, including U( SCN),,4DMA, have been reportedfor the temperature range 8 6 - 3 0 0 " ~ . ~ ~ A spectrophotometric study of thenitrate complexes of uranium(m) indicates the presence of the four species,U4+, UOH3+, UNOS3+, and H2U(N0,),.21 The sulphate complexes ofneptunium have been examined polarographically ; while there is evidencefor NPSO,~+ and Np(SO,),, there are no stable sulphate complexes of nep-tunium(m).22The white protactinium(v) fluoride is isomorphous with P-UF, and canbe distilled in wacuo above 500".Thermal decomposition of the hydrate,PaF5,2H20, at 160" yields a new hygroscopic oxfluoride, Pa,OF,; it decom-poses at 800", giving PaF, and an unidentified residue.23 A very simple andmost useful preparation of PaC1, (and also of NbCl, and TaC1,) involves thereaction of the quinquevalent metal hydroxide with thionyl chloride at roomThorium(rv) iodide has a novel layer structure in the solid state.l4 A. Zalkin, J. D. Forrester, and D. H. Templeton, Inorg. Chem., 1964, 3, 639.K. W. Bagnall, D. Brown, P. J. Jones, and P. 8. Robinson, J . Chem. Soc., 1964,B. Sahoo and K. C. Satapathy, J . I w g . Nuclear. Chem., 1964, 26, 1379.l7 R. A. Penneman, F. H. ECTuse, R. S. George, and J. S. Coleman, Inorg. Chem.,lap.Gans and B. C. Smith, J. Chem. SOC., 1964, 4177.lo P. Gans and B. C. Smith, J . Chm. SOC., 1964, 4172.2o K. W. Bagnall, D. Brown, and R. Colton, J . Chem. SOC., 1964, 2527.21 H. A. C. McKay and J. L. Woodhead, J. Chem. SOC., 1964, 717.22 M. C. Musikas, Radiochim. Acta, 1963, 1, 92.2a L. Stein, Inorg. Chem., 1964, 3, 995.2531.1964, 3, 309150 INORGANIC CHEMISTRYtemperature for twenty-four hours. Hexachloroprotactinates(v), MPaC1,(M = Cs, Me,N, or Ph,As), and the octachloroprotactinate(v), (Me4N),PaC1,,have been prepared from thionyl chloride solutions of PaC15.24 Anhydrousuranium( v) fluoride is very soluble in concentrated aqueous hydrogenfluoride, giving stable uranium( v) solutions. Blue crystals of HUF,,2-5H20are formed on cooling a 5M-sohtion of uranium(v) from 25" to -10"; thesalts, CsUF, and RbUF,, are precipitated readily on addition of the alkali-metal fluorides to the solution at room temperat~re.~~ In addition to theisolation of several hexachlorouranates and (Me,N),UCl, from thionylchloride solutions of uranium( v) chloride, conductimetric evidence has beenobtained for the existence of the UC1,2- ion in these solutions.26 Hydrogenbonding between alkylammonium and hydronium cations as donors and thecomplex anions UC1,2- and UBr,2- has been demonstrated spectrophoto-metrically.This hydrogen bonding partially distorts the octahedral fieldaround the U4+ ion, thereby allowing the normally forbidden electric dipole-induced internal 5felectronic transitions to occur.27 The absorption spectrumof the uranium(v) ion in carbon tetrachloride solutions of UC1,,SOC12 andU(OEt), have been measured, and energy levels have been assigned on thebasis of a 5f1 configuration for the uranium(v) ion.28 Oxidation of aqueoussuspensions of neptuniumtv) hydroxide by ozone at 18" and 90" givesNpO3,2H,O and NpO,,H,O, respectively.Thermal decomposition of thelatter hydrate above 300 " yields black neptunium(v) oxide, Np20 ;29 thisoxide is also formed in the reaction of metallic neptunium with lithiumperchlorate or when ozone is bubbled through molten lithium perchloratecontaining the Np02+ ion.30Uranium( VI) fluoride reacts with hydrogen sulphide at 25 ", givingUF4,SF, and hydrogen fluoride ; with carbon disulphide, the complexUF4,SF4 is again formed along with (CF,),S2 and (CF3),S,.3l Some additioncompounds of uranyl nitrate, i.e., U02(N03)2,N204, U02(N0,),,2MeCN, andU02(N0,),,2EtOAc, have been isolated and the anhydrous uranyl nitratehas been obtained on thermal decomposition of the N20, adduct at 163".32The red precipitate formed when quinolin-8-01 is added to a neutral solutionof the uranyl ion contains three quinolinol molecules co-ordinated to theuranium atom, but these are not all equivalent; all three phenolic oxygenatoms are co-ordinated, but only in two of the ligand molecules is the nitrogenbonded to the uranium.33 The crystal structures of the body-centredtetragonal Li4U05 and Na4U05 are interesting in that they represent auranium-oxygen configuration which does not contain the uranyl group ;U042- rather than UOz2+ characterises the24 K.W. Bagnall and D. Brown, J . Chem. SOC., 1964, 3021.25 L. B. Asprey and R. A. Penneman, Inorg. Ghem., 1964, 3, 727.26 K. W. Bagnall, D. Brown, and J. G. H. du Preez, J . Chem. SOC., 1964, 2603.27 J. L. Ryan, Inorg. Chm., 1964, 3, 211.2* D. G. Karraker, Inorg. Chem., 1964, 3, 1618.29 K. W. Bagnall and J. B. Laidler, J . Chem. SOC., 1964, 2693.30 D. Cohen and A. J. Walter, J . Chern. SOC., 1964, 2696.31 L. E. Trevorrow, J. Fischer, and W. H. Gunther, Inwg. Chem., 1963, 2, 1281.32 C. C. Addison, H. A. J. Champ, N. Hodge, and A. H. Norbury, J . Chem. Soc.,33 D. Hall, A. D. Rae, and T. N. Waters, Proc. Chem. Soc., 1964, 21.8 4 H. Hoekstra and S. Siegel, J .Inorg. Nuclear Chem., 1964, 26, 693.1964, 2354NICHOLLS : THE TRANSITION ELEMENTS 151!Citanium, Zirconium, and Hahitlm.-Zirconium(Ir) fluoride has beenprepared by the action of atomic hydrogen on thin layers of zirconium(1v)fluoride at about 350". It is a black solid which, when warm, ignites in air;a t 800 " it disproportionates to zirconium and zirconium(Iv) fluoride.35Titanium(m) chloride reacts with 1 ,P-dioxan, 174-thioxan, morpholine, andketones to form TiC1,,3L, TiCl,,ZL, and TiCl,,L, the product dependingupon the experimental conditions and the ligand used ; ethylene glycoldimethyl ether gives a compound of empirical formula TiCl,,l-S(CH,*OMe),,and the spectra of the complexes are discussed.36 By reaction of TiC13,3THFor TiC14,2THF (THF = tetrahydrofuran) with LiPR, (R = cyclohexyl),brown crystals of Ti(PR,), are obtained; oxidation of this compound withiodine gives products TiI,(PR), and TiI,(PR,).37 Two phosphates of com-position Ti,0,,3P,05 have been obtained.Titanium(@ tetrametaphos-phate, Ti4( P4012)3, forms bright-blue crystals having cyclic anions containingfour PO4 tetrahedra ; the purple-blue polyphosphate, Ti(P0,) 3, has chainsof ( P03)zz- anions.38 Zirconium(II1) chloride has been prepared from zir-conium(1v) chloride and metallic zirconium at 500" and 60 atm.39 and in atemperature gradient at 1 atm.40 Electronic energy-level diagrams for thecomplex, TiF63-, have been calculated on a molecular-orbital scheme, byassuming ideal octahedral co-ordination and taking n-bonding into account,but not considering ligand-ligand interactions.The value of 17,500 cm. -lfor lODp obtained from calculated energy levels compares favourably withthat observed in the spectra of TiF6,- salts.41The nitride halides of titanium(1v) and zirconium( 1v) have received extensivestudy. There are two niodifications of ZrNCl and ZrNBr ; the high-tempera-ture p-forms have structures characterised by a hexagonal random sequenceof XZrNNZrX layers. Ammonolysis of zirconium(rv) iodide at 500" givesZrNI as orange platelets, very sensitive to moisture ; at 750" the ammonolysisproduces a dark-blue zirconium nitride, Zr,N (0.94 > z > 0.81) which at1000" is transformed into metallic ZrN.43 Hydrazine reacts violently withtitanium(1v) halides and causes reduction in non-aqueous solvents ; sub-stituted hydrazines solvolyse the halides, forming, e.g., TiCl,( NH*NHPh) andTiCl,(NH*LMe,), in admixture with the hydrazine hydrochlorides.44 Withtertiary aromatic amines, phosphines, and arsines, titanium(rv) chloride andbromide form TiX,,L or TiX4,2L complexes ; zirconium halides give onlyZrX,,ZL compounds.The thioxan adducts TiX,,2C4H,0S have bondingfrom sulphur With the tritertiary arsine, MeAs[(CH,),*AsMe,],A review has appeared on structural aspects of zirconium35 F. K. McTaggart and A. G. Turnbull, AustruE. J. Cihem., 1964, 17, 727.36 G. W. A. Fowles, R. A. Hoodless, and R. A, Walton, J . Chem. SOC., 1963, 5873.37 K. Issleib and E. Wenschuh, Chem. Ber., 1964, 97, 715.38F.Liebau and H. P. Williams, Angew. Chem., 1964, 76, 303.39 H. L. Schliifer and H.-W. Wille, 2. anorg. Chem., 1964, 327, 253.40 B. Swaroop and S. N. Flengas, Cunad. J. Chem., 1964, 42, 1494.41 H. D. Bedon, S. M. Homer, and S. Y. Tyree, Inorg. Chem., 1964, 3, 647.4 2 A. Clearfield, Rev. Pure AppE. Chem. (Amtrdia), 1964, 14, 91.43 R. Juza and J. Heners, 2. anorg. Chem., 1964, 332, 159; R. Juza and W. Klose,ibid., 1964, 327, 207; R. Juza, A. Gabel, A. Rabenau, and W. Klose, ibid., 1964, 329,136; R. Juza and I. Nitschke, ibid., 1964, 332, 1.44 D. Nicholls and R. Swindells, J. Chem. SOC., 1964, 4204.45 G. W. A. Fowles and R. A. Walton, J. Chem. SOC., 1964, 4330152 INORGANIC CHEMISTRY(TAS) the composition of the adduct differs for each titanium(rv) halide.Thus products obtained are (TiF,),,TAS (white), (TiCl,),,TAS (crimson),TiBr4,TAS (crimson) , and [TiI,,TAS]I (pale yellow) .46 In methyl cyanide,titanium( IT) chloride is strongly solvated and conductance data 47 indicatethat the solvate dissociates according to the equationBTiCl,(CH,*CN), [TiCl,(CH,*CN),]+ + [TiCI,(CH,*CN)]-Ultraviolet spectra of the methyl and ethyl cyanide adducts of titanium(rv)and zirconium(Iv) halides have been recorded.48 Isocyanates of titanium(rv)have been obtained by reaction of silver isocyanate with alkoxytitanium(1v)halides; (EtO),Ti(NCO) forms colourless crystals and gives a 1 : 1 adductwith ammonia.4g Charge-transfer complexes, e.g., bright-yellow 2TiCl,,HMB,have been isolated from titanium@) chloride and hexamethylbenzene (HMB)or phenanthrene by precipitation from inert solvents.50Contrary to earlier beliefs the do system titanium(Iv) forms strongercomplexes with sulphur than with oxygen donors; solid complexes, TiX4,2L(L=Me,S, Et,S, tetrahydrothiophen, or tetrahydrothiopyran; X = C1 or Br),have been isolated.51 Crystals of ZrF4,3H,0 are triclinic with two moleculesin the unit cell; the molecule is dimeric and best formulated with fluorinebridges, i.e., as di-p-fluorohexafluorohexaquodizirconium(Iv) .52 The hydratesof hafnium(rv) fluoride and oxyfluoride, HfF4,3H,0, HfF4,H,0, Hf20F6,H,0,and the oxyfluorides, Hf,0F6 and Hf3O2F8, have been ~haracterised.~, Incarefully dried benzene, the molecular weight of titanium(1v) ethoxide isindependent of concentration in the range 2-100 x 1 0 - s ~ ; a single trimericspecies appears to be present in contrast to the tetrameric nature of thes0lid.6~ While the association of Ti(OEt), is insensitive to whether benzene,or dioxan is the solvent, novel association is observed for the n-propyl,n-butyl, and n-pentyl alkoxides in dioxan, so that solvation occurs here andlarge solute aggregates are created by the bifunctional dioxan moleculebridging [Ti( OR),], species in Partial hydrolysis of tetrakis-(trimethy1siloxy)zirconium in dioxan yields solid polymeric compounds,[ZrO,( OSiMe,)(, 2sjJn, which are soluble in organic solvents.56 Alkane- andarene-sulphonic, -phosphinic, and -boronic acids solvolyse titanium(1v)halides or alkoxides, forming (YO),TiX,, [Y = Me*S02, p-CH,*C6H4*S0,,PhP(:O)H, or PhB(0H); n = 1 or 2; X = C1 or The infrared spectrasf the 1 : l adducts formed between titanium(rv) chloride and rneta- andpara-substituted acetophenones show that with the exception of adductsformed by 4-aminoacetophenone the bonding from the ligand is throughd6 G.A. Barclay, I. K. Gregor, and S. B. Wild, Chrn. and Ind., 1964, 1710.47 I. M. Kolthoff and F. G. Thomaa, J . EZectrochern. SOC., 1964, 111, 1065.48 G. W. A. Fowles and R. A. Walton, J . Chem. Soc., 1964, 2840.49 H. Biirger, Monatsh., 1964, 95, 671.50H.-L. Krauss and H. Huttmann, 2. Naturforsch., 1963, 18b, 976.K. Baker and G. W. A. Fowles, Proc. Ghem. Xoc., 1964, 362.62 T. N. Waters, Chem. and Id., 1964, 713.C. E. F. Rickard and T.N. Waters, J . Inorg. Nuclear Chem., 1964, 26, 925.54 D. C. Bradley and C. E. Holloway, Inorg. Chern., 1964, 3, 1163.55 C. G. Barraclough, R. L. Martin, and G. Winter, J . Chem. Soc., 1964, 758.56 D. C. Bradley and C. Prevedorou-Demas, J . Chem. SOC., 1964, 1580.67 R. Feld, J . Chem, Xoc., 1964, 3963NICHOLLS : THE TRANSITION ELEMENTS 153the carbonyl-oxygen atom.58 Reaction of anhydrous irop(m) chloride withdi( pentane-2,4-diono)titanium( IV) dichloride in glacial acetic acid leads tothe formation of tri-(pentane-2,4-diono)titanium(rv) tetrachloroferrate(m),[Ti( acac) ,]+FeC1,-.59 Zirconium oxychloride, Zr OCl,, forms white crystalsthat decompose at 250"; it is prepared by reaction of equimolar amounts ofzirconium(1v) chloride and chlorine monoxide in carbon tetrachloride.60Some pyridine N-oxide complexes having the compositions ZrO(Py0) B(C104)2,Th(PyO),(ClO,),, and UO,( PyO)5(C10,), have been prepared ; they appearto contain seven-co-ordinate zirconium and uranium, and eight-co-ordinatethorium.When di- (n-cyclopentadienyl)zirconium( IV) chloride is treatedwith acetic, valeric, or heptanoic acid, both chlorine atoms and one cyclo-pentadiene ring are replaced to give the compounds (C,H,)Zr( O*CO*R),;with trifluoroacetic acid the solvolysis proceeds only as far as(C,H,),Zr(O*CO*CF,),.62Vanadium, Niobium, and Tantalum.-In the vanadium-selenium system,a phase of probable composition V,Se, and tetragonal structure is found insamples quenched from 750°.63 Niobium nitrides are prepared from niobiumpowder and nitrogen a t temperatures of 1200-1500" and pressures up to160 atm.; their maximum nitrogen content corresponds to the formula-NbN,.,6.64 One of the phases in the niobium-tellurium system is thetetragonal NbTe,; the Nb1+.Se2 phase has a homogeneity range betweenNb,.,,Se, and Nb,.,,Se, where the addition of niobium results in solidsolution.65 Three new intermediate phases have been identified in theniobium-arsenic and -antimony systems.They are NbAs, (monoclinic),Nb5Sb, (tetragonal), and NbSb, (monoclinic) ; the phases Nb,Sb and Nb,Sb,show weak, temperature-independent paramagnetism.66The vaporisation reactions of the vanadium halides have been investigate&in some detail; there is no disproportionation of vanadium(I1) halides in therange 750-950"~.I n the presence of bromine, vanadium(m) bromide isvaporised as vanadium(1v) bromide. Solid VBr, can be isolated from thedisproportionation reaction2VBr3(4 S v B r ~ ( ~ ) + VBrqg)by condensation of the vapour a t -78"; it is stable a t -45" but decomposesto vanadium( 111) bromide and bromine a t higher temperatures.67 Prepara-tions hitherto thought to be K,VCl,,nH,O have been shown to be mixturesof KVCl,,nH,O and KC1; two distinct substances have been characterised,a green 6-hydrate and a red 1~5-hydrate.~~ Vanadium@) chloride forms asimple adduct, VCl,,6NH2Me, with monomethylamine, but vanadium(1II)t5 8 G. P. Rossetti and B. P. Susz, Helv. Chinz. Ada, 1964, 47, 289, 2053.R. J. Woodruff, J.L. Marini, and J. P. Fackler, Inorg. Chem., 1964, 3, 687-60 K. Dehnicke and K.-U. Meyer, 2. anorg. Chem., 1964, 331, 121.6 2 E. M. Brainina and R. Kh. Freidlina, Izvest. Akad. Naurl: S.S.S.R., Ot&l. j&m,133 E. Rost and L. Gjertsen, 2. anorg. Chem., 1964, 328, 299.64 G. Brauer and H. Kirner, 2. anorg. Chem., 1964, 328, 34.6iK. Selk and A. Kjekshus, Ada Chem. Scund., 1964, 18, 690, 697.66 S. Furuseth and A. Kjekshus, Ada Cmim. Smnd., 1964, 18, 1180.67 R. E. McCarley, J. W. Roddy, and K. 0. Berry, Inmg. Chem., 1964,3, 50, 54, 60,* 8 S. M. Horner and S. Y. Tyree, Inorg. Chem., 1964, 3, 1173.R. Murthy and C. C. Patel, Canad. J . Chem., 1964, 42, 856.Nauk, 1963, 835 (756)154 INORGANIC CHEMISTRYchloride undergoes solvolysis of one V-C1 bond upon reaction with primaryand secondary aliphatic amines.69 Allcyl cyanides form adducts VC14,2RCNwhen they react with vanadium(1v) chloride in an inert solvent; in thepresence of an excess of the cyanide, however, quantitative reduction occurswith the formation of VC1,,3RCN complexes.70 When vanadium(n) andvanadium(rv) are mixed in aqueous acid perchlorate solutions, a highlycoloured intermediate is formed ; it has been identified as VOV4+, a hydrolyticdimer of vanadium(~~~).~l An analysis of the optical and magnetic propert'iesof vanadium(@ complexes has been given on the basis of the ligand-fieldmode1.72Fluorination of vanadium(m) chloride at 180" gives a new light-greenmodification of vanadium( ~ v ) fluoride. When the complex, PC1,,VC14,dissolved in arsenic trichloride, reacts with arsenic trifluoride the mixedhalides v&&t?5 and VClF, are produced.73 In (NH,)2VO(NCS)4,5H,0 thevanadium atom is co-ordinated to the vanadyl oxygen and four nitrogenatoms of the isothiocyanate groups, these five atoms being at the verticesof a tetragonal pyramid; there is a close approach of a water molecule inthe remaining " octahedral " p0sition.7~ Two new diamagnetic compoundsof niobium(1v) have been prepared. The addition of pyridine to niobium(1v)chloride in ethanol gives [NbC1(OEt),,C5H5NJ2 which is believed to be halogen-bridged with metal-metal bonding accounting for the diamagnetism. Thereaction of sodium ethoxide with the latter dimer gives the diamagneticNb(OEt),.75 Preparative methods for TaCl, (from Ta + TaCl, at 600°),TaCl,, and TaCl,., have been gi~en.7~The volatility of vanadium(v) oxide in the presence of water vapourhas been investigated a t 500-650" ; a heterogeneous equilibriumyielding the new gaseous vanadium compound is believed to occur.77 Con-ditions for preparing well-crystallised niobium( v) iodide from the elementshave been determined; it has a monoclinic crystal lattice with four NbI,units in the unit cell.78 The pentahalides of niobium and tantalum formdiamagnetic, monomeric non-electrolytes, MX,,RCN, with alkyl cyanides ;with pyridine and y-picoline, however, reduction occurs and complexesMX4,2L of the quadrivalent metals are formed.2,2'-Bipyridyl and 1,lO-phenanthroline also cause reduction of the pentahalides, forming MC14,L(L = bidentate ligand).V9 As with titanium(Iv), the do systems niobium(v)and tantalum(v) chlorides form stronger complexes with sulphur than withoxygen donors.Thus reaction of the crystalline etherates, NbCl,,OEt,,v205(S) f 2H20(g)8V203(OH)4(g)69 G. W. A. Fowles and P. G. Lanigan, J . Less-Common Metals, 1964, 6, 396.7 0 M. Duckworth, G. W. A. Fowles, and R. A. Hoodless, J . Chem. Sdc., 1963, 5665.?IT. W. Newton and F. B. Baker, Inorg. Chem., 1964, 3, 669.7 2 R. M. Macfarlane, J . Chem. Phys., 1964, 40, 373.75 L. Kolditz, V. Neumann, and G. Kilch, 2. anorg. Chem., 1963, 325, 275.?4 A. C. Hazell, J . Chem. SOC., 1963, 5745.7 5 R. A. D. Wentworth and C. H. Brubaker, Inorg. Chem., 1964, 3, 47.7 6 H. Schiifer, H.Scholz, and R. Gerken, 2. anorg. Chem., 1964, 331, 154.7 7 0. Glemser and A. Miiller, 2. anorg. Chem., 1963, 325, 220.7t3 W. Littke and G. Brau3r, 2. anorg. Chem., 1963, 325, 122.?9 K. Feenan and G. W. A. Fowles, J . Chem. SOC., 1964,2842; M. Allbutt, K. Feenan,and G. W. A. Fowles, J . Lms-Commm Metals, 1964, 6, 299NICHOLLS : THE TRANSITION ELEMENTS 155NbCl,,OPr<, and TaCl,,OEt,, with the corresponding dialkyl sulphidescauses replacement of the ethers and the formation of the sulphide com-plexes. Niobium(v) and tantalum(v) chlorides abstract the oxygen atomfrom sulphoxides, forming the oxyhalide which then co-ordinates furthermolecules of the sulphoxide, e.g.,*l(the last-mentioned product decomposes to give Cl*CH,*SMe and hydrogenchloride).With dinitrogen tetroxide, these halides give solvated nitrato-dioxides NbO,-NO, and TaO,*NO, which are probably polymeric; withdinitrogen pentoxide, tantalum(v) chloride yields TaO(NOJ3.*2 Sodiumdisilylamide reacts with isopropoxyvanadium( v) oxide chloride and withvanadium(v) oxide chloride, giving silylamino-substituted vanadium com-pounds, e.g., (PriO),VO~(SiR,),]3-, (n = 1 and 2).83 Equilibrium ultra-centrifugation techniques have been used to establish that the singleisopolyanion in aqueous solutions of tantalum(v) is essentially the same asthat found in the crystalline tantalate,84 i.e., [Ta,Ol,ls-. The reactionof niobium with sulphur monochloride leads to the formation of NbS,Cl,;this and similar compounds, e.g., NbSe,I,, can also be prepared from theelements at around 500" in a temperature gradient.85Chromium, Molybdenum, and Tungsten.-Hexakis( trifluoroph0sphine)-chromium(0) and -molybdenum(O) have been prepared by the reaction ofthe phosphine with bis(benzene) compounds of the metals, e.g.:NbCIs + 3MeaSO ---+ NbOC1,,2MeaS0 + MeaSC1,The compounds are colourless, crystalline, and diamagnetic. The tricarbonylcomplexes, M(PF3)3(C0)3 (M = Cr or Mo), are similar, and are prepared byreaction of the phosphine with Cr(NH,),(CO), and tricarbonyl mesitylene-molybdenum.86 The chromium(0) compounds, Cr( bipy) , and Cr(phen),,have been prepared by a new namely, reaction of the carbonyl withthe ligand at 190". With 2,2',2"-tripyridyl the Group VI hexacarbonylsyield the compounds M ( t r i p ~ ) , .~ ~The oxidation stoicheiometry and kinetics of the aquated chromium( 11)ion with a variety of metal oxides have been studied in detail. With MnO,,PbO,, Tl,O,, Mn,03, Co203, and CeO, the predominant form of the chrom-ium (111) product is the Cr(H,0),3+ ion; when Pb,O, or Ca,PbO, reacts, thechromium(n1) dimer or a higher polymer is formed.89 The binuclearchromium(n1) species formed by oxygen-oxidation of Cr2+ solutions has beenD. B. Copley, F. Fairbrother, and A. Thompson, J. Chem. SOC., 1964, 315.81 D. B. Copley, F. Fairbrother, K. H. Grundy, and A. Thompson, J . Less-Common8 2 K. W. Bagnall, D. Brown, and P. J. Jones, J. Chm. Soc., 1964, 2396.83 H. Biirger, 0. Smrekar, and U. Wannagat, Mmtsh., 1964, 95, 292.84 W.H. Nelson and R. S. Tobias, Inorg. Chem., 1964, 3, 653.H. Schlifer, D. Bauer, W. Beckmenn, R. Gerken, H.-G. Nieder-Vahrenholz,8 6 T. Kruck, Chem. Ber., 1964, 97, 2018; T. Kruck and A. Prasch, 2. Naturforsch.,87 H. Behrens and N. Harder, Chem. Ber., 1964, 97, 426.Metals, 1964, 6, 407.K.-J. Niehues, and H. Scholz, Natururiss., 1964, 51, 241.1964, 19b, 669.H. Behrens and U. Anders, 2. Naturforsch., 1964, 19b, 767.B. A. Zabin and H. Taube, I)iorg. Chem., 1964, 3, 963.156 INORQANIO CHEMISTRYshown by 180 exchange t o be [Cr(H,0)40H]24+.go Molybdenum@) chlorideforms a diamagnetic ammoniate, (Mo,CI,)C1,,4NH3, when it reacts withliquid ammonia a t the boiling point; molybdenum(m) chloride is ammono-lysed in liquid ammonia a t room temperature, the product beingMoC12NH,,2NH,.91 Carboxylates of rnolybdenum(I1) can be obtained byinteraction of mono- and di-carboxylic acids with hexacarbonylmolybdenum.The monocarboxylates appear to have a dimeric structure (1) involving bothbridging and chelathg carboxylate groups and tetrahedrally co-ordinatedmolybdenum. 92RL RAnhydrous chromium(m) chloride forms an ammoniate, CrCl,(NH,),,which decomposes a t about 240" to a green mixture containing the amido-chloride : 93CrCl,(NH,), + CrNH,Cl,,NH, + NH,ClAt lower temperatures, hexamminechromium( m) chloride decomposes via[Cr(NH,),Cl]CI, to CrC13(NH3)3.94 The tetrachlorochromate(m) ion may bethe first chromium(m) compound with a co-ordination number other thansix; magnetic data on PCrC18 are consistent with its formulation as[PCI.J+[CrCl,]-, containing ions with approximately tetrahedral ~ymrnetry.~5The previously reported tungsten(1n) complex, K,[W3C1,,], has been shownto be a mixture of K,[W2Clo] andK3[W(OH)Cl,].ga Anhydrous chromium(m)nitrate is obtained as a green precipitate when &nitrogen pentoxide andhexacarbonylchromium react in carbon tetrachloride ; it is involatile anddecomposes a t 60" in V ~ U O .~ ~ The spectra of chromium(m) acetylacetonatehave been recorded a t 77" and 4 " ~ ; the vibrations associated with the2 E c 4A, transition have been identified in the 12,000--15,000 cm.-I regionand the 2T, level has been located.93 Triquinolinolatochromium(rn)reversibly absorbs hydrogen halides; the Cr-N bond is probably disruptedby an initial reaction which places a proton on the nitrogen and a chlorideion on the chromium.99Chromium(rv) fluoride is surprisingly inert, not reacting with ammonia,pyridine, sulphur dioxide, or sulphur trioxide.I n boiling bromine trifluorideor selenium tetrafluoride it is reduced to lower fluorides; complex fluorides,R. W. Kolaczkowski and R. A. Plane, Inorg. Chem., 1964, 3, 322.9lD. A. Edwards, J . Less-Common Metab, 1964, 7 , 159.92T. A. Stephenson, E. Bannister, and G. Wilkinson, J . Chem. Soc., 1964, 2538.93 J. Lamure and P. de Gelis, Compt. Rend., 1964, 258, 2071.94 W. W. Wendlandt and C. Y. Chou, J . Irwrg. Nuclear Chem., 1964, 26, 943.OaD. J. Machin, D. F. C. Morris, and E. L. Short, J . Chem. SOC., 1964, 4658.D6 E.Konig, Inorg. Chem., 1963, 8, 1238.97 C. C. Addison and D. J. Chapman, J . Chern. SOC., 1964, 539.96 P. X. Armendarez and L. S. Forster, J . Chem. Phys., 1964, 40, 273.99 M. M. Jones, K. V. Dandh, and G. T. Fisher, J . Inorg. Nuclear Chem., 1964,26, 773NICHOLLS: THE TRANSITION ELEMENTS 157MCrF, (M = K, Rb, or Cs), and &CrF6 (M = K or Cs), have been prepared.loOMolybdenum(Iv) chloride is prepared as a black solid (p = 0.93 B.M. at 25')simply by refluxing the pentachloride in benzene :lol2MoC1, + c6H6 + 2MoC1, + c6H,cI + HCICrystalline tungsten(Iv) chloride and bromide have been prepared byreduction of the higher halides with aluminium in sealed, evacuated tubesunder a controlled temperature gradient. Disproportionation of the quadri-valent halides at 450-500" provides a convenient synthesis of the bivalentcompounds :The reduction of transition-metal halides by pyridine has recently been ofconsiderable interest.Tungsten(=) chloride and tungsten(v) bromide arereduced to WX,,Zpy complexes, and now the oxidation product of thepyridine has been identified as the l-4'-pyridylpyridinium ion.10, Alkylcyanides bring about similar reductions of the higher halides to MX,,ZRCN(M = Mo or W; X = C1 or Br); these complexes are valuable starting mat-erials for the preparation of other molybdenum(Iv) and tungsten(w) com-plexes.lo3 Molybdenum(Iv) oxide chloride is obtained by reaction of molyb-denum(m) chloride with molybdenum(vr) oxide and isolated as crystals byusing chemical transport by means of chlorine or molybdenum( v) chloride.l0*Pure molybdenum(1v) oxide crystals have been grown by electrolyticreduction of Mo03-Na2Mo04 mixtures lo5 at 675".The unstable chromium(v) oxide fluoride, CrOF,, is formed in the fluorina-tion of chromium(vI) oxide with halogen fluorides.log Above 200", molyb-denum(v) oxide chloride volatilises and begins to disproportionate accordingto the reaction 9 0 73WX4(,) * w x 2 ( s ) 3- 2WX5(,)3MoOC1, MoOC14 + MoO,Cl, + MoCl,(NH&Mo0Br5,( Quin H)MoOBr4 and MOO( OH),Br,,4H20, the bromo-complexes, have been prepared.An investigation of the equilibriumbetween molybdenum(vr), molybdenum(v) , and Br,- in 8.6~-hydrogenbromide led to the conclusion that both the molybdenum(v) andmolybdenum(vI) species are dimeric.lO* Primary aliphatic amines solvo-lyse tungsten(v) chloride and bromide forming benzene-soluble dimers[WX2(NHR),], ; with secondary amines, reduction and solvolysis occurs,giving, e.g., WX,(NMe,),,NHMe, and WX,NEt2,2N€€Et2.109 Reaction oftungsten(vI) chloride with alkali-metal halides gives green hexachlorotung-states(v) with liberation of halogen.If tungsten(v) chloride is heated withtwo equivalents of potassium chloride, K,WCI, can be obtained. Atloo H. C. Clark and Y. N. Sadana, Canad. J . Chern., 1964, 42, 50.lolM. L. Larson and F. W. Moore, Inorg. Chem., 1964, 3, 285.loaR. E. McCarley and T. M. Brown, Inorg. Chem., 1964, 3, 1232.lo3 E. A. Allen, B. J. Brisdon, and G. W. A. Fowles, J . Chem. SOC., 1964, 4531.lo* H.Schilfer and J. Tillack, J . Less-Common Metab, 1964, 6, 152.lo6 A. Wold, W. Kunnmann, R. J. Amott, and A. Ferretti, Inorg. Chem., 1964,losH. C. Clark and Y . N. Sadana, Canud. J . Chem., 1964, 42, 702.lo' I. A. Glukhov and S. S. EliSeev, Zhur. necwg. Khim., 1963, 8, 100 (50).lo* J. F. Allen and H. M. Neumann, Inorg. Chem., 1964, 3, 1612.loD B. J. Brisdon and G. W. A. Fowles, J . Leas-Common Metals, 1964, 7, 102.8, 546158 INORGANIC CHEMISTRY280-300" in vmuo the MwC1, complexes are converted into M2WCl, withSulphides of molybdenum and tungsten in the composition range MS, toMS, have been investigated ; the trisulphides are amorphous ; the disulphidesobtained by thermal decomposition of MS, are hexagonal.lf1 Molyb-denum(v1) oxide chloride is conveniently prepared 112 by refluxing molyb-denum(v1) oxide with thionyl chloride; the solution is evaporated and greencrystalline MoOCl, sublimed at 50-60 '.Diethylenetriamine (dien) formsa crystalline monomeric complex with molybdenum(v1) oxide, Moo,( dien) ;in this complex the molybdenum atom is co-ordinated in a distorted octa-hedron by three mutually-cis oxygen atoms and three nitrogen atoms;intermolecular hydrogen bonding is extensive.Il3 A detailed study has nowbeen made by a variety of techniques of the aggregates formed on acidifica-tion or alkali-metal molybdate solutions. On acidification of Na2Mo04solutions at appreciable concentration, the first important species found isMO,O~,~-; at higher acidification the octanier M0,02,4- is formed andpolymeric species are present in solutions containing several molar hydrogenchloride in an excess of molybdic acid.lf4 In a freshly prepared solution ofsodium paratungstate, the main tungstate species is the W12041'*- ion.This ion hydrolyses slowly to yield a mixture of W1204110- and HW,02,5-;at higher acidities, W1203Q6- is formed.ll5Manganese, Technetium, and Rhenium.-Anhydrous manganese( 11)and cobalt(=) chlorides react with chlorine nitrate or dinitrogen pentoxideto give the dinitrogen tetroxide adducts of the anhydrous nitrates; theseadducts are readily desolvated therrnally.ll6 The crystal structure of[Mn(N2H4),]Cl2 is formed by chains of pseudo-octahedrally co-ordinatedmanganese atoms held together by hydrazine bridges.ll7 Di( acetylaceto-nato)manganese(II) is trimeric in hydrocarbon solvents ; its adducts withone mol.of pyridine, although monomeric and five-co-ordinate in freshlyprepared benzene solution, slowly decompose in solution, probably forminga condensed six-co-ordinate species.ll8 Manganese( 11) forms eight-co-ordinate complexes with oxine, Mn(CQH6N0),,2C,H,N0, and thioxine,Mn(C,H6NS)2,2C,H,NS.11Q New compounds of technetium in low oxidationstates are reported ;l20 by reduction of technetium(1v) with hydroxylamine,the chloride of a complex cation has been isolated containing technetium(@110 R. N. Dickinson, S. E. Feil, F. 37. Collier, W. W. Horner, S. M. Horner, andS. Y. Tyree, Inwg. Chem., 1964, 8, 1600; I. V. Vasil'kova, N. D. Zaitseva, and P. S.Shapkin, Zhur.neorg. Khim., 1963, 8, 2360 (1237); N. D. Zaitseva, ibid., p. 2365 (1239);I. V. Vail'kova, N. D. Zaitseva, and V. A. Petrova, ibid., p. 2369 (1241); cf. Ann.Reports, 1963, 211.111 J. C. Wildervanck and F. Jellinek, 2. unorg. Chena., 1964, 328, 309.R. Colton, I. B. Tomkins, and P. W. Wilson, Austral. J . Chem., 1964, 17, 496.113 W. F. Marzluff, Inorg. Chem., 1964, 3, 395; F. A. Cotton and R. C. Elder, ibid.,114 J. Aveston, E. W. Anaclrer, and J. S. Johnson, Inorg. Chem., 1964, 3, 735.116 J. Aveston, Inorg. Chem., 1964, 3, 981.116 K. Dehnicke and J. Strahle, Chem. Ber., 1964, 97, 1502.117 A. Ferrari, A. Braibanti, G. Bigliardi, and F. Dallavalle, 2. Krwt., 1963, 119,284.118 D. P. Graddon and G. M. Mockler, Austral. J . Chem., 1964, 17, 1119.119 Yu.A. Bankovskii, A. F. Ievin'sh, M. R. Buka, and E. A. Luksha, Zhur. neorg.120 J. D. Eakins, D. G. Humphreys, and C. E. Mellish, J . Chem. Soc., 1963, 6012.loss of WC16.110p. 397.Khim., 1963, 8, 110 (56)NICHOLLS : THE TRANSITION ELEMENTS 159with ammonia and hydroxylamine as ligands. Technetium chemistry hasbeen reviewed.121The polynuclear chemistry of rhenium( 111) has been extensively investi-gated. After last year's report that the ReC1,- anion is trimeric with atriangle of bonded rhenium atoms, it has now been found that anhydrousrhenium(=) chloride has a structure build up of well-defined Re3CJg units;these clusters have approximately the same structure as the Re3C1, unitsfound last year in Cs,Re3C11, and more recently in Re3C1,(PEt2Ph)3.122The structures of [Re3Cl1,]3- and [Re3Cll1]2- are essentially the same exceptfor the lack of one terminal chlorine atom in the latter and a consequentreduction in its symmetry from D3h.It is suggested that the bonding inthese two anions can be simply explained in terms of seven-fold co-ordination(using d3sp3 hybrid orbitals) around the rhenium.123 Rhenium( III) bromidesimilarly gives rise to numerous compounds containing the Re,Br, group ;thus Re,Br,(PEt,Ph) is isomorphous with the corresponding chloride andthe presence of the Re3Br, group has been conclusively demonstrated inM,Re,Br,, (M = quinolinium, pyridinium, or tetraethylarnmoni~m).~~~ Aswell as the [Re3Brl,]3- and the [Re3Brl,l2- anion, the [Re,Br,,]- anion hasbeen isolated with a number of cations.Treatment of [Ph,PH]Re3Brl,with more than three mol. of pyridine yields Re,Br,(~y),.l~ The chemistryof tervalent rhenium in the light of its pronounced homophilicity has beenreviewed.l26 Tri(acetylacetonato)manganese(m) consists of discrete mole-cules linked together by van der Waals forces; the distortion from octahedralsymmetry about the manganese atom appears to be the result of altered0-Mn-0 bond angles rather than of a Jahn-Teller mechanism.12' Theabsorption spectra of aqueous manganese( III) with and without the additionof halide ions have been studied.l2* The distinct splitting of the 5T2,t 5Egband in the presence of added fluoride ions is shown to be consistent withthe formation of MnF2+.The preparation and magnetic properties of ReCl,, ReCl,, and ReC1,have been described.Rhenium( VI) chloride shows Curie-Weiss dependence,but the rhenium-(Iv) and -(v) chlorides show marked deviations below 220"and 100 OK, respecti~e1y.l~~ Hitherto unreported hexachlororhenates(1v)(which are more soluble in hydrochloric acid than is the chloride of theassociated cation) have been obtained l30 by reaction of perrhenates withcarbon tetrachloride at 440". Pyrolysis of the phosphonium salts,[PHR3],ReX6 (X = C1 or Br) gives the phosphine complexes, ReX,(PR,),(PR, = PPh, or PEt,Ph). The rhenium(v) complexes, ReOCl,(MR,),(M = P or As), are most conveniently prepared by ligand displacement from121 K. Schwochau, Angew. Chm., 1964, 76, 9.l z 2 F . A.Cotton and J. T. Mague, Inorg. Chem., 1964, 3, 1094, 1402; cf. Ann.123 J. E. Fergusson, B. R. Penfold, and W. T. Robinson, Nature, 1964, 201, 181.124 F. A. Cotton and S. J. Lippard, J. Amer. Chem. SOC., 1964, 86, 4497.125 J. E. Fergusson and B. H. Robinson, Proc. Chem. SOC., 1964, 189.la* F. A. Cotton, N. F. Curtis, C. B. Harris, B. F. G. Johnson, S. J. Lippard,J. T. Mague, W. R. Robinson, and J. S. Wood, Science, 1964, 145, 1305.lz7 B. Morosin and J. R. Brathovde, Acta Cryst., 1964, 17, 705.12* J. P. Fackler and I. D. Chawla, Inorg. Chem., 1964, 3, 1130.129 D. Brown and R. Colton, J. Chem. SOC., 1964, 714.Reports, 1963, 60, 213.W. W. Homer F. N. Collier and S. Y. Tyree, Inorg. Chem., 1964, 3, 1388160 INOBGANIC CHEMISTRYtra~-[ReOCl,(PPh,).J.l~~ Interaction of the latter complex with pyridinegives salts of the ion [Re02py4]+; these and similar ethylenediamine com-plexes are believed to have a trans O=Re=O gr0~ping.l~~ The complex,Re203Clqpy4, has been isolated and shown to be an intermediate in theconversion of trans-[ReOCl,( PPh ,),I into trans-[ Re02pyJC1.133 In com-bination with tertiary phosphine ligands, rhenium(v) has a strong tendencyto form multiple bonds to nitrogen.Three new series of compounds contain-ing such bonds are [ReX,(NAr)(PR,),], [ReNX,(PR,),], and [ReNX,(PR,),](X = halogen, Ar = aryl, R = alkyl or aryl).lS4 The cyanide ion alsoenhances the formation of nitrido-compounds ; thus reduction of potassiumperrhenate by hydrazine hydrate in the presence of cyanide ion givesK[ReN(H,O)(CN),] as well as K,[Re0,(CN)4]. The latter is also formed inthe hydrolysis of potassium octacyanorhenate( v).135When rhenium(m) oxide and ammonium perrhenate are treated withthionyl chloride, the sulphuryl chloride complexes, (ReO,Cl),,SO,Cl, and(NH 3) 2Re02C14, S O,CI,, are produced, respecti~e1y.l~ Further molecular-orbital calculations on the permanganate ion 137 cor.&m that the lowestunoccupied orbital is of e symmetry; the electronic spectrum has beenassigned and the value of A in %04- estimated to be 26,000 cm.-l.Iron, Ruthenium, and Osmium.-Pure ruthenium metal can be depositedfrom di-(mcyc1opentadienyl)ruthenium at 595 O in a hydrogen gas stream.138The reaction of pentacarbonyliron with trifhorophosphine at elevatedtemperatures and pressures gives a mixture of Fe(C0) 5.-z(PF3)s compounds ;all the compounds have been isolated, including Fe(PF,), which reacts onlyalowly with water.13g A direct synthesis of this compound has been achievedby treating anhydrous iron@) iodide with pure trifluorophosphine a t 140"and 500 atm.in the presence of copper powder.140The magnetic susceptibilities of several high-spin complexes of iron( n)[Fe(phen),X,] (X = C1, Br, I, N,, SCN, or SeCN) have been determined overthe range 100-300°~. The moments found are somewhat lower than thoseexpected for rigorously octahedral complexes and are essentially independentof temperature except for the SCN- and SeCN- compounds in which themoment decreases sharply from -5 to -1.5 B.M.at lower temperatures.lUThe ionic model has been used to account for possible tetragonal distortionsof iron(=) compounds; it is concluded that where the force constant fordistortion is small, e.g., in Fe(H,O),,+, it is likely that distortions of about0.1 A O C C U T . ~ ~ ~ Iron(=) bromide and copper(1) bromide react with131 J. Chatt, J. D. Garforth, N. P. Johnson, and G. A. Rowe, J . Chem. SOC., 1964,601.132 N. P. Johnson, C. J. L. Lock, and G. Wilkinson, J. Chem. SOC., 1964, 1054.laa N. P. Johnson, F. I. M. Taha, and G. Wilkinson, J. Chern. Soc., 1964, 2614.134 3. Chatt, J. D. Garforth, N. P. Johnson, and G. A. Rowe, J . Chem. SOC., 1964,136 C. J. L. Lock and G. Wilkinson, J. Chem. SOC., 1964, 2281.la* I(. W. Bagnall, D. Brown, and R. Colton, J .Chem. Soc., 1964, 3017.lS7 A. Viste and H. B. Gray, Inmg. Chem., 1964, 3, 1113; R. F. Fenske and C. C.1 3 8 D . E. Trent, B. Paris, and H. H. Krause, Inorg. Chem., 1964, 3, 1057.lasR. J. Clark, Inorg. Chem., 1964, 3, 1395.140 T. Kruck and A. Prasch, Angew. Chem., 1964, 76, 892.1 4 l W. A. Baker and H. M. Bobonich, Inwg. Chem., 1964, 3, 1184.142 W. E. Hatfield and T. S. Piper, Inorg. Chem., 1964, 3, 1295.1012.Sweeney, ibid., p. 1105NICHOLLS : THE TRANSITION ELEMENTS 161LiP(c6Hll),, forming phosphides ; Fe[P(C6H11)2]2 is monomeric h benzene,and, in an excess of the lithium phosphide, the product LiFe[l?(c6Hll)2]3 isformed.’43 The ligand 2,2f,2‘f,2”‘-quaterpyridine forms mono- and bis-complexes with Fez+ and a monocomplex Fe( quaterpy)8+ ; these complexesdiffer considerably in reactivity from those of 2,2’-bipyridine and 2,2’,2“-terpyridine.144X-Ray diffraction and spectral studies demonstrate that the structure ofa concentrated aqueous solution of iron(m) chloride is strongly influencedby the presence of acid.While the co-ordination about Fe3+ is largelyoctahedral in neutral solutions, the addition of acid results in the formationof a polymer consisting of alternating PeCl, (tetrahedral) and FeC14(H20)2(octahedral) units with adjacent units sharing a chloride ion.l*5 Four com-plexes have been identified in the Fe3+-tartaric acid system ; in each complexthe Fe3+ ion is combined with the two ionised carboxyl groups of the acid;the monomer FeL (tartaric acid = H2L) has additional participation fromone or both alcoholic hydroxyl groups.146 Iron@) chloride and cobalt@)chloride react with NaN[SiMe,], to give green, sublimable, monomericdisilylamido-compounds such as Fe[N( SiMe,)2],.147The structural unit in ruthenium(v) fluoride is a tetramer with rutheniumatoms at the corners of a rhombus.The metal atoms are linked by non-linear fluorine bridging atoms and the fluorine atoms form a distorted octa-hedral arrangement around each ruthenium The structures of anumber of osmyl complexes of the form [Osv10,X,X‘,]2- have been investi-gated by measurement of their infrared s p e ~ t r a . 1 ~ ~ The perosmates areformulated as [OsvnT04X,]2- and the oxy-osmyl salts as [OsWO,( OH),X2j2-.Cobalt, Rhodium, and l[ridium.-The cobalt(1) complex, [Co(phen),]ClO,,has been prepared by reduction of triphenanthrolinecobalt(n) perchlorate withsodium borohydride in aqueous ethanol at -5O.150 In the blue anhydrousammonium tetrachlorocobaltate(n) the magnetic moment (per = 4-77 B.M.)and relatively large Weiss constant indicate a distorted tetrahedral structurefor the anion; the violet hydrate (NH,),[Co(H,O),ClJ has peff = 5.18 B.M.,indicating a distorted octahedral ~tructure.1~~ Bond lengths and bondangles are reported for the COC~,~- ion from a least-squares analysis of thethree-dimensional X-ray data for Cs3CoC1,.The deviation from stricttetrahedral symmetry around the cobalt atom is due to angular distortionsrather than bond stretching or contraction.’52 The temperature-dependenceof the paramagnetic susceptibilities of single crystals of Cs,CoCl,, Cs2C0Cl4,and K2Co(CNS),,4H,0 have been measured over the range 80-300”~.Thesplitting of the excited 4T2 term by low-symmetry crystal fields is of thelP3 K. Issleib, W. Wenschuh, 2. Nakurforsch., 1964, 19b, 199.144 A. Bergh, P. O’D. Offenhartz, P. George, and G. P. Height, J . Chem. Soc.,145 G. W. Brady, M. B. Robin, and J. Varimbi, Inorg. Chem., 1964, 3, 1168.148 C. F. Timberlake, J. Chem. SOC., 1964, 1229.lC7H. Biirger and U. Wannagat, Monatsh., 1963, 94, 1007.148 J. H. Holloway, R. D. Peacock, and R. W. H. Small, J . Ckm. Soc., 1964, 644.14* W. P. GrifEth, J. Chem. SOL, 1964, 245.150 N. Maki, M. Yramagami, and H. Itatani, J. Amer. Chm. SOC., 1964, 88, 514.151 N.Fogel, C. C. Lin, C. Ford, and W. Grindstaff, Inorg. Chem., 1964, 3, 720.lS1 €3. N. Figis, M. Gerloch, and R. Mason, A& Cryst., 1964, 17, 606.1964, 1533162 INORGANIC CHEMISTRYorder of 1000 cm.-l; the magnitudes of the observed splitting8 are calculatedin a semiquantitative way by comparing details of the molecular geometrywith crystal-field theory for a distorted tetrahedron.l53 In non-co-ordinatingsolvents di(acetylacetonato)cobalt(n) exists to some extent as dimers,trimers, and higher oligomers. The monomer CoA, is tetrahedral, while theoligomers are believed to be built up of CoA, units in which the four oxygenatoms form an approximately square array about the cobalt atoms; thesearrays combine by further sharing of oxygen atoms.15* The crystal structureof the anhydrous salt is that of a centrosymmetric tetramer ; there are threedistinct types of acetylacetonate rings, those with both oxygen atoms bondedto only one terminal cobalt atom, those with one oxygen serving as a bridgebetween two cobalt atoms, and those with both oxygen atoms serving asbridges.155 Complexes between substituted pyridines, a-, B-, and y-picoline,2,6-lutidine, s-collidine, and acridine with cobalt(=) halides have beenprepared and their thermal decomposition studied.156 Stepwise, controlledthermal decomposition of [Co( bipy) ,]Cl,,H,O and [Ni( bipy) ,]C1,,7H20 hasyielded M(bipy),Cl,, M,(bipy),Cl, (M = Co and Ni), Ni(bipy)Cl,, a- and#?-Co(bipy)Cl, (two distinct stereochemical configurations), Co(bipy),.aoC1,,and M( bipy) ,. 5C1,.157 Four histidine cobalt(=) complexes have been dis-tinguished in aqueous solution. A weak 1 : 1 complex at pH < 4 has onlythe histidine-carboxyl group bonded to the metal; strong 1 : l and 2 : l(histidine : cobalt) complexes formed a t pH 4-10 contain histidine, behavingas a tridentate ligand, and a tetrahedral 2 : 1 complex at high pH hasthe ligaiid bonded via the amino-group and an imidazole-nitrogen atom.158The red, diamagnetic compound of empirical formula Co( CNMe) 5(C104)2 hasa dimeric cation [(MeNC),CoCo(CNMe)J4f with a structure analogous to thatof Mn,(CO) Thioureacobalt(rr) complexes, Co(Tu),Cl,, Co(Tu),Br,,Co(Tu),(ClO,),, and Co(Tu),SO,, contain tetrahedrally co-ordinated cobaltwhile Co(Tu),(NO,), is an octahedral complex.160 With the chelatingsulphur donors 2,Ei-dithiohexane and 3,6 -dit hio- octane, cobalt ( 11) halidesform octahedral complexes ; Co(Cl0,),(2,5-dithiohexane), has p,ff = 3-23B.M., so it may be square-planar or involve cobalt in more than one stereo-chemical arrangement .161F'rom the infrared spectra of cobalt(1n) complexes with dimethylglyoxime,good evidence has been obtained for the trans-configuration in all thebis( dimethylglyoximato) cobalt (111) compounds.l62 The trans-octahedral con-fipration has been found for a number of cobalt(m) complexes with sub-stituted ~alicylaldimines.~~~ Hydroxyethylethylenediaminetriacetic acidforms sexidentate complexes with cobalt(m) in which the oxygen of the163 B.N. Figgis, M.Gerloch, and R. Mason, Proc. Roy. SOC., 1964, A, 279, 210.154 F. A. Cotton and R. H. Soderberg, Inorg. Chern., 1964, 3, 1.155 F. A. Cotton and R. C. Elder, J . Arner. Chem. SOC., 1964, 86, 2294.156 J. R. Allen, D. H. Brown, R. H. Nuttall, and D. W. A. Sharp, J . Inorg. Nuclear157 R. H. Lee, E. Griswold, and J. Kleinberg, Inorg. Chem., 1964, 3, 1278.158 C. C. McDonald and W. D. Phillips, J . Amer. Chem. SOC., 1963, 85, 3736.15QF. A. Cotton, T. G. Dunne, and J. S. Wood, Inorg. Chem., 1964, 3, 1495.1 6 o F . A. Cotton, 0. D. Faut, and J. T. Mague, Inorg. Chern., 1964, 3, 17.16lR. L. Carlin and E. Weissberger, Inorg. Chem., 1964, 3, 611.162 R. D. Gillard and G. Wilkinson, J . Chem. SOC., 1963, 6041.163 M. Gampolini, F. Maggio, and F. P. Cavmino, Inorg.Chem., 1964, 3, 1188.Chem., 1964, 26, 1895NICHOLLS : THE TRANSITION ELEMENTS 163hydroxyethyl group is co-ordinated ‘to cobalt, as well as quinquedentatemon~aquo-complexes.~~4 The role of alcohol in facilitating the synthesisof chloropyridinerhodium(m) compounds has been traced to its ability togenerate catalytic amounts of a lower oxidation state of rhodium, e.g., in thereaction of &[Rh(H,O)Cl,] with pyridine to form truns-[Rh(py),C1,]C1.1e5The reactions of chlororhodium(m) species with pyridine under aqueous andnon-aqueous conditions have been re-examined and the nature of theproducts has been clarified.166 With tertiary phosphines and arsines,monomeric complexes RhX,(M3t3), (X = halogen) having the trans-configuration may be obtained.In addition, rhodium forms two types ofhalogen-bridged binuclear complexes, namely, [Rh,X6( MR,) s] and[ R h2X 6( MR ,) cis - and trans - Isomers of dia quodioxalatorhoda t e( III )have been separated by anion-exchange.lG8Tervalent iridium forms three types of complex with 1,lO-phenanthroline ;these are the trichelated [Ir(phen),[X,,nH,O (X = C1, Br, I, or ClO,), thedichelated complex [Ir(phen),X,]X,nH,O (X=C1 or Br), and those containinga dichelated cation and a monochelated anion,[Ir(phen),X,][Ir(phen)X,],nH,O(X = C1, Br, or I ) . l S Q Physical measurements on the complexes of formula[Ir(Et,S),Cl,] have shown the yellow form to be the cis-1,2,3 isomer, and thered form to be an electrolytic ‘‘ polymerisation ’’ isomer, truns-[Ir(Et,S),Cl,]-trans-[Ir(Et,S),C1]4.170Nickel, Palladium, and Plathm.-Tetrakis(trialkyl phosphite)nickel(O)complexes, Ni[P(OR),],, have been synthesised by reduction of nickel(@halides with trialkyl phosphites in the presence of an amine.l71 A largenumber of complexes of nickel(=) halides with substituted pyridines hasbeen reported.l7, Pseudo-tetrahedral complexes are formed by nickel( 11)chloride and bromide with 2,3-, 2,4-, and 2,5-lutidine, but nickel(@ iodidegives diamagnetic and distorted square-planar compounds.The nitratecomplexes, NiL2(N03)2 (L = 2,3-, 2,4-, or 2,G-lutidine) have distortedoctahedral structures, the nitrate groups probably acting as bidentatechelating ligands. Co-ordination of the perchlorate ion (monodentate),occurs in the distorted octahedral complexes, NiL,(ClO,), (L = 33-lutidine, 3-bromopyridine, or 4-iaopropylpyridine).There is spectrophoto-metric evidence for the formation of a five-co-ordinate species, Ni(DTP),,py,in the reaction of pyridine with bis-( OO’-diethyl dithiophosphato)nickel(n) ;successive equilibrium constants for the reactions producing Ni(DTP),,py164 P. B. Wood and W. C. E. Higginson, J . Chem. SOC., 1964, 1484.165 J. V. Rund, F. Basolo, and R. G. Pearson, Inorg. Chem., 1964, 3, 658.IB6 R. D. Gillard and G. Wilkinson, J . Chem. Soc., 1964, 1224.16’ J. Chatt, N. P. Johnson, and B. L. Shaw, J . Chem. Soc., 1964, 2508.lsaR. D. Gillard and G. Wilkinson, J . Chem. SOC., 1964, 870.169 B. Chiswell and S. E . Livingstone, J . Inorg. Nuclear Chem., 1964, 26, 47.170 G.B. Kauffman, J. H-San Tsai, R. C. Fay, and C. K. Jmgensen, I w g . Chem.,1963, 2, 1233.171R. S. Vinal and L. T. Reynolds, Inorg. Chern., 1964, 3, 1062.173 S. Buffagni, L. M. Vallarino, and J. V. Quagliano, Inorg. Chem., 1964, 3, 480;W. Ludwig and G. Wittman, Helu. Chim. Acta, 1964, 47, 1265; E. Uhlig, J. C. Szar,and M . Maaser, 2. anorg. Chem., 1964, 331, 324.173 S. Buffagni, L. 39. Vallarino, and J. V. Quagliano, Inorg. Chem., 1964, 3, 671;L. E. Moore, R. B. Gayhart, and W. E. Bull, J . Inorg. Nuclear Chem., 1964, 26,897164 INORGANIC CHEMISTRYand Ni(DTP),,2py have been ca1c~lated.l'~ The crystal structure of thebright purple and diamagnetic dibromo-( 2,5-dirnethylpyrazine)nickel(n)consists of infinite chains of (2,5-dmp)NiBr2, the nickel atoms being linkedto each other through the nitrogen atoms of the pyrazine ring; the con-figuration of the nickel atom is ~quare-planar.~~~ Quantitative spectra ofsingle crystals of nickel, palladium, and platinum dimethylglyoximates inpolarised light show extinction coefficients much smaller than earlier valuesobtained for polycrystalline specimens.This evidence, and arguments basedon band polarisations, cast serious doubt on previous assignments of thevisible band to an allowed p 4 transition.176 The nickel@) ion attainsa variety of stereochemical environments when co-ordinated to substitutedthioureas; Ni(naptu),Cl, and Ni(etu),X, [naptu = l-l'-naphthyl-2-thiourea;etu = ethylenethiourea (2-thioimidazolidine)] are octahedral; Ni(naptu),X,(X = Br or I) are tetrahedraI; and Ni(etu),X, (X = ClO, or NO,) are square-planar. The blue dichlor o t etrakis - ("'- diet hylt hiourea )nickel ( II) is diamag -netic a t low temperatures (77-194"~) and attains partial paramagnetismas the temperature is raised; the nickel atom resides in a weak tetragonalfield, and the magnetic moment is governed only by the thermal populationof a low-lying paramagnetic level.l77 The spectra of the blue compounds,Ni(diamine),(ONO), and Ni(py),(ONO), (diamine = a C- or N-substitutedethylenediamine), are in accord with their formulation as nitrito-complexes ;steric factors appear to play an important part in the adoption of oxygenco-ordination by the NO,- ion, in contrast with the more usual mode ofbonding through nitrogen .I78 Five - co - ordinate complexes , [ Ni (TAP) XI +(X = monodentate anion), having a trigonal bipyramidal structure areformed with the tetradentate ligand tris-(3-dimethylarsinopropyl)phos-phine.179 A crystal structure determination on di-iodo-(o-phenylenebis-dimethylarsine)nickel(n) shows the molecule to be monomeric and to havetwo diarsine ligands arranged about the nickel atom in the form of a squarewith two iodine atoms in octahedral sites.lsO Square-planar sulphurcomplexes, Ni(SR),L, (L = Ph,P or PhMe,P; L, = Ph$*CH,*CH,*PPhJ,are obtained by oxidation of Ni(CO),L, with R2S2 or by reaction of NiCl,L,with RSNa.lslSeveral different crystalline modifications of the Lifschitz stilbenediaminecomplexes of nickel(=) dichloroacetate have been described.Crystab ofthe blue form contain octahedrally co-ordinated nickel; in the yellow form,two out of three of the nickel atoms are paramagnetic and octahedral whilethe remaining nickel atom is diamagnetic and planar. Equilibrium betweenthe blue and the yellow form occurs in ethanol and in acetone-water solutions17* R. L. Carlin, J. S. Dubnoff, and W. T. Huntress, Proc. Chem. Soc., 1964,17aF. D. Ayres, P. Pading, and G. B. Robertson, Inwg. Ch., 1964, 3, 1303.176 G. Basu, G. M. Cook, and R. L. Belford, Inorg. Chem., 1964, 3, 1361.177 S. L. Holt and R. L. Carlin, J . Amr. Chem. Soc., 1964, 88, 3017; S. L. Holt,17* D. M. L. Goodgame and M. A. Hitchman, Inorg. Chem., 1964, 3, 1389.179 G. 8. Benner, W. E.Hatfield, and D. W. Meek, Imrg. Chem., 1964, 3,laoN. C. Stephenson, Act& Cryst., 1964, 17, 592.lslR. G. Hayter and F. S. H d w , J . Inorg. Nuclear Chem., 1964, 26, 807.228.R. J. Bouchard, and R. L. Carlin, ibid., p. 519.1644NICHOLLS : THE TRANSITION ELEMENTS 165of the complex.182 The existence of a planar tetrahedral structuralequilibrium similar to those reported last year has been established insolutions of three isomeric groups of bis- (o- hydroxynaphthaldimine)nickel( II)complexes. These and the related di- (N-R-salicylaldimine)nickel(n) com-plexes exhibit isotropic hyperfine contact shifts in their proton resonancespectra.183 A similar structural equilibrium exists when the green diamag-netic di- (p-keto-amine)nickel(n) complexes are dissolved in non-co-ordinatingsolvents ; these complexes are synthesised by using the reaction :laB ~ O H (Et4N),NiBr4 + 2Ac*CH:CMe*NRR + 2KOBut ,-+Ni[Ac*CH:CMe*NR], + ZEt,NBr + 2ButOH + 2KBrA series of ring-substituted di- (N-alkylsalicylaldimine)nickel( 11) complexeshas been studied.In the solid state the n-propyl derivatives are planar,and the t-butyl derivatives pseudo-tetrahedral ; the s-alkyl complexes areeither planar or pseudo-tetrahedral, depending on the nature and positionof the ring substituent.185 A crystal-structure determination of di-(N-ethylsalicylaldimine)palladium( 11) shows that the bonds around palladiumhave the trans-planar arrangement with non-planar chelate rings.lS6 Avariety of Schifl-base complexes containing quadridentate ligands has beenobtained in the reactions of various aldehydes and ketones with complexesof nickel(I1) with ethylenediamine, trimethylenediamine, triethylenetetra-mine, and 2-mer~aptoalkylamine.1~~ The ligand-field spectra of twelveoctahedral nickel(=) complexes containing ligands having the -N=C-C=N-chelate rings have been interpreted,l*s and the complete octahedral energy-level diagram for nickel(=) is calibrated in the region of high Dq (>1200cm .-l).The halogen-bridged anion in tetraethylammonium tetrabromo-,up'-dibromoplatinum(n), (Et,N)Pt,Br,, is practically planar and structurallyconsistent with the use of 5 ~ ? ( , ~ - , ~ , 6 ~ 6 p ~ bonding orbitals by the platinum.1sgMononuclear complexes, cis-[PtX,L(PR,)], are formed as the halogen-bridged compounds [Pt,X4(PR3),] react slowly with carbon monoxide andsimple mono-olefins.190 Far-infrared spectra of cis- and trans-[PtX,LJ(X = C1 or Br; L = neutral ligand) and trum-[PtXR(PEt,),] have beenrecorded.The wide ranges of v(Pt-X) indicate considerable dependence ofthe platinum-halogen bond strength on the nature of L when L is in thetrans-position to the halogen, but in the trans-complexes v(Pt-X) is almostW. C. E. Higginson, S. C. Nyburg, and J. S. Wood, Inorg. Chem., 1964, 3, 463;S. C. Nyburg and J. S. Wood, ibid., p. 468.lS3A. Chakravorty and R. H. Holm, Inorg. Chem., 1964, 3, 1010; R. H. Holm,A. Chakravorty, and G. 0. Dudek, J. Amer. Chern. Soc., 1964,86, 379; cf. Ann. Reports,1963, 60, 218.lS4 G. W.Everett and R. H. Holm, Proc. Chem. Soc., 1964, 238.ls6 1;. Sacconi, M. Ciampolini, and N. Nmdi, J . A m r . Chem. Soc., 1964, 86, 819.Ie6 E. Frasson, C. Panattoni, and L. Sacconi, Acta Crgat., 1964, 17, 85.Ie7 D. A. House and N. F. Curtis, J. Arner. Chern. SOC., 1964, 86, 1331, 223; M. C.M. A. Robinson, J. D. Curry, and D. H. Busch, Inorg. Chem., 1963, 2,Thompson and D. H. Busch, ibid., p. 213.1178.189 N. C. Stephenson, Acta Cryst., 1964, 17, 587.loo J. Chatt, N. P. Johnson, and B. L. Shaw, J. Chern. Sm., 1964, 1662166 INORGANIC CHEMISTRYinsensitive to the nature of L.lS1 In the dihydride,the Pt-H stretching frequency is the lowest observed, suggesting that thebridging phosphido-group has an even stronger tram-effect than the CN-The Pt-0 bond in 1-(4-substituted pyridine N-oxide)-3-ethylene-2,4-dichloroplatinum( 11) complexes is essentially a a-bond with little, if any,back- bonding contribution from the meta1.193Contrary to previous reports, platinum(1v) fluoride is diamagnetic whenpure, and attempts to confirm the existence of platinum(I1) fluoride havebeen unsuccessful.194 Ethylenediamine-NN'-diacetic acid forms tri- andquadri-dentate complexes with platinum(Iv).The oxidation of the quadri-dentate platinum( 11) compound by PtC1e2- is particularly interesting in thatthe incoming chloride groups are situated cis to each other.lg5Palladium(@ acetate and propionate are trimeric in benzene at 37"whereas at the b.p. they are monomerfc; the trimer-monomer system seemsto involve both bridge and chelate groups for the former and only chelategroups for the latter.lge The method reported earlier for the preparationof cis-dinitrodia.mminepalladium(n) yields instead ( PdN02(NH3)3]C1.197 Inbis-(2,2'-dipyridyliminato)palladium(rr) (2) the palladium(n) ion and t'hedonor nitrogen atoms are exactly coplanar and it is the ligands (surprisingly)which are considerably distorted from planarity.lg8t~a~[Pt,H,(PPh,),(PEt,),,Copper, Silver, and Gold.-Triethylamine forms 1 : 1 complexes withcopper(1) halides ; at -45 O copper(@ chloride forms yellow-green, crystallineCuC1,,2Et3N which on warming to 0 O undergoes internal electron-transferto give the diamagnetic, solid copper(1) c0mplex.19~ Complex acetylides ofsilver(I), K[Ag(C i CR),], have been prepared in liquid ammonia from thepotassium and silver salts of the acetylene HC i CR (R = H, Me, or Ph).A stable polymeric KC i CAg and a highly unstable silver acetylide AgC i CHlgl D.M. Adams, J. Chatt, J. Gerratt, and A. D. Westland, J . Chem. SOC., 1964, 734.lg2 J. Chatt and J. 31. Davidson, J . Chem. SOC., 1964, 2433.lgS S. I. Shupack and M. Orchin, Inorg. Chem., 1964, 3, 374.lg4 M. Bartlett and D. H. Lohmann, J . Chem. SOC., 1964, 619.lD5 C. F. Liu, Inorg. Chem., 1964, 3, 680.1913 S. M. Morehouse, A. R. Powell, J. P. Heffor, T. A. Stephenson, and G. Wilkinson,19' J. 5. Coe, R. Hulme, and A. A. Malik, J . Chern. SOC., 1964, 138.H. C. Freeman, J. F. Geldard, F. Lions, and M. R. Snow, Proc. Chem. SOC.,lgD J. T. Yoke, J.F. Weiss, and G. Tollin, Inorg. Chem., 1963, 2, 1210; 1964, 3,Ch.ern. and Ind., 1964, 544.1964, 258.1344NICHOLLS : THE TRANSITION ELEMENTS 167are also described.200 The oxidation of copper powder by silver per-chlorate in methyl cyanide gives crystalline [Cu(MeCN)dC104, and goldpowder gives [Au(MeCN)QClO, similarly.201The crystal structure of yellow (NH.J2CuCl4 contains discrete planarCuCI42- ions. It now becomes clear that the light-yellow copper(=) chloridecomplexes which exhibit thermochromism contain square-planar CUC~,~-ions, and the orange complexes contain nearly tetrahedral C ~ c 1 , ~ - ions.202The latter have been found in melts of czsium chloride and tributyl-2,4-dichlorobenzylphosphonium chloride.203 The absorption spectra of four-,five-, and six-co-ordinate chloro-complexes of copper(I1) have been measuredand interpreted in terms of the ionic mode1.204 The thermal dissociationof copper( 11) ammines, e .g., [Cu( NH 3) JBr2, [Cu( NH 3) s]S04, and [Cu( NH 3)J12,leads to stable lower ammines; on further heating, reduction to copper(1)0ccurs.20~ The copper(I1)-pyridine system has been the subject of a detailedstudy.Contrary to previous reports, there is no spectral evidence for theexistence of complexes with more than four pyridine molecules, but evidencewas found for ion-pair association and for the formation of the dichloro-dippidine complex in pure pyridine.206 The 2-methylpyridine complexes,(Z-mepy),CuCl, and ( 2-mepy),Cu(N03),, are probably monomeric, withdistorted tetrahedral structures ; [(Z-am~y)~( OH)CuC104], (2-ampy = 2-aminopyridine) reacts with 2,2’-bipyridyl to give [(bipy)( OH)CuClO,],, whichmust be a dihydroxo-bridged dimer in view of the ionic per~hlorate.~O7 Theunusual [for copper( 11) complexes] trigonal bipyramidal structure is foundin the iodobis-( 2,2’-bipyridyl)copper(11) catian.208 The copper(I1) chelateswith N-isopropyl- and N-s-butyl-salicylideneamine are isomorphous withthe analogous nickel(@, cobalt(=), and zinc(n) complexes and are thuspseudotetrahedral, in contrast to the N-n-alkyl complexes which are ~ l a n a r .~ * ~In contrast to the unfluorinated complex, bis(trifluoroacety1acetonato)-copper(=) readily adds two mol. of a base; a marked preference for six-co-ordination as opposed to five-co-ordination being shown.210Copper( 11) complexes with subnormal magnetic moments have been thesubject of a review.211 The nature of the copper-copper interaction incopper( 11) acetate dihydrate has been reconsidered from the molecular-orbital viewpoint and a bonding scheme proposed which appears to beadequate for explaining the magnetic and spectral properties of the complex.212The low magnetic moments (1.40 -+ 0.03 B.M.) found for the monoureaaddition compounds of copper( 11) allcanoates indicate that their structureis analogous to that of copper(=) acetate monohydrate.Copper(I1) salicylateR. Nast and H. Schindel, 2. anorg. Chem., 1963, 326, 201.201 G. Bergorhoff, 2. anorg. Chem., 1964, 357, 139.202 R. D. Willett, J .Chem. Phys., 1964, 41, 2243.203 G. P. Smith and T. R. Grif€iths, J . Arner. Chem. SOC., 1963, 85, 4051.204 W. E. Hatfield and T. S. Piper, Inorg. Chem., 1964, 3, 841.205 J. P. Smith and W. W. Wendlandt, J . Inorg. Nuclear Chem., 1964, 26, 1157.2oe J. Bjerrum, Acto Chem. Scand., 1964, 18, 843.207 W. R. McWhinnie, J . Chem. SOC., 1964, 2959.208 G. A. Barclay, B. F. Hoskins, and C. H. L. Kennard, J . Chem. SOC., 1963, 5691.209 L. Sacconi and M. Ciampolini, J . Chem. SOC., 1964, 276.210 R. D. Gillard and G. Wilkinson, J . Chein. SOC., 1963, 5885.211 M. Kato, H. B. Jonassen, and J. C. Fanning, Chem. Rev., 1964, 64, 99.212E. A. Boudreaux, Inorg. ChRm., 1964, 3, 506168 INORQANIC CHEMISTRY(anhydrous) and its tetrahydrate can be obtained in two different crystallineforms, in one of which the magnetic moment per copper atom is normalwhile in the other it is low.Ahhydrous copper@) benzoate forms threemodifications ; its addition compounds with benzoic acid, ethanol, and ureashow low moments, characteristic of some crystalline copper(@ carboxylateshaving the binuclear structure of copper at0ms.2~3 The susceptibility of anew series of monoamine adducts of copper(rr) acetate and butyrate, havebeen reported over an 80-350 OK range. Antiferromagnetic behaviour isobserved from which the separation between singlet and triplet states ofthe dimeric species are deduced. The absorption spectra of these compoundsstill resist complete el~cidation.~l4 Overlap of the dzs orbitals on copperatoms has been proposed to account for the low experimental magneticmoments of a series of binuclear copper(=) or-amine oxime complexes.215The reaction of silver(1) with cobalt(m) in perchlorate media consistsof a rapid equilibrium producing silver@) and cobalt@), followed bydecomposition of the The absorption spectra of three tetraco-having silver( 11) in a square-planar configuration have been measured.217Preliminary X-ray data on gold(m) fluoride indicate that it is not isostructuralwith any known fluoride.218 The stable pyridinium tetrabromoaurate(m)has been used for a chemical determination of the atomic weight of gold;thermal decomposition and analysis leads to an average value of196.97 & O*Ol.219Zinc, Cadmium, and Mercup.-Dielectric measurements of a number ofmolecular complexes of bivalent zinc, cadmium, mercury, and berylliumhalides are consistent with tetrahedral configurations for the undissociatedzinc, cadmium, and beryllium complexes; in the mercury complexes, theobserved polarisation is due to dissociation of the compounds in solution.220No clear relation has been found between the metal-halogen stretchingfrequency and the type of ligand used in halide complexes of zinc(@,cadmium(n), and mercury(n); at least in the solid state, the complexesL2CdC12 seem to have distorted octahedral rather than tetrahedral environ-ments about cadmium.221 The 1 : 1 adducts of zinc halides and substitutedanilines formed in ether solution fall into two classes.The stronger basesand acids tend to produce anilinium-type species whose spectra closelyresemble those of the corresponding anilinium ions; the adducts of weakbases have different spectra and are best described as charge-transferspecies.222 Bis(dipivaloylmethanido)zinc(n) has a tetrahedral structure ;the rings formed in the complex have delocalised n-bonding comparableOrbated complexes, [Ag(bipy),lS208~ [Ag(py)4]Sz08, and Ag(C,O4H*N),,21s M.Kishita, M. Inoue, and M. Kubo, Inorg. Chem., 1964, 3, 237, 239.214 E. Kokot and R. L. Martin, Inorg. Chem., 1964, 3, 1306.216 J. B. Kirwin, F. D. Peat, P. J. Proll, arid L. H. Sutcliffe, J . Phys. Chem., 1963,217 R. S. Banerjee and S. Basu, J . Inorg. Nuclear Chem., 1964, 26, 821.218 L. B. Asprey, F. H. Kruse, K. H. Jack, and R. Maitland, Inorg.Chem., 1964,21s G. Rienacker and G. Blumenthal, 2. anorg. Chem., 1964, 328, 8.220 S. R. Jain and S. Soundararajan, J . Imrg. Nuclear Chem., 1964, 26, 1265.221 G. E. Coates and D. Ridley, J . Chem. SOC., 1964, 166.2s2D. P. N. Satchel1 and J. L. Wardell, J . Chem. SOC., 1964, 4296.J. E. Young, R. K. Murmrtnn, J . Phg.9. Chem., 1963, 67, 2647.07, 2288.3, 602NICHOLLS : THE TRANSITION ELEMENTS 169with that generally postulated for acetylacetonate rings.223 Potentiometricstudy of the mercury(=)-aniline system has revealed 1 : 1 and 1 : 2 complexes ;a 1 : l aniline-mercury(1) complex has been confirmed from its ultravioletabsorption spectrum. The stability constants of ammonia and guanidinecomplexes of mercury(=) have been measured, and a general discussion ofthe mercury(=) complexes with nitrogen bases has been presented.224 Thechemistry of halogenomercurate( a) complexes has been reviewed.225 Thelower mercaptides of mercury(@, Hg(SMe), and €€g(SEt),, have molecularstructures with weak intermolecular Hg-S bonds ; the t-butyl mercaptidehas a polymeric structure with mercury surrounded by sulphur atoms in ahighly distorted tetrahedral arrangement, the sulphur of the mercapto-groupacting as a bridge between two neighbouring mercury atoms.226 The alkali-metal oxomercurates(n), M,HgO,, have been obtained as colourless,moisture-sensitive, tetragonal crystals.227a25 F.A. Cotton and J. S. Wood, I w g . Chem., 1964, 3, 245.22eT. H. Wirth and N. Davidson, J . Amer. Chem. SOG., 1964, 86, 4314, 4325.225 G.B. Deacon, Revs. Pure Appl. Chm. (Australia), 1963, 13, 189.r 2 a D. C. Bradley and N. R. Kunchur, J . Chm. Phys., 1964,40,2258; N. R. Kunchur,227 R. Hoppe and H.-J. Rohrborn, 2. unorg. Chem., 1964, 329, 110.Nature, 1964, 204, 4684. COMPLEXESBy D. Nicholls( The Donnan Laboratories, The University of Liverpool)General.-The complexity of ligands is ever increasing and a multitude ofco-ordination compounds has been prepared throughout the year, usinglarge organic molecules containing nitrogen, oxygen, or sulphur donor atoms.The more exciting experimental advances, however, have been concernedwith the co-ordination chemistry of simpler ligands, e.g., nitrate and bidentatesulphur donors, and with the chemistry of compounds containing metal-metal bonds.The latter will be discussed under a separate heading at theend of this section. Useful reviews have appeared on complexes of thetransition metals with phosphines, arsines, and stibines and on complexesof tetradentate ligands containing phosphorus and arsenic.2The recent progress made in the study of anhydrous metal nitrates andnitrato-complexes has been the subject of two extensive review^.^ The termnitrate is suggested for those compounds containing ionic M-NO, bondsand the prefix nitrato where the NO, group is covalently bonded throughone or more of its oxygen atoms. It has now been established that anhydrouscopper(I1) nitrate exists in two crystalline forms. The a-form is obtainedby heating the adduct Cu(NO,),,N2O4 in vacuo to 100" and is converted intothe p-form by vacuum-sublimation at 200"; the two forms may be dis-tinguished by their infrared spectra and X-ray powder photograph^.^ Thefull report of the structural determination of gaseous copper(I1) nitrate byelectron diffraction has now been publiahed and the structure found to differfrom that reported earlier.The nitrate groups are bidentate (l), the centralcopper atom having four nearest oxygen atoms at 2.00 & 0.02 and twonitrogen atoms at 2.30 & 0.03 k5 The nitrate groups are similarly bidentatein crystalline tetranitratotitanium(rv) ; they are disposed around the metalin a flattened tetrahedral arrangement. It now becomes possible to assignthe 1630 cm.-l band in the spectra of titanium(Iv) and tin(Iv) nitrates tothe terminal N=O stretching frequency of a bidentate nitrate; it becomesapparent also that those nitrates possessing strong oxidising powers havebidentate nitrate groups, whereas unidentate groups are present in the un-reactive nitrates.6 The finding of bidentate nitrate groups last year in1 G.Booth, Adv. Inorg. Chem. Radiochem., 1964, 6, 1.2L. M. Venanzi, Angew. Chem., 1964, 76, 621.3 C. C. Addison and N. Logan, Adv. Inorg. Chem. Radiochem., 1964, 6, 72; B. 0.4N. Logan, W. B. Simpson, and S. C. Wallwork, Proc. Chem. SOC., 1964, 341.6 R. E. Lavilla and S . H. Bauer, J . Amer. Chem. SOC., 1963, 85, 3597.6 C. C. Addison, C. D. Garner, W. B. Simpson, D. Sutton, and S . C. Wallwork,Field and C. J. Hardy, Quart.Rev., 1964, 18, 361.Proc. Chem. Soc., 1964, 367NICHOLLS : COMPLEXES 171Co(Me,P0),(NO3), prompted the structural determination of[~Ph412ID(NO23) 43a complex having magnetic and spectral properties characteristic of tetra-hedrally co-ordinated cobalt(@. The nitrate groups are indeed bidentate,the cobalt being eight-co-ordinate in a dodecahedra1 complex. ,4 usefulstructural principle may be inferred from these findings, namely, that apolyatomic ligand in which two chemically equivalent atoms are held muchcloser together than such a pair of atoms would be if independent of eachother, has a tendency to interact through both of the equivalent atoms insuch a way that the mean positions of the pairs of atoms lie roughly a t thevertices of one of the usual (e.g., octahedral or tetrahedral) co-ordinationpolyhedra.jr New volatile anhydrous nitrato-complexes prepared includeHf(N03)4,N206, In(NOs),, and Pd(N0,)2.sThere has been widespread interest in complexes of the general formula~S,C4R4I2 formed by bidentate sulphur donors with bivalent transition-metal ions. One of the most significant results of these investigations isthe discovery that these compounds undergo reversible and unusually readyelectron-transfer which has permitted the synthesis of a wide variety ofcomplexes with a total charge z = 0, -1, or -2. In particular, the maleo-nitriledit,hiolate (MNT) complexes (R = CN) have received detailed attention ;L(2)these are invariably square-planar (2) as shown, for example, by crystal-structure determinations on (Me,N),[Ni(MNT),] and (BU~~N),[CO(M.NT),].~In the copper(m) complex (Bun,N),[Cu(MNT),], the anion has the planarstructure but, in contrast to the metal atoms in the cobalt salt, the copperatoms are not well separated, the shortest Cu-Cu distances being 4.026 and4.431 B.lo The green rhodium complex (Bun,N),[Rh(MNT),] is isomorphouswith the nickel analogue and so is the first example of square-planarrhodium( 11) .ll The synthesis a,nd characterisation of the series of complexes,[MS,C4RJZ ( z = 0, - 1, or -2; R = CN, CF,, or Ph; M = Cu, Co, Ni, Pd, Pt,or Au) has yielded the first four-co-ordinate paramagnetic complexes ofpalladium and platinum.12 The solid-state magnetic properties of(Et,”M(MNT),IF. A.Cotton and J.G. Bergman, J . Amer. Chem. Soc., 1964, 86, 2941; cf. Ann.Reports, 1963, 60, 222.B. 0. Field and C. J. Hardy, J. Chem. Soc., 1964, 4428.OR. Eisenberg, J. A. Ibers, R. J. H. Clark, and H. B. Gray, J . Amcr. Ohem.SOC., 1964, 86, 113; J. D. Forrester, A. Zalkin, a-nd D. H. Templeton, Inorg. Chm.,1964, 3, 1500.lo J. D. Forrester, A. Zalkin, and D. H. Templeton, Inorg. Chem., 1964, 3, 1507.l1 E. B a g , S. I. Shupack, J. H. Waters, R. Williams, and H. B. Gray, J . Amer.Chem. SOC., 1964, 86, 926.la A. Davison, N. Edelstein, R. H. Holm, and A. H. Maki, Inorg. Chem., 1963,2, 1227, 1964, 3, 814; E. Billig, R. Williams, I. Bernal, J. H. Waters, and H. B. Gray,Inorg. Chem., 1964, 3, 663172 INORGANIC CHEMISTRYcomplexes wherein the metal ion formally has an odd-number of d electrons(M = Fe, Ni, Pd, or Pt) indicate that they exist in a singlet ground statewith a corresponding low-lying triplet state; it is suggested that spin cor-relation occurs through sulphur-atom d orbital interaction with the metalion of an adjacent chelate m01ecule.l~ The observed bands in the electronicspectra of the nickel, palladium, and platinum complexes are due to M,ligand-to-metal and metal-to-ligand charge transfer, and intrdigand transi-tions.Evidence to support the formulation of some of these [M(MNT),)-complexes as composed of M(1) and radical-anion ligands has been discussed.l*The cobalt compound (Bu",N)[Co(MNT),] is diamagnetic in the solid stateand in cyclohexanone solution; in dimethyl sulphoxide it gives peff = 2-81B.M.and there is a shift in the spectral band from 790 to 715 mp. The solu-tion in pyridine is green and the diamagnetic complex, (Bu",N)[Co(MNT),py],can be isolated; this compound and the similar triphenylphosphine adductare the first examples of diamagnetic, five-co-ordinate cobalt (m) ~omp1exes.l~An unusual route to aryl, arylalkyl, and alkyl-ap-dithioketone complexesof nickel, Ni(S,C,R,),, involves the reaction of nickel(n) sulphide withdiphenylacetylene, l-phenylpropyne, and but-2-yne.l6 With vanadium andthe Group VI transition metals several six-co-ordinate complexes of thegeneral formula [MS,C,R,]" have been characterised. The complexes aresimilar to the related bis-complexes in that they contain metals stabilised inseveral different oxidation states and complexes of given R and M can beinterconverted by simple oxidation-reduction.The vanadium compound (3)has especial significance in the problem of formulation of t.he ground statesof these complexes containing bidentate unsaturated sulphur donors ; thusit may be formulated as tri-( cis-stilbene-@-dithiolato)vanadiurn(vI) ortris(dithioben~il)vanadium(O).~~ Other sulphur ligands used this yearinclude the tridentate di-(2-3'-pyridylethyl) sulphide (bpes) which forms acopper complex Cu( bpe~)(ClO,)~ having one complex- bonded perchlorate~ O U P , ~ ~ zbnd the newly synthesised 2-2'-thienylpyridine and methyl a-picolylsulphide.l@ Highly coloured, non-ionic complexes (CrL3,1*5H,0, MnL,,H,O,FeL,, CoL3,2H,O, NiL,, and CuL,) are formed by chelation of the oxygenIs J.F. Weiher, L. R. Melby, and R. E. Benson, J . Amer. Chem. SOC., 1964, 86,4329.l4 S. I. Shupack, E. Billig, R. J. H. Clark, R. Williams, and H. B. Gray, J . Amer.Chem. SOC., 1964, 86, 4594.16 E. Billig, H. B. Gray, S . I. Shupack, J. H. Waters, and R. Williams, Proc.Chem. am., 1964, 110; C. H. Langford, E. Billig, S . I. Shupack, and H. B. Gray,J . Amer. Chm. SOC., 1964, 86, 2958.1' A. Davison, N. Edelstein, R. H. Holm, and A. H. Maki, J. Amer. Chm. Soc.,1964, 86, 2799; J. H. Waters, R. Williams, H. B. Gray, G. N. Schrauzer, and H. W.Finck, ibicE., p. 4198; G. N. Schrauzer, H. W. Finck, and V. Mayweg, 2. Natqfwsch.,1964, 19b, 1080.18 E. Uhlig and G. Heinrich, 2. a w g . Chem., 1964, 530, 40.Is K.Kahmann, H. Sigel, and H. Erlenmeyer, Helv. Chim. Acta, 1964, 47, 1764.G. N. Schrauzer and V. Mayweg, 2. Naturforsch., 1964, 19b, 192NICHOLLS : COMPLEXES 173and sulphur atoms from 1-hydroxypyridine-2-thione (L).20 Studies on thespectral and magnetic properties of tris( dithio-oxalato) complexes ofchromium(m) and cobalt(m) have been interpreted in terms of the simplecrystal-field picture. It seems that, while the ligand field strength of sulphurin its compounds vanes enormously and is frequently not strong, sulphurleads to an exceptional decrease in interelectron repulsion on the centralmetal ion so that it appears to act as a strong field donor atom.21Transition-metal complexes of mercapto-amines react with alkyl halidesto give complexes in which the co-ordinated mercapto-group is transformedinto a bound thio-ether group, e.g., [Ni(NH2=CH2*CH2*S),] gives octahedral[Ni(NH2*CH,*CH,*SR),X2]. An extension of these reactions, in whichBrH2C- - c\H2RC=N: 1 ,Ni I ,S--CH~QMeC=N, I )S-CHzH;C f CH2Br (41dihalides are used, has led to the synthesis of macrocyclic ligands in situ;e.g., reaction of (a-diketonebismercaptoethylimine)nickel(n[) complexes witha'-dibromo-o-xylene gives it product (4).22 Some planar quadridentatechelate compounds have been prepared from butane-2,3-dione di-( 2-pyridylhydrazone) and transition-metal salts favouring square-planar co-ordination [Cu(n), Ni(n), and Pd(n)] ; tridentate chelating agents have beensynthesised by condensation of a-diketones with N-heterocylic hydrazines.aComplexes with seven- and eight-membered rings are formed from anhydroustransition-metal perchlorates in methanol with o-xylylenediamine and2-aminornet hylphenet hylamine, respe~fively.~4 The complex compoundsc~-di(pyridine-2-aldoxime)-copper(n), -palladium(@, and -platinum(rc) havethemselves been successfully used as oxygen-donor bidentate ligands ;homopolynuclear chelates of copper(I1) ( 5 ) are easily isolated as the iodide,0-0-. I\.u(5)perchlorate, or sulphate.25 The Synthesis, separation, and characterisationof the three isomeric M(tfac-),(acac-) complexes and of M(tfac-)(acac-),20M. A.Robinson, J . Inorg. Nuclear Chem., 1964, 26, 1277.21R. L. Carlin and F. Canziani, J. Chem.Phye., 1964, 40, 371.2 2 D. H. Busch, D. C. Jicha, M. C. Thompson, J. W. Wrathall, and E. Blinn,J . Amy. C h y . Soc., 1964,86,3642; M. C. Thompson and D. H. Busch, ibid., p. 3661.2a B. Chiswell and F. Lions, Inorg. Chem., 1964, 3, 490; B. Chiswell, F. Lions,and M. L. Tomlinson, ibid., p. 492.zrR. C. Brasted, T. D. O'Brien, and W. L. Heino, Inorg. Chem., 1964, 3, 503.25 C. F. Liu and C. H. Liu, Inorg. Chm., 1964, 3, 678174 INORGANIC CHEMISTRY(tfac- = anion of 1 ,l,l-trifluoropentane-2,4-dione, acac- = anion of pentane-2,4-dione) for both cobalt(m) and chromium(II1) has been achieved.26 TheDq values for the tri( acetylacetonate) complexes of some tervalent transitionmetals have been calculated from thermochemical data alone and found tobe in fair agreement with those obtained by spectroscopic methods.27 Thecrystalline acid salt, Mn,(HY),,lOH,O (H4Y = EDTA), contains seven-co-ordinate [Mn(0H2)Y12- ions and these are formed into quasi-infinitechains [Mn(OH2)YHInn- by hydrogen bonding with the acid protons; seven-co-ordinate anions [Fe(OH,)YJ- occur also in Rb[Fe( OH2)YIH20 andLi[Fe( OH2)YJ2H,0.2*A calorimetric study has established an upper limit for the lODq valuesfor some hexacyano-complexes of bivalent transition-metal ions.29 Froman infrared study of anhydrous complex cyanide acids it is concluded that,while the H4M(CN), (M = Fe, Ru, or 0 s ) acids contain unsymmetricalN-H..*N hydrogen bonds, symmetrical N-H-N bonds are present inHAu(CN),, H,Pd(CN),, H2Pt(CN),, H3Rh(CN),, and H31r(CN)6.30 Somecomplex cyanides are reduced in molten potassium cyanide at -500";K,&(CN), is reduced to a green cyano-complex containing manganese@)and manganese( 111), and K4Mo( CN) gives K2Mo( CN) 5.31 The reductionand subsequent complex formation of some transition-metal halides withmethyl cyanide has been dealt with in section 3.Manganese(@ and nickel(@chlorides and bromides form octahedral complexes MX2,2MeCN, and cobaltforms tetrahedral complexes, CoX2,3MeCN, which contain one mol. ofunco-ordinated methyl cyanide; the iodides of these three metals apd ofiron form the complexes [M(MeCN),I2+[MIJ2-. Iron reacts with chlorineor bromine in methyl cyanide to give crystalline complexes in whichtwo-thirds of the iron is present as tetrahedral iron(m) and one-third asoctahedral iron( 11) , e.g., [Fe( MeCN) 6]2+[FeBr4]2-.32 Isocyanato- complexes,(Et,N),M(NCO),, (M = Mn, Ni, or Zn) containing the tetrahedral tetraiso-cyanatornetallate( 11) anions have been de~cribed.~3 The 14N chemical shiftsin soluble, diamagnetic metal thiocyanate complexes have been used todetermine whether the thiocyanate ligand is bonded to the metal throughsulphur or nitrogen.34 In transition-metal compounds containing thetricyanomethanide ion, M[C(CN),],,xH,O (M = Mn, Fe, Co, Ni, or Cu), themagnetic and spectral properties suggest weak field octahedral co-ordinationand a polymeric structure is proposed.35Far-infraredspectra of metal-pyridine complexes enable one to distinguishbetween tetrahedral, planar, tetragonal, monomeric octahedral, and poly-meric octahedral stereochemistry irrespective of the electronic configuration28 R.A. Palmer, R. C. Fay, and T. S. Piper, Inorg. Chem., 1964, 3, 875.27 J. L. Wood and M. M. Jones, Inorg. Chem., 1964, 3, 1553.28 S. Richards, B. Pedersen, J. V. Silverton, and J. L. Hoard, Inorg. Chem., 1964,3, 27; M. D. Lind and J. L. Hoard, ibid., p. 34; M. J. Hamor, T. A. Hamor, andJ. L. Hoard, ibid., p. 34.29 F. H. Guzzetta and W. B. Hadley, Inorg. Chem., 1964, 3, 259.80 D. F. Evans, D. Jones, and G. Wilkinson, J . Chem. SOC., 1964, 3164.81 W. L. Magnuson, E. Griswold, and J. Kleinberg, Inorg. Chem., 1964, 3, 88.82 B. J. Hathaway and D. G. Holah, J . Chem. SOL, 1964, 2400, 2408.a8 D. Forster and D. M. L. Goodgame, J.Chem. Soc., 1964, 2790.8 p 0. W. Howarth, R. E. Richards, and L. 31. Venanzi, J . Chem. SOC., 1964, 3335.8 5 J. H. Enemark and R. H. Holm, Inorg. Chem., 1964, 3, 1516NICHOLLS : COMPLEXES 175of the metal.86 The thermal decomposition of di( quinoline)metal( II) halideshas been studied; the quinoline complexes of manganese(=) and nickel(=)chlorides, together with monoquinolinenickel(n) bromide, have octahedralco-ordination about the metal, while the quinolinecobalt(nc) chlorides anddi( quinoline)nickel(n) bromide have tetrahedral co-ordination.87 The in€ra-red spectra of some bis-( 2,2’-bipyridy1)metal complexes have been studiedand it is concluded that complexity in the 700-800 cm.-l region is probablydue to a cis-configuration of the two bidentate ligands; the spectrum ofCu( bipy)S04,2H20 is consistent with a polymeric structure involving bridgingsulphate groups.38 Some complexes of the new ligand, bipyrazinyl (6), havebeen prepared ; their stoicheiometries are similar to those obtained with2,2’-bipyridy1.8@ Imidazole and imidazolate complexes have been character-ised for nickel(II), copper(=), zinc(=) and silver(1) and their heats of formationdetermined, By comparing data on the N-methylimidazole complex withthose of the imidazole complex of silver(1) the site of complex formation ofthe imidazole molecule has been shown to be the hydrogen-free nitrogenatom.40 Some new cationic complexes of hexamethylphosphoramide(HMPA), OP(NMe,),, have been de~cribed;~~ [Fe(€€MPA)4’2+ is the firsttetrahedral cation of iron@) ; tervalent iron and chromium form octahedralcations [M( HIMPA),J3+.Octamethylpyrophosphoramide(Me&) ,OP*O*PO (We,)can form six-membered rings with metal ions in which the rings includeonly phosphorus, oxygen, and the The donor properties of thepositively charged ligands [Me3N+*[CH2]2*NE€2] and [Mefl+*[CH,],.NH,]have been investigated, and complexes with these ligands of the types[M(L+)6](c104)8 [M = CO(II) and Ni(n)] and [M(L+),](ClO,), [M = Cu(n),Zn(n), Cd(n), and Pd(n)] have been isolated.& Crystalline complexes con-taining BH, as an electron-accepting group have been obtained by treatingdiborane with Group VII metal carbonyl anions; salts of [Re(CO),]-,[Mn(CO) 5]-, and [Ph,PMn(CO),]- give monoborane complexes and salts ofa bis(borane) complex, [(H,B),Re(CO),]-, have also been is0lated.4~ Theinfrared spectra of compounds of the type [MA4X2JX,HX,2H20 (&I = Cr,36 R.J. H. Clark and C. S. Williams, Chem. and Ind., 1964, 1317.37 D. H. Brown, R. N. Nuttall, and D. W. A. Sharp, J. Inorg. -Nuclear Chem.,W. R. McWhinnie, J . Inorg. Nuclear Chem., 1964, 26, 15.8D A. B. P. Lever, J. Lewis, and R. S. Nyholm, J. Chem. SOC., 1964, 1157.40 J. E. Bauman and J. C. Wang, Inorg. Chern., 1964, 3, 365.41 J. T. Donoghue and R. S . Drago, Inorg. Chem., 1963, 2, 1158.4 2 M. D. Joesten and K. M. Nykerk, Inorg. Chein., 1964, 3, 548,1964, 26, 1161.J. V. Quagliano, J. T. Summers, S. Kida, and L. M. Vallarino, Inorg. Chem.,1964, 3, 1657.4& G.W. Parshall, J . A n w . Chem. SOC., 1964, 86, 361176 INORGANIC CHEMISTRYCo, or Rh; A = ien, Qpn, i p s ; X = C1 or Br) confirm the presence ofthe diaquohydrogen ion [H50,]+; new compounds of this type reported46are trarts-[Rhen,Cl 2]( H 50 2)C12, trcms-[Rhen ,Br ,](I3 2)Br,, and alsotram-[Rh( bipy),Cl,]( H502)C12.A cryostat has been described in which magnetic susceptibility measure-ments may be made by audio-frequency mutual-induction technique attemperatures down to 0.35 OK ; powdered Co( OAc),,4B20 and Ni( OAc),,4H20are paramagnetic at the lowest temperatures attained.4s Diffuse reflectancespectra of anhydrous transition-metal halides MX, and MX, (M = do to d6metal) have been measured, values of Dq for chloride ion have been obtained,and the conclusion has been reached that there is very little differencebetween the ligand field strength of terminal and bridging chloride ions.*'The absorption spectra of all the dipositive metal ions from titanium tocopper, in molten aluminium(m) chloride, can be interpreted on the basisof octahedral configurations of chlorides about the metal ions; this is incontrast to the situation in molten alkali-metal chlorides where, with theexception of V2+, the dipositive 3& ions display four-fold co-ordination.48The wave-numbers of charge-transfer bands in 1 : 1 complexes between anoxidising metal and a series of reducing ligands have been plotted againstthose for other metals with the same ligands; the resulting straight-line plotshave been used to discuss the stereochemistry of copper, redox potentials,the spectra of thiocyanate complexes, and solvent effects.49 Simple crystal-field calculations of the contributions of the field-crystal stabilisation energyto the activation energy for a series of trisoxalato-complexes of tervalenttransition metals have led to an order of reactivity which is in qualitativeagreement with the experimental order.jO The Mulliken-Wolfsberg-Helmholz L.C.A.O.molecular-orbital treatment of complexes has been testedby calculating the &-orbital splittings in [Cr(NH,),]3+, [cO(NH,)6l3+,[co(NH,)6]2+, and [Ni(NH3)s]2+; it is found that strict adherance to a fixedset of rules for the choice of atomic-orbital energies and a fixed value forthe proportionality constant relating resonance integrals Hij to the productof the overlap integral 8 i j and the geometric mean of the integrals Hii andHij fails to afford uniformly accurate re~ults.5~ Ligand-field theory predictsthat truly octahedral complexes m6 could exist in which low- and high-spintypes are in thermal equilibrium at ordinary temperatures ; the magneticand spectral properties associated with nearly equi-energetic high- and low-spin states should be singularly sensitive to temperature, pressure, and minorchemical changes in the ligands.Some experimental data presented foriron(m) NN-dialkyldithiocarbamates, i.e., FeS,-type compounds, illustratethese features qualitatively ; the reciprocal magnetic susceptibility passesthrough a maximum and then a minimum with increasing temperature, theelectronic spectrum is temperature-dependent, and different alkyl sub-p5 R.D. GiIlard and G. Wilkinson, J . Chem. Soc., 1964, 1640.46 J. T. Schriempf and S. A. Friedberg, J . Chem. Phys., 1964, 40, 296.4 7 R. J. H. Clark, J . Chem. SOC., 1964, 417.48 H. A. 0ye and D. M. Gruen, Inorg. Chem., 1964, 3, 836.5O R. W. Olliff and A. L. Odell, J . Chem. SOC., 1964, 2417.61 F. A. Cotton and T. E. Haas, Inorg. Chem., 1964, 3, 1004.J. C. Barnes and I?. Day, J . Chm. Soc., 1964, 3886NICHOLLS : COMPLEXES 177stituents in the ligand drastically affect the magnetic properties."2 Analternative, and possibly preferable, energy-level diagram for an octahedraltransition-metal complex MX, (X = Halogen) has been suggested relevantto the case of silver(0) in alkali-metal halides.=The inconsistency of empirical criteria for the determination of absoluteconfiguration of complexes has been pointed out.In all cases where theelectronic transitions of the chromophore considered are degenerate in thezero order, the empirical comparison of Cotton-effect curves is an unreliableguide to absolute configuration unless the compounds into which thedegenerate transition is split in the dissymmetric molecule are identifiedand the Cotton effects of the individual components are compared." Theabsolute configuration of ( + )-trans-cyclopentane- 1,2-diamine has beencorrected by utilising the optical rotatory dispersion curves of its complexcompounds with cobalt(@. By using the principle that the conmationof the most stable isomer of [M(diamine),]"+ is determined by the absoluteconfiguration of the diamine, the configurations of a number of complexeshave been determined.55 A molecular-orbital model for the optical activityof trigonal co-ordination compounds has been de~eloped.~~Mechamsms * of Readions of Inorganic Complexes.-The assumption thatsubstitution reactions of octahedral complexes in aqueous solution proceedthrough an intermediate aquo- or hydroxo-complex has now been seriouslyquestioned ; even in monosubstituted aquo-complexes such as [Cr( H20) JI2+direct substitution of C1- for I- occurs without intermediate formationof [Cr(H20),]3+.67 The importance of steric factors in replacement hasbeen pointed out; the low-spin d8 complex [Pd(Etddien)C1]+(Et4dien =Et,N*CH,*CH,*NH*CH,*CH,*NEt,) reacts like an octahedral complex, Le.,the rates of its replacement reactions do not depend upon the reagent andit has consequently been called a pseudo-octahedral complex.58 The rates ofsome such reactions of palladium(=)-acetylacetonate complexes have beenmeasured; the order of nucleophilic reactivity found and the kinetic formof the observed rate constants suggest that palladium and platinum systemsreact by similar 8 ~ 2 mechanisms.59The reaction, 1 ,2,6-[Rh(py),C13] + py ---+ trans-[Rh(py),Cl,]Cl is catalysedvery effectively by molecular hydrogen at room temperature and atmosphericpressure; a similar catalysis is observed in the aquation of rhodium(m)chloride, and intermediate hydride formation is thought to be responsiblefor the catalysis.6o Quantitative estimates of the kinetic trans-effect inoctahedral complexes have now been obtained from a study of the reactionsof tmm-[Rh en2X2]+ (X = Halide) with other halide ions; the trans-effect280, 235.280, 259.63 A.H. Ewald, R. L. Martin, I. G. Ross, and A. H. White, Proc. Roy.Soc., 1964, A ,rsM. C. R. Symons, J . Chem. SOC., 1964, 1482.6 * A. J. McCaffery, S. F. Mason, and B. J. Norman, R o c . Roy. SOC., 1964, A ,6K J. H. Dunlop, R. D. Gillsrd, and G. Wilkinson, J . Chena. Soc., 1964, 3160.56 A. G. Karipides and T. S. Piper, J . Chem. Phys., 1964, 40, 674.57M. Ardon, Proc. Chm. Soc., 1964, 333.6a W. H. Ehddley and F. Basolo, J . Amer. Chem.Soc., 1964, 86, 2075.Kn R. G. Pearson and D. A. Johnson, J . Amer. Chem. SOC., 1964, 86, 3983.*OR. D. Gillazd, J. A. Osborn, P. B. Stockwell, and G. Wilkinson, Proc. Chem.SO&, 1964, 284178 INORGANIC CHEMISTRYof I- is 850 times that of C1- when a Rh-Cl bond is being broken and 97 timesthat of Br- when a Rh-Br bond is being broken.61 The kinetic aspects ofthe trans-effect have been strikingly demonstrated in a study of the reversibleacid and base hydrolyses of the [PtC13NH3]- ion; thus, the isomer formedmost rapidly is the thermodynamically unstable one.62 Studies on themechanisms of octahedral replacement reactions in non-aqueous solventshave been initiated in dimethyl sulphoxide 63 and continued in liquidElectron-transfer reactions have now been studied for metals which inboth their oxidised and reduced states give complexes that do not readilyundergo replacement reactions.The products of the reduction of the ion[(NH3),RhXI2+ (X = C1 or Br) by chromium(n) ions are ammonium ion,metallic rhodium, and an aquochromium(rn) complex containing the ligandX.65 Kinetic studies have been made of reactions of the ammine ionRu(NH,),~+ with complex ions of the type (NH3),Co111L for a variety ofligands L. These reactions are necessarily of the outer-sphere type and therelative specific rates of reaction are comparable with the relative rates ofreduction of the same cobalt(m) complexes by other agents that requirethe same type of activated complex.68 A detailed study has been madeof aromatic and heterocyclic carboxylates as bridging groups in oxidation-reduction ; from the specific rates of reduction of a large number of carboxyl-atopenta-amminecobalt(m) complexes with Cr2+, it is found that most ofthe reactions proceed by the usual electron-transfer path through the co-ordinated carboxylato-group with formation of carboxylatochromium(m)complex.67 In the reactions of Cr2+ with the sexidentate complex, ethylene-diaminetetra-acetatocobaltate(m), Co(Y)-, or CO(C,O,),~-, the nature of thechromium( rn) product depends upon the hydrogen-ion concentration of thereaction mixture; below 0 .0 1 ~ for co(Y)-, and below 0*02M for C O ( C ~ O ~ ) ~ ~ - - ,at least 90% of the chromium(m) product is attached to three carboxylato-groups.68The temperature- jump technique has been used to provide evidence forthe presence of tetrahedral ions, Co(H20),2+ and Zn(H20),2+, in aqueoussolutions of Co2+ and Zn2+, respectively.69 A flow technique has been usedin a study of the reaction of Co3+ with chloride ion; the rate constants forcomplex formation have been measured at 25" for the system:70hk-1C O ~ + + C1- C0Cl2+Carbonyls.-The method for analysing and assigning carbonyl stretching61 F.Basolo, E. J. Bounsall, and A. J. Poe, Proc. Chem. SOC., 1963, 366.6 2 M. A. Tucker, C. B. Colvin, and D. S. Martin, Inorg. Chm., 1964, 3, 1373.63 3%. L. Tobe and D. W. Watts, J . Chem. SOC., 1964, 2991; C. H. Langford, Inorg.64 H. H. Glaeser and J. P. Hunt, Inorg. Cbm., 1964, 3, 1245.6s G. T.Takaki and R. T. M. Framr, Proc. Chem. SOC., 1964, 116.68 J. F. Endicott and H. Taube, J . Amer. Chem. Soc., 1964, 86, 1686.67 E. S. Gould and H. Taube, J . Amer. Chem. SOC., 1964, 86, 1318.66 P. B. Wood and W. C. E. Higginson, Proc. Chem. SOC., 1964, 109.69 T. J. Swift, Inorg. Chem., 1964, 3, 526.70 T. J. Conocchioli, G. H. Nancollas, tmd N. Sutin, Proc. Chem. SOC., 1964, 113.Chern., 1964, 3, 228NICHOLLS : COMPLEXES 179frequencies reported last year in octahedral metal carbonyls has beenextended. A relation between carbonyl bond orders and carbonyl forceconstants is delineated and, from differences in the calculated carbonylstretching constants, is used to deduce the changes in carbonyl bond orders ;absolute values of the bond orders may be e~timated.7~ Carbonyl bendingfrequencies in complex carbonyls have been observed in the range 468-682 cm.-1;72 the influence of the solvent on the stretching frequencies ofnitrosyl and carbonyl attached to metal has been discussed in some detail.73The molecular structure of the octacarbonyl, CO,(CO)~, is very nearly thatof the nonacarbonyl, Fe,(CO),, less one bridging carbonyl group.74 Thenew compound, Fe2(CO)J2, has a structure almost certainly analogous tothat of M~I,(CO)~,, the two axial carbonyl groups being replaced by iodineatoms; the red form of Co(CNMe),(CIO,), has been shown to be a dimer,isostructural with Mn,(CO),,.75 The carbonylation of iridium(m) oriridium(rv) iodide, either alone or mixed with potassium iodide, gives awhole series of iridium carbonyl iodides; the salts, K[IrBk,(CO)] andK[IrCI,(CO)], are obtained by the action of bromine and chlorine, respectively,on the corresponding iodo-derivatives.76 The stable molecdar-oxygencarrier, O,IrCl(CO)(PPh,),, has been isolated ; determination of its X-raymolecular structure shows that the two oxygen atoms are equidistant fromiridium and therefore equivalent, and the 0-0 distance is intermediatebetween those in O2 and O,2-.77 The new carbonyl, C5H,Ta(CO),, as wellas the vanadium and niobium analogues, can be prepared by reaction ofequimolar mixtures of mercury( II) chloride and cyclopentadienylsodiumwith the hexacarbonylmetallates in dimethoxyethane at room temperat~re.'~Halogenocarbonylmanganese anions, [Mn(CO),Xyl- (X and Y = C1, Br,I, or CN) have been isolated as their tetra-alkylammonium salts; the actionof halide ions on MII,(CO),~ gives salts of [Mn,(CO)aX,]2-.79 Oxidation ofthe N-methylpyridinium salts, [C,H,NMe][M(CO),I] (M = Mo or W), byiodine has led to the unexpected discovery of the diamagnetic derivatives,[C,H,NMe][M(CO),I,], containing heptacovalent anions.80 In liquid am-monia, the bipyridyl complexes, M(CO),bipy (M = Cry Mo, or W), reactwith potassium cyanide to form K,[Cr(CO),(CN),] and K,[M(CO),(CN),](M = Mo or W);81 with potassium acetylides, KC i CR, the complexes,M(co)3(N&)3 (M = Mo or W), give diamagnetic tricarbonyltrialkinyl-rnetallates(O), K,[M(CO),(C I CR),].S2 Tricyanomethylmetal carbonyls have71 F.A. Cotton, Inorg. Chem., 1964, 3, 702; cf.Ann. Reports, 1963, 60, 232.72D. M. Adams, J . Chem. Soc., 1964, 1771.73 W. Beck and K. Lottes, 2. Naturforsch., 1964, 19b, 987.7 4 G. G. Sumner, H. P. Klug, and L. E. Alexander, Acta Cryst., 1964,17, 732.7 6 F. A. Cotton, T. G. Dunne, B. F. G. Johnson, and J. S. Wood, Proc. Chem.76 L. Malatesta, L. Naldini, and F. Cariati, J . Chem. SOC., 1964, 961.7 7 L. Vaska, Science, 1963, 140, 809; J. A. Ibers and S. J. La Placa, ibid., 1964,78 R. P. M. Werner, A. H. Filbey, and S. A. Manastyrskyj, Inorg. Chem., 1964,7Q E. W. Abel and I. S. Butler, J . Chem. SOC., 1964, 434; R. J. Angelici, Inorg.Soc., 1964, 175.145, 920.3, 298.Chem., 1964, 3, 1099.R. B. King, Inorg. Chem., 1964, 3, 1039.H. Behrens and N. Harder, Chem. Ber., 1964, 97, 433.82 R.Nast and H. Kohl, Chem. Ber., 1964, 97, 207180 INORGANIU CHEMISTRYbeen obtained from the potassium salt, K[C(CN),], and metal carbonylhalides; thus, Mn(CO),Cl gives air-stable, yellow crystals of a, compound,Mn(C0) &( CN) ,. Disubstituted cationic carbonyls of manganese(1) andrhenium(1) react with potassium alkoxides forming acyloxy-carbonyls,M(CO),L,CO,R (L = PPh, or o-phen).84Photochemical replacement reactions of metal carbonyls and theirderivatives have been reviewed.s5 Pyrrolidine and morpholine give sub-stitution products L,M(CO),-, (n = 1 and 2) with Group VI metal carbonyls;with molybdenum and tungsten hexacarbonyls, piperazine gives the com-pounds, (C,H,gN2)[M(CO)5]2.ss The diamagnetic cations [C,H,M(CO),L]+(M = Mo or W; L = NH, or N2H4) are obtained when the tricarbonylcyclo-pentadienylmetal chlorides react with the ligands in methylene chloride.87Pentacarbonylmethylmanganese reacts with cyclohexylamine in ethers, togive CH,*CO*Mn( CO),( amine) a t a rate which is of the first order in MeMk(C0)but independent of amine concentration; the mechanism of this reaction isfound to depend markedly on the solvent, the concentration of the nucleophilebecoming important only in solvents of very low co-ordinating ability.88Isocyanide derivatives of metal carbonyls have been studied for nickel,molybdenum, manganese, and iron ; the existence of metal-to-ligand a-bond-ing in these compounds is c0nfirrned.8~Phosphine and araine .substitution products of metal carbonyls havereceived detailed study.Many new complexes Ni(CO),.L, have beenprepared with a wide variety of phosphines (L); the difference in mbondingbetween PR, and PF, is negligible and cannot account for the large observedvariations in the carbonyl stretching frequencies, which are thus due to adifference in the extent of transfer of a-bonding electrons.g0 Dipole-momentmeasurements for some of these complexes confirm a proposed schemeconcerning the competitive action of ligands on the metal of complexes.51With a large excess of &phosphorus tetrachloride the substitution product,Ni(C?O)2(P2C14)2, is obtained; the ligand reacts, however, as a bifunctional batsein the presence of a large excess of Ni(CO)4, forming (CO),NiP2CI,Ni(CO),.s2Tertiary phosphines also give replacement products from hexacarbonylvanadium,Qa e.g., V(CO),(PR,),; and a simple photochemical route has beendescribed to iron pentacarbonyl derivatives, Fe(CO),L and l?e(CO),L,(L = PPh, or ASP^,).^^ In solvents such as 1,Z-dichloroethane and in the8s W.Beck, R. 33. Nitzschmann, and G. Neumair, Angew. Chem., 1964, 76, 346.84T. Kruck and M. Noack, Chem. Ber., 1964, 97, 1693.E 6 W. Strohmeier, Angew. Chern., 1964, 76, 873.86 G. W. A. Fowles and D. K. Jenkins, Inorg. C h . , 1964, 3, 251.87E. 0. Fischer and E. Moser, J . Organmet. Chm., 1964, 2, 230.86 R. J. Mawby, F. Bmolo, and R. G. Pemon, J . Amer. C h . Soc., 1964, 86,3994.M. Bigorgne, J . Organornet. Chmn., 1963, 1, 101; K. K. Joshi, P. L. Pauson,and W.li. Stubbs, ibid., p. 51; R. C. Taylor and W. D. Horrocks, Inorg. Chem., 1964,3, 584.9oM. Bigorgne, J . Imorg. Nuclea?. Chem., 1964, 26, 107.9l M. Bigorgne and C. Messier, J . Organornet. Chem., 1964, 2, 79; M. Bigorgne,ibid., p. 68.VaC. B. Lindahl and W. L. Jolly, Inorg. Chern., 1964, 3, 1634.Qs W. Hieber and E. Winter, Chern. Ber., 1964, 97, 1037.94 J. Lewis, R. S. Nyholm, S. S. Sandhu, and M. H. B. Stiddmd, J. Chem. Soc.,1964, 2825NICHOLLS : COMPLEXES 181presence of trifluoroacetic acid, Fe(C0) , and Fe(CO),(PPh,) undergo rapidexchange of carbon monoxide even below -20”; Fe(CO), exchanges by adissociative mechanism, two carbonyl ligands exchanging more rapidly thanthe other three. 95 Decacarbonyldimanganese reacts with tertiary phosphinesunder ultraviolet irradiation, giving dimers [Mn(CO),PR3]2;g6 with theligands (CF,),PX (X = C1, Br, I , S-CF,, or SeCF,) and (CF,),AsI, the volatilebinuclear compounds, Mn,(CO) ,P(CF,),X and Mn,(CO),As(CF3),I, areformed.g7 The preparation and properties of the iridium(m) complexes,[IrX,(GO)L,] (X = Halogen; L = tertiary phosphine, arsine, or stibine)have been described and the reduction of the various isomers of“l,(CO 1 (PEtZPh)21in boiling alcoholic potassium hydroxide has been investigated.For theseoctahedral complexes it appears that chlorine in a trans-position to eitheranother chlorine or a carbon monoxide ligand is inert to replacement byhydrogen, while chlorine in a transposition to a phosphine is readily replaced,forming [IrHCl,( CO ) ( PEt ,Ph),].Tetrasubstituted diphosphines and diarsines react with metal carbonylsto form two types (7 and 8) of binuclear phosphorus- and arsenic-bridgedcomplexes (M = Ni, Fe, Cr, Mo, W, Mn, or Go); the cyclic complexes (8)are usually formed at a higher temperat~re.~~ Cyclic phosphine- and arsine-bridged complexes of iron have also been prepared from Fe(CO),(NO)2 inwhich the terminal ligands are all nitric oxide.l*O Two types of complexesare formed in the reactions of the bidentate ligands, 1,2-bisdiphenylphosphino-ethane (diphos) and o-phenylenebisdimethylarsine (diars), with tricarbonyl-cyclopentadienylmanganese ; these are those in which the ligands act asbridging groups, e.g., [C,H,Mn(CO)J,(diars) and those in which the ligandsoccupy normal chelate positions, e.g., C,H,Mn(CO)(diph0~).~01 The com-pound, [C,H,Co(PPh,)],, formed in the reaction of C,H,Co(CO), with tetra-phenyldiphosphine is diamagnetic and hence probably contain3 a metal-metal bond in addition to the phosphorus bridges.lo2 Mononuclear com-plexes, [C,H5M(As(CF,),)(CO),1 (M = Fe, n = 2 ; or M = Mo, n = 3) formedin the reactions of As,(CF,), with the iron and molybdenum cyclopentadienyl-metal carbonyl dimers, dimerise on ultraviolet irradiation, giving products,95 F.Basolo, A. T. Brault, and A. J. P&, J . Chem. Soc., 1964, 676.s6 A. G. Osborne and M. H. B. Stiddmd, J . Chm. Soc., 1964, 634.97 J. Grobe, 2. anorg. Chm., 1964, 331, 63.9a J. Chatt, N. P. Johnson, and B. L. Shaw, J. Chm. Soc., 1964, 1625.99 J.Chatt and D. T. Thompson, J . Chem. Soc., 1964, 2713; J. Chatt and D. A.Thornton, ibid., p. 1005; R. G. Hayter, Inorg. Chem., 1964, 3, 711; J . AWT. Chem.Soc., 1964, 88, 823.loo R. G. Hayter and L. F. Williams, Inorg. Chem., 1964, 3, 717.lol R. S . Nyholm, S. S. Sandhu, and M. H. B. Stiddmd, J. Chem. Soc., 1963, 5916.lo9R. G. Hayter and L. F. Williams, J . Inorg. Nuclear Chem., 1964, 26, 1977182 INORGANIC CHEMISTRY[C5H,M(As(CF3),) (C0),,,],.103 The actions of halogens on Cr(CO),(diars)producea complexes of chromium(m), namely, Cr(diars)X, (X = Br or I);oxidation of the bisdiarsine compound, Cr(CO),(diars),, with a halogen atroom temperature, however, produces seven-co-ordinate complexes ofchromium(n), [Cr(CO),(diars),X]X, isomorphous with the correspondingmolybdenum(I1) and tungsten(rx) complexes reported last year.104Acetylacetone and other B-diketones react with tetracarbonyl-p-dichlorodirhodium(1) in the presence of a base, to give monomeric ato-complexes, (p-Diketone)Rh( CO), ; the carbonyl groups can be replaced byolehs and in part by triphenyl-phosphine, -arsine, or -stibine.l05 Octa-carbonyldicobalt reacts with ethanethiol and ethyl disulphide in hexane atroom temperature, giving a mixture from which Co,(CO),(C,H,S), andCo4(C0),(C2H,S), can be crystallised.lo6 A new route to organosulphurderivatives of metal carbonyls involves thermal or photochemical decarbon-ylation of compounds of general formula, MeS*[CH,];M( CO),(C,H,), (whichdo not contain metal-sulphur bonds) ; these are readily available from metalcarbonyl anions and the chloroalkyl methyl sulphides, MeS*[CHJ,*C1.107 Incontrast to the large number of metal carbonyl sulphides in which thesulphur atom acts as a bridging group, the dimethyl- and diethyl-dithio-carbamate complexes of metal carbonyls are monomeric and evidentlycontain bidentate dithiocarbamato-ligands.108Nitrosyls,-Trifluorophosphine reacts with [Co(NO),Cl], at 50"/350 atm.in the presence of copper, to give the red-brown, volatile Co(NO)(PF,),;dimeric nitrosyl iron bromide similarly gives diamagnetic Fe(NO),(PF,),.logThe preparation and properties of some stable nitrosylnickel complexes ofgeneral formula NiX(NO)L, has been reported.The reaction of nitric oxidewith nickel carbonyl in various solvents leads to a variety of compoundsderived from the species [NiNO]+ ; above atmospheric pressure, however, alight-blue product, Ni(NO)(NO,), is almost exclusively obtained.l1° Thenitrosyl halides, Mo(NO),Cl, and W(NO),Cl,, are reactive dark-green solids,prepared by the action of nitrosyl chloride on the metal hexacarbonyls; withneutral ligands they form complexes, M(NO),Cl,L,, and with tetraphenyl-arsonium chloride they form salts of the complex anions, [M( N0)2C14]2-.111Crystalline C,H,PtNO has been prepared by treating Pt,(CO),Cl, in benzenewith nitric oxide to give a red precipitate which is then brought into reactionwith cyclopentadienylsodium in hexane.l12 Cyclopentadienylmetal nitrosylswith bridging nitrosyl groups, i.e., [C5H5Cr(NO),], and [C,H,Mn(CO)NO],,are obtained by reduction of C,H,Cr(NO),Cl and [C,H,Mn(CO),NO][PF,]los W.R. Cullen and R. G. Hayter, J . Amer. Chem. SOC., 1964, 86, 1030.l o p J. Lewis, R. S. Nyholm, C. S. Pande, S. S. Sandhu, and M. H. B. Stidda,rd,l o 5 F. Bonati and G. Wilkinson, J . Cltem. Xoc., 1964, 3156.106 E. Klumpp, L. Marko, and G. Bor, Chem. Ber., 1964, 97, 926.lo' R. B. King and M. B. Bisnette, J . Amer. Chem. SOC., 1964, 86, 1267.108 F. A. Cotton and J. A. McCleverty, Inorg. Chem., 1964, 3, 1398.lo9 T. Kruck and W. Lang, Angew. Chem., 1964, '76, 787.l 1 0 R. D. Feltham, Inorg, Chem., 1964, 3, 116, 119; R. D. Feltham and J. T. Carriel,111 F. A. Cotton and B. F. G. Johnson, Inorg. Chew%., 1964, 3, 1609.112 E. 0. Fischer and H.Scliuster-Woldan, 2. Naturforsch., 1964, 19b, 766.J . Chem. SOC., 1964, 3009; cf. Ann. Reports, 1963, 60, 235.ibid., p. 121NICHOLLS : COMPLEXES 183with sodium borohydride.113 Five monomeric nitrosylruthenium chloro-complexes, [RuNOC~,(H,O),-,]~ (n = 1-5; x = 2+ to 2-), have beenisolated by ion-exchange in acid media.ll4 The red isomer ofis shown 115 by conductivity studies to be [(NH,),CoON=NOCo(NH,)J4+.The remarkable difference in the electron spin resonance spectra of theisoclectronic ions [Cr(CN) 5N0]3- and [Mn(CN),N0I2- cannot be accountedfor if the M-N-0 atoms are linear; the spectral results can, however, beaccommodated if the NO group makes an angle of 45' with the z-axis, theoxygen atom then lying between two of the cyanide ligands.l16Olefinic, n-AllyIic, and Acetylenic Complexes.-The first olefin complexesof gold are reported ; crystalline gold(1) and gold(n1) chloride complexeswith cyclo-octa-l,5-diene are formed in the reaction of chloroauric acid withthe cycloalkene in ethers.ll? The norbornadienecopper( I) chloride complexexists as tetramers [C,H,CuCl], in the solid state; the distorted trigonal-planar co-ordination about copper is similar to that found in cyclo-octa-tetraenecopper( I) chloride.ll* While co-ordinated olefins are generallyregarded as being rigidly attached to metal ions, evidence has been presentedfrom nuclear magnetic resonance studies that ethylene co-ordinated t orhodium(1) in the compound, C5H5Rh(C2HJ2, may rotate with the co-ordination bond as axis.ll9 Chelate complexes, LPtX, (X = C1, Br, or I),are formed by tertiary phosphines and arsines containing the pent -4-enylgroup; the palladium compound, LPdC1, (L = CH, : CH*[CH,],*PPh,) isdimeric and the olehic double bond is not co-ordinated to the metal.120The complex K[Pt(acac),Cl] which is known to contain one acetylacetoneligand bonded conventionally (oxygen bidentate group) and the other[CO (NH3 )5NOI (NO31 ,,0*5H,Obonded through the y-carbon atom, forms, on acidification, a bright-yellowo l e h complex (9) which when kept in benzene becomes a red binuclearcomplex, di-p-chlorobis(acetylacetonato)diplatinum(n).121 Olefin exchangeby platinum(@ complexes containing pyridine N-oxides trans to the olefinhas been investigated; the relevant equilibria are affected by the substitnentsllS R.B. King and M. B. Bisnette, Inorg. Chem., 1964, 3, 791.11* E. E. Mercer, W. M. Campbell, and R. M. Wallace, Inorg. Chem., 1964, 3, 1018.115 R. D. Feltham, Inorg. Chem., 1964, 3, 1038.116 D. A. C. McNeil, J. B. Raynor, and M. C. R. Symons, Proc. Chem. SOC., 1964, 364.117 A. J. Chalk, J . Amer. Chem. Soc., 1964, 86, 4733.118 N. C. Baenziger, H. L. Haight, and J. R. Doyle, Inorg. Chem., 1964, 3, 1535;llS R. Cramer, J . Amer. Chem. SOC., 1964, 86, 217.120 M. A. Bennett, H. W. Kouwenhoven, J. Lewis, and R. S. Nyholm, J . Chem.121 G. Allen, J. Lewis, R. F. Long, and C. Oldham, Xature, 1964, 202, 589.N. C. Baenziger, G. F. Richards, and J. R. Doyle, ibid., p. 1529.SOG., 1964, 4570184 INORGANIC CHEMISTRYon the olefin but to a greater extent by the substituents on the pyridineoxide.122 The crystal-structure determination of the carbonyl-2,3-dimethyl-buta-I ,4-dieneosmium complex which has a ligand :metal ratio of 1 : 2, showsthat one osmium atom is surrounded by five carbon atoms in a squarepyramid while the other is octahedrally surrounded; a single Os-0s bond isimplied by the observed separation of 2-74 A, and the corrected molecularformula of the complex is C,H,OS,(C~),.~~~ Complexes of 2-allylpyridinewith copper(I), silver(I), and platinum(=) contain the ligand co-ordinatedthrough both the pyridine-nitrogen atom and the olefinic group ; l Z 4 tricarbonyl-n-cinnamaldehydeiron similarly contains a bidentate ligand bonded throughthe aldehydic carbonyl group as well as through the ethylenic doublebond.lZ5Some new ally1 derivatives of tungsten have been prepared.The cr-ally1compound (10) reacts with hydrogen chloride, forming the cation (11)containing a propene group, and reduction of this with sodium borohydride(12) oc cogives the isopropyl complex (12) ; the n-ally1 compound (13) is obtained uponultraviolet irradiation of the o-ally1 isomer.lZ6 The ethylenic cations,[C5H5Fe(CO),*CH,=CHR]+ and [(CO),Mn*CH,=CH,]+ are formed by hyd-ride-ion abstraction from the alkyls, [C5H5Fe(CO),R] and (CO),MnEt ; thecations, [C,H,Fe(CO>,-CH,=CR~O~+, are readily obtainedlz' by protonationof the newly characterised oxoalkyl complexes,[C,H,Fe(CO),-CH,*COR].n-Allylic complexes have now been obtained directly from allene; benzenesolutions of dichlorobisbenzonitrilepalladium( 11) react with allene, methylal-128 S.I. Shupack and M. Orchin, J . A ~ T . Chem. SOC., 1964, 86, 586.128 R. P. Dodge, 0. S. Mi&, and V. Schomaker, Proc. Ohm. Soc., 1963, 380.la4R. E. Yingst and B. E. Douglaa, Inmg. Chem., 1964, 3, 1177.135 K. Stark, J. E. Lancaster, H. D. Murdoch, and E. Webs, 2. N&UTfOr8Ch., 1964,I t s M. L. H. Green and A. N. Stear, J . Organmet. Chem., 1964, 1, 230.187 M. L. H. Green and P. L. I. Nagy, J . Organomet. Chem., 1963, 1, 58; J. K. P.19b, 284.Ariyaratne and M. L. H. Green, J . Chem. SOC., 1964, 1NICHOLLS : COMPLEXES 185lene, and 1 , l -dimethylallene, giving chloro-bridged materials, [Pdz,C1,(n-Allylic palladium complexes are also formed in high yield when carbonmonoxide is passed through a mixture of an allylic chloride and a palladiumsalt dissolved in methanol ;I29 unsaturated six-, seven-, and eight-memberedcyclic hydrocarbons give n-ally1 compounds with palladium( 11) chloride in50% acetic acid.130 Cycloheptatrienyl derivatives of chromium, molyb-denum, and cobalt have been described ; irradiation of octacarbonyldicobaltwith an excess of cycloheptatriene in toluene gives a low yield of a dark-redliquid, C,H,Co(CO),, the proton magnetic resonance spectrum of whichconfirms the n-allylic bonding of the cycloheptatriene ring.*3f Allylbis-cyclopentadienyltitanium(II1) has been obtained as purple crystals, stableat room temperature under nitrogen ; infrared evidence suggests t,hat theally1 group is n- bonded to titanium.132 On treatment with silver perchlorateor borofluoride, halogeno-n-allyliroii carbonyls are converted into saltscontaining the tricarbonyl-n-allyliron cation ; reductive dehalogenation ofhalogeno-n-allyliron tricarbonyls with sodium pentacarbonylmanganate( - 1 )affords di(tricarbony1-n-allyl)iron, which co-exists in solution with the para-magnetic tricarbonyl-n-allyliron.The chemistry of diene-iron carbonylcomplexes has been reviewed.133 The action of heat on the 1 : l aciduct ofpentacarbonylphenylmanganese with butadiene results in the sublimationof a complex (14) which contains the novel five-electron n - ~ y s t e i n . ~ ~ ~The violet, crystalline complex, CO,(CO)~(C,HBU~),(C,H,), has a mostunusual structure (15) in which the six-carbon chain, formed by fusion ofthe three alkyne groups, acts as a fly-over rather than as a bridge.Themetal-carbon distances show that each cobalt atom is bonded to four ofthese six carbon atoms, and this arrangement is interpreted as a diallylstructure.13s Disubstituted alkynes such as hex-3-yne, diphenylacetylene,and methylphenylacetylene react with tricarbonyltri(acetonitri1e)tungstenor pentacarbonylacetonitriletungsteii to give the doubly n-complexed com-pounds, (RC=CR),WCO ; with the t'ri(acetonitri1e) complexes of chromiumlS8 R. G. Schultz, Tetrahedron Letters, 1964, 301; M. S. Lupin and B. L. Shaw,120 W. T. Dent, R. Long, and A. J. Wilkinson, J . Chem. SOC., 1961, 1585.I3O R.Huttel, H. Dietl, and H. Christ, Chern. Ber., 1964, 97, 2037.131 R. B. King and M. B. Bisnette, Inorg. Chem., 1964, 3, 785.132 H. A. Martin and F. Jellinek, Angsw. Chem., 1964, 76, 274.133 G. F. Emerson, J. E. Mahler, and R. Pettit, Chern. and Ind., 1961, S36; H. D.Murdoch and E. A. C. Lucken, Helv. Chim. Acta, 1964, 47, 1617; R. Pettit and G. F.Emerson, Adv. Organornet. Chem., 1964, 1, 1.134 W. D. Bannister, M. Green, and R. N. Haseldine, Proc. Chern. SOC., 1961, 370.13s 0. S. Mills and G. Robinson, Proc. Chenz. Soc., 1964, 187.ibid., p. 883186 INORGANIC CHEMISTRYand molybdenum, cyclisation occurs, giving hexa-alkylbenzene or tetra-phenyIcy~lopentadienone.~~6Complexes with Aromatic Sptems.-There has been a great deal ofinterest aroused this year in organometallic compounds containing ringsbonded to a metal by one n- and two a-bonds.Such bonding has now beenestablished in tricarbonyloctafluorocyclohexa- 1,3-dieneiron (1 6), l3 7 n- cyclo-pentadienyIhexakis( trifluoromethyl) benzenerhodim ( 17),138 and tetrakis-(trifluoromethyl)cyclopentadienone-n-cyclopentadienylcobalt, the conforma-tion of which is similar to that in n-cyclopentadienyl-l -phenylcyclopenta-dienylcobalt (reported last year).lSQ The rhodium analogues of these last twocobalt compounds, i.e., [ ( CF3),C50]Rh( C5H5) and C,H5Rh( C,H5*C5H5),have now been prepared.l*O The nuclear magnetic resonance spectralassignments of these compounds with substituents on the ring in the ezo-position with respect to the metal atom have been revised, and the spectraof tricarbonyl-z-1 -methylcyclohexadienylmanganese and of other substitutedn-cyclohexadienyl complexes are in accord with exo-sub~titution.~~~ A mostimportant paper has appeared concerning the molecular structures of somecyclopentadienylmetal complexes. The compounds discussed are(C,H,)&JloH,, (C,H5)Mo(CO)&, (CJ&)Rh[C,(CF3),] (17), and(C5H5)Co[OC5 (CFd41;in each C,H, ring the individual C-C bond lengths are different, varyingbetween 1-35 and 1.51 8.The molecular geometries are distinguished bya lack of cylindrical symmetry around the metal ion, and the authors suggestconsequential localisation of electron density in the cyclopentadienyl ring,i.e., removal of the metnl-orbital degeneracy in fields of less than cylindricalsymmetry also serves to remove the degeneracy of the bonding orbitals onthe cyclopentadieiie ring.l42Stable tetraphenylcyclobutadiene complexes of molybdenum are obtainedin the reactions of hexacarbonylmolybdenum and tricarbonyl- (1,2-dimethoxy-136 D.P. Tate, J. M. Augl, W. 35. Ritchey, B. L. Ross, and J. G. Grasselli, J. Amer.137 11. R. Churchill and R. Mason, Proc. Chem. SOC., 1964, 226.138 31. R. Churchill and R. Mason, Proc. Chem. SOC., 1964, 365.139 M. Gerloch and R. Mason, Proc. Roy. SOC., 1964, A , 279, 170; cf. Ann. Reports,1963, 60, 239.140 R. S. Dickson and G. Wilkinson, J . Chem. SOC., 1964, 2699; R. J. Angelici andE. 0. Fischer, J . Anzer. Chern. SOC., 1963, 85, 3733.141 D. Jones and G.Wilkinson, J . Chem. SOC., 1964, 2179.Io2 M. J. Bennett, M. R. Churchill, M. Gerloch, and R. Mason, Nature, 1964, 201,Chem. SOC., 1964, 86, 3261.1318NICHOLLS : COMPLEXES 187ethane)molybdenum with diphenylacetylene ; surprisingly, bis(pentapheny1-cyclopentadieny1)molybdenum is also formed in these reactions.lM Thenovel reaction of cyclopentadiene vapour with metal halides has been usedto prepare complexes of the types (C,H,)ZrX, and (C,H,)JrX, (X = C1,Br, or I), and (C,H,)TiCl, ;la4 other newly prepared cyclopentadienylmetalhalides include [ (C 5H ,),MX +X- and [ (C ,H ,),Rex,] + X- (M = Mo or W ;X = C1 or Br) l45 and the blue-green, dimeric (C,H,)FeCl,. The infraredand Raman spectra of n-complexes between metals and C,H, rings havebeen reviewed.l4, The first sandwich compound of a bivalent lanthanide,Eu(C5H,), has been prepared by reaction of cyclopentadiene with a solutionof europium in liquid ammonia.la7' fhaferrocene " (n-cyclopentadienyl-n-pyrrolyliron) has been prepared bytwo routes; it is a red crystalline substance, isomorphous with ferrocene buthaving lower thermal and oxidative stability.148 Some oxo- and oxochloro-c y clopent adienylmolybdenum complexes have been investigated ; t et raoxo -p-oxodicyclopentadienyldimolybdenum [C5H5M00&0 forms pale yellowcrystals decomposing a t 100-150°.149 Slow oxidation of (C,H,),TiCl yieldsbiscyclopentadienyltitanoxane polymers.150 Hexacarbonylvanadium reactswith benzene, toluene, p-xylene, and mesitylene to give red, crystalline, andionic complexes [V(CO),(arene)][V(CO)6,151 The unexpected dipole momentof 1 .7 8 ~ found for bis(hexamethylbenzene)cobalt(O) excludes the possibilityof a centrosymmetric structure analogous to that in dibenzenechr~mium(O).~~~A new synthetic route to (C5H,)M(C6H6) n-complexes involves the elbnina-tion of carbon monoxide from carbonyls by reaction with hydride ions; thusvestigated include [V(C,H,Me,),]+ 154 and [M(C6Me6),]'+ [M = Co(1) orRh(I), x = 1 ; or M = CO(II) or Rh(rr), x = 2].155 The crystal structure ofC6H6CuA1C14 contains tetrahedrally co-ordinated copper(1) and aluminium ;there is distortion of the benzene ring towards a cyclohexatriene systemwith one of the short C-C bonds nearest the copper.l56 Duroquinone-(cyclopentadieny1)metal complexes of rhodium and indium have beendescribed ; their infrared spectra suggest that the n-bonded duroquinonemolecule is non-planar.15' The reaction of chromium(m) chloride withethereal isopropylmagnesium bromide in the presence of azulene, followedby methanolysis, yields green, diamagnetic, n-azuleniumchromium( 0 )[ (C,H,)MO( C,H,)( CO)]PF, yields C,H,MOC,H6.153 New arene cations in-143 W.Hubel and R. Merenyi, J. Organomet. Chem., 1964, 2, 213.14* A. F. Reid and P. C. Wailes, J . Organmet. Chem., 1964, 2, 329.145 R. L. Cooper and M. L. H. Green, 2. Natwforsch., 1964, 19b, 652.146 H. P. Fritz and L. Schiifer, 2. Naturforsch., 1964, 19b, 169; H. P. Fritz, Adv.14' E. 0. Fischer and H. Fischer, Angew. Chem., 1964, 76, 52.14* K.K. Joshi, P. L. Pauson, A. R. Qazi, and W. H. Stubbs, J. Organomet. Chem.,14@ M. Cousins and M. L. H. Green, J . Chem. SOC., 1964, 1567.150 S. A. Giddings, Inorg. Chem., 1964, 3, 684.151 F. Calderazzo, Inorg. Chem., 1964, 3, 1207.152 E. 0. Fischer and H. H. Lindner, J . Organmet. Chem., 1964, 2, 222.153 E. 0. Fischer and F. J. Kohl, Angew. Chem., 1964, 76, 98.154 F. Calderazzo, Inorg. Chem., 1964, 3, 810.lS5 E. 0. Fischer and H. H. Lindner, J . Organomet. Chem., 1964, 1, 307.156 R. W. Turner and E. L. Amma, J . Amer. Chern. SOC., 1963, 85, 4046.Organomet. Chem., 1964, 1, 1.1964, 1, 471; R. B. King and M. B. Bisnette, Inorg. Chem., 1964, 3, 796.G. N. Schrauzer and K. C. Dewhirst, J. Amer. Chem. SOC., 1964, 86, 3265.188 INORGANIC CHEMISTRYn-azulenide which contains the metal bound to both a, cationic seven-membered and an anionic five-membered ring.158-Bonded Organometallic Compounds of the Transition Elements.-Tetraphenyltitanium has been prepared from phenyl-lithium and titanium( IV)chloride in benzene at -70"; it decomposes at -10" into biphenyl and theblack, pyrophoric Ti(C6H5)2.159 Complexes of tetramethyltitanium withnitrogen donor ligands, e.g., (bipy)TiMe,, have higher thermal stability thanthe uncomplexed material, but are readily oxidised and hydrolysed.160 Thefirst alkyls of niobium and tantalum, Me,MCl,, have been isolated; Me,NbCl,forms golden-yellow crystals, indefinitely stable at - 78" but slowly decom-posing at room temperature.161 The reactions and reacting ratios of benzyl-magnesium chloride with chromium(1nc) chloride have been examined indetail;lB2 new a-bonded organochromium compounds have been preparedfrom chromium(m) chloride and ortho- and para-substituted phenyl-lithiumsin ether.ls3 Perfluorophenyl derivatives of the transition metals are con-veniently prepared from perfluorophenylmagnesium bromide ; thus,Mn(CO),Br gives C,F,Mn(CO),; and C,H,Fe(CO),I yields C5H5*C6F5Fe(CO),.When bis(cyclopentadienyl)titanium(rv) chloride reacts with C,F,*MgBr orC,F5Li, a mixture is produced from which a complex, (C5H,),Ti(CGF,)CI,can be separated chromatographically; this compound and (C5H5),Ti(C,F5),exhibit remarkable thermal and oxidative stabilities in comparison withtheir hydrocarbon analogues.16* Further perfluoroalkyl derivatives of nickelhave been prepared ; the deep red, air-stable liquid, C,H,Ni(CO)C,F5,reacts with triphenylphosphine, giving (C,H5)Ni(PPh3)C,F,.165 At 90-200 O, pentacarbonylmethylmanganese adds across the double bond of tetra-fluoroethylene to give CH,*CF,-Mn(CO),; by using Mn(CO),H and ClFC : CF,the two isomers CHFCl*CF,.Mn(CO) and CHF,*CFCl*Mn(CO), have beenobtained and characterised.l66 Rhodium and iridium halogenocarbonylbis-(trialkyl- or triaryl-phosphines) react readily with active organic halides(e.g., methyl or ally1 iodides, benzyl chloride, or methyl iodoacetate) in inertsolvents, giving good yields of crystalline akylrhodium and alkyliridiumcomplexes :l 7RX' + MX(CO)(PR',), +P RMXX'(CO)(PR,'),Ultraviolet irradiation of the acyl derivatives R*CO*Fe(CO),C,H, (R = CF,,Et, C,F,, Ph, or CH, : CH) produces the corresponding alkyls, RFe(CO),C,H,;with the molybdenum acyls, R*CO*Mo(CO),C,H,, heat alone is sufficient to168 E. 0.Fischer and J. Muller, J. Organomet. Chem., 1964, 1, 464.lSsV. N. Latjaeva, G. A. Razuvaev, A. V. Malisheva, and G. A. Kiljakovrt, J.160 K.-H. Thiele and J. Muller, 2. Chem., 1964, 4, 273.161 G. L. Juvinall, J. Amer. Chem. Soc., 1964, 86, 4202.162 F. Glockling, R. P. A. Sneeden, H. Zeiss, and R. Bonfiglioli, J. Organornet. Cheim.,163 F. Hein and D. Tille, 2. amorg. Chem., 1964, 329, 72.16* M. D. Rausch, Inorg. Chem., 1964, 3, 300; M. A. Chaudhari, P. M. Treichel166 D. W. McBride, E. Dudek, and F. 0. A. Stone, J. Chem. SOC., 1964, 1752.166 J.B. Wilford, P. M. Treichel, and F. G. A. Stone, J. Organornet. Chem., 1964,167 R. F. Heck, J. Amer. Chem. SOC., 1964, 86, 2796.Orgafiomet. Chem., 1964, 2, 388.1964, 2, 109.and F. G. A. Stone, J. Organomet. Chem., 1964, 2, 206.2, 119NICHOLLS : COMPLEXES 189cause the decarbonylation.l68 A new series of organocobalt compounds isformed in the reduction of alkyl and aryl halides with pentacyanato-cobaltate(n)~[CO(CN),]~- + Ph-CH,Br + [Ph*CH,.Co(CN),13- + [Co(CN),BrI3-Alkyl- and aryl-platinum( 11) olefin compounds (olefin)PtR, and (o1efin)PtRXare formed in the reactions of Grignard reagents with platinum(@ compoundscontaining cyclic diolehs.l70Trimet h yl ( sali c ylalde hydat 0) - and t rimet hy 1 ( quinolin- 8 - olat 0) -platinumcontain six-co-ordinate platinum? the six-fold co-ordination being maintainedby the sharing of oxygen atoms.l7l The stability of dialkylgold(1n) deriva-tives can be increased by complex formation with NN-dialkyldithiocarb-amates.172 Dialliyl- and diaryl-zincs form very stable 1 : 1 complexes withbidentate oxygen, nitrogen? phosphorus, and arsenic ligands ; trimethylamineand triphenylphosphine form 2 : 1 (ligand : metal) complexes.173 Dimethyl-cadmium similarly gives crystalline chelate compounds, e.g., CdMe,(bipy),which are more stable to oxidation than the uncomplexed alkylcadmium;the complexes of monodentate ligands, e.g.CdMe,(pyridine), readily dis-sociate into their components at low temperature.174Molecular Hydrides of the Transition Elements.-Two papers havediscussed the large high-field shifts in the proton magnetic resonance spectraof transition-metal hydrides; it is believed that distortion of the partly filledd-shell by the magnetic field is the main contributor to the chemical shiftof the hydrogen atom.175 A black, diamagnetic, pyrophoric tungstenhydride, WH(LiPh),, is formed when WPh4(LiPh),,3Et2O reacts withhydrogen in the absence of air and moisture.176 A crystallographic studyof hydridopentacarbonylmanganese shows that the five carbon atoms occupyfive corners of a nearly regular octahedron? the molecular symmetry ofthe Mn(CO), group being C,, and not that reported earlier from infraredstudies ; the hydrogen atom probably completes the octahedral co-ordinationaround manganese.l" A neutron-diffraction study on the rhenium hydridereported previously as K,ReH, has established its composition as K2ReH, ;l78it can be prepared by reduction of ammonium hexabromorhenate(1v) withpotassium in liquid arnm011ia.l~~ Reduction of ammonium pertechnatewith potassium in ethylenediamine yields K,TcH, which is isostructural168 R.B. King and M. B. Bisnette, J. Organomet. Chem., 1964, 2, 15.169 J. Halpern and J. P. Maher, J. Amer. Chem. SOC., 1964, 86, 2311.l70 C. R. Kistner, J. H. Hutchinson, J. R. Doyle, and J. C. Storlie, Inorg. Chem.,171 J . E. Lydon, M. R. Truter, and R. C. Watling, Proc. Chem. SOC., 1964, 193.172 H. J. A. Blaauw, R. J. F. Nivard, and G. J. M. Van der Kerk, J. Organomet.173 J . G. Noltes and J. W. G. Van den Hurk, J. Organomet. Chem., 1964, 1, 377;174 K.-H. Thiele, 2. anorg. Chem., 1964, 330, 8.175 A. D. Buckingham and P. J. Stephens, J. Chem. Soc., 1964, 2747; L. L. Lohr176 B. Sarry, M. Dettke, and H. Grossman, 2. anorg. Chem., 1964, 329, 218.1 7 7 5. J. La Placa, W. C. Hamilton, and J. A. Ibers, Inorg. Chem., 1964, 3, 1491;17* S. C. Abrahams, A. P. Ginsberg, and K. Knox, Inorg. Chem., 1964, 3, 558.179 C. L. Ottinger, I. E. McFall, and C. W. Keenan, Inorg. Chem., 1964, 3, 1321.1963, 2, 1255.Chem., 1964, 2, 236.K.-H. Thiele, 2. anorg. Chem., 1963, 325, 156.and W. N. Lipscomb, Inorg. Chem., 1964, 3, 22.J . Amer. Chem. SOC., 1964, 06, 2288190 INORGANIC CHEMISTRYwith rhenium hydride.18O The red, crystalline, diamagnetic hydride,CoH(Ph,P*C,H,-PPh,), has been prepared by reducing a mixture of cobalt (11)bromide and the phosphine with lithium aluminium hydride or sodiumborohydride ; the very stable hydride of rhodium(I), RhH(Ph,P*C,H,*PPh,),,has been obtained similarly.181 The compounds [MHR( R,P*C,H,*PR,),](M = Ru or 0 s ; R = alkyl or aryl) have been described; they are the firstexamples of compounds containing both a hydrogen atom and a a-bondedorganic group attached to the same metal atom.182 A spectroscopic studyof d-d transitions in a number of hydrido-complexes of rhodium(@ contain-ing nitrogen ligands has shown that the hydride ion lies fairly low in thespectrochemical series, between water and amm0nia.18~ A complex con-taining hydrogen and an olefin bonded to the same metal has now beenprepared ; hydridocyclo-octa- 1,5-&eneiridium( m) forms cream-colouredcrystals, decomposing above 200 0.184 A most intriguing synthesis of hydrido-carbonyls involves the reactions of osmium( ~ v ) or ruthenium(m) halideswith tertiary phosphines in alcohols, e.g. :[Ru2C13(PEt2Ph),]C1 + 2KOH + 2EtOH +2[RuHCl(CO)(PEt,Ph),] + 2CH4 + 2KC1 + 2H20In the formation of the air-stable, crystalline osmium compounds,[OsHX(CO)L,] (X = C1 or Br; L = Ph,P or AsPh,), tracer studies withD- and 14C-labelled alcohols have established that the hydride and carbonylligands originate from the alcohol solvent .IE5Transition-me t a1 Compounds containing Met &-Metal Bonds.-Metal-me talbonds have been the subject of a review.186 Substances containing metal-metal bonds can be classified into four main types: metals, concentratedmetal compounds [e.g., (Nb14),J, covalent compounds [e.g., Mn,(CO)lo], andmetal-donor compounds [e.g., bis(dimethylglyoximato)nickel(~~)]. Metal-metal bond formation is favoured by (i) a metal atom having the requiredunpaired electron(s) available [as in the dS Co(0) atom] or capable of beingmade readily available by unpairing [as in Fe(O)], and (ii) orbitals havingthe required energy, i.e., able to overlap at distances comparable withordinary bond lengths. The electronegativity of the dl0s1 atoms has beenconsidered and the formal similarity of the latter with the halogensemphasised. A general reaction between (Ph3P)AuC1 and salts of the[Mn(CO),] -, [Pe(C0)J2-, and [Co(CO),]- ions leads to the compounds(Ph,P)AuMn(CO),, (Ph,PAu),Fe(CO),, and (Ph,P)AuCo(CO),. Similarly,(triars)CuBr [triars = Me*C(CH,*AsMe,) ,] reacts with sodium pentacarbonyl-manganate( - l), giving the air-stable and diamagnetic (t8riars)CuMn(CO),.187.180 A. P. Ginsberg, Inorg. Chem., 1964, 3, 567.181 F. Zingales, F. Canziani, and A. Chiesa, Inorg. Chem., 1963, 2, 1303; A. SaccolS2 J. Chatt and R. G. Hayter, J. Chcm. Soc., 1963, 6017.J. A. Osborn, R. D. Gillard, and G. Wilkinson, J. Chem. SOC., 1964, 3168.lE4 S. D. Robinson and B. L. Shaw, Tetrahedron Letters, 1964, 1301.lB5 L. Vaska, J. Amer. Chem. SOC., 1964, $6, 1943; J. Chatt, B. L. Shaw, and A. E.and R. Ugo, J. Chem. SOC., 1964, 3274.Field, J. C?Lem. SOG., 1964, 3466.H. Schiifer, Angew. Chem., 1964, 76, 833.C. E. Coffey, J. Lewis, and R. S. Nyholm, J. Chem. SOC., 1964, 1741; A. S.Kasenally, R. S. Nyholm, and M. H. B. Stiddard, J. Amer. Chem. Xoc., 1964, $6, 1884NICHOLLS: COMPLEXES 191The o-phenylenebisdimethylarsine complex [V(CO),(diars)], is diamagneticin the solid state and in solution, indicating that it is metal-metal bonded;the complexes, (Ph,P)AuV(CO), and [C,H,(ASM~,),ASM~]CU~(~~)~, provideexamples of seven-co-ordinate vanadium(0).188 Heptaco-ordinate tantalumis found in EtHg*Ta(CO),, a compound prepared from ethylmercury(n)chloride and his( dimethoxyetkane)sodium hexacarb~nyltantalate.~~~ Man-ganese rhenium decarbonyl, (CO) ,MnRe(CO),, forms lemon-yellow, air-stablecrystals with a manganese-rhenium distance of 2.96 & 0.01 8; its infraredspectrum has been measured and assignments have been proposed.lso Acrystal-structure analysis of Ph,SnMn(CO),(PPh,) shows the tin, manganese,and phosphorus atoms to be linked colinearly, with the Sn-Mn distancemarkedly shorter than the sum of the individual metallic radii.lbl InPh,Sn[Mn(CO),], the four bonds from tin are disposed tetrahedrally, theMn-Sn-Mn angle being larger than the C-Sn-C angle through mutualrepulsion of the bulky (Mn(CO), g r o ~ p s . 1 ~ ~ Compounds with metal-metalbonds can sometimes be obtained by reaction of a metal halide with acomplex carbonyl of another metal; two examples are :Ifi3[C,H,Fe(CO),], + SnCl, ---+ [C,H,Fe(CO),],SnCl,(Ph,P),Ir(CO), + HgCl, ---+ (Ph,P),(CO)Cl,IrHgClBinuclear mixed carbonyls [L,(CO),-,MM'(CO),] (n = 0) and their sub-stitution products with o-phenanthroline (L, = C&8N2) can be prepared bythermal decomposition of carbonyl salts such as [M(CO),-,L,] +[M'( CO),]-[M = &(I) or Re(r); M' = Co(-1) or Mn(-1); n = 4 or 51. Thus, orangebrown diamagnetic enneacarbonylrhenium-cobalt is obtained by thereaction :I94[Re(CO),][Co(CO),] + (CO),ReCo(CO), + CODicobalt iron nonacarbonyl sulphide Co,Fe( CO),S is formed when thiophen ,sulphur, or ethanethiol reacts with a mixture of octacarbonyldicobalt andpentacarbonyliron under hydroformylation conditions ; a trigonal-pyramidalstructure is proposed, with a triangle formed by two cobalt and one ironatoms, each metal being bonded to three carbonyl groups and an apicalsulphur atom.lg5 The first example of a compound containing three differentmetal atoms covalently bonded, namely, (C,H,)(CO),FeHgCo(CO),, is an air-stable, orange, crystalline solid formed by stirring a solution of monocaxbonyl-n- cyclopentadienyliron-p-dicarbonyl( tricarbonylco balt ) in hexane withmercury.1gs The yellow germanium-platinum complex, (Et,P),Pt( GePh,),,60'lS8 A. S. Kasenally, R. S. Nyholm, R. J. O'Brien, and M. H. B. Stiddard, Nature,189 K. A. Keblys and M. Dubeck, Inorg. Chem., 1964, 3, 1646.lgo A. N. Nesmeyanov, K. N. Anisimov, N. E. Kolobova, and I. S. Kolomnikov,Isvest. Akad. Nauk S.S.S.R., Otdel. khirn. Nauk, 1963, 194 (178); N. Flitcroft, D. K.Huggins, and H. D. Kaesz, Inorg. Chem., 1964, 3, 1123.lS1 R. F. Bryan, Proc. Chem. SOC., 1964, 232.lg2 B. T. Kilbourn and H. M. Powell, Chem. and Ind., 1964, 1578.lS3 F. Bonati and G. Wilkinson, J. Chem. SOC., 1964, 179; R. S. Nyholm andlQ4 T. Kruclr and M. Hofler, Angew. Chem., 1964, 76, 786.lS5 S. A. Khattab, L. Marko, G. Bor, and B. Marko, J. Organomet. Chern., 1964,lg6 S. V. Diglie and M. Orchin, J. Amer. Chem. SOC., 1964, 86, 3895.1964, 204, 871.K. Vrieze, Chem. and Ind., 1964, 318.1, 373192 INORGANIC CHEMISTRYis prepared by the reaction of triphenylgermyl-lithium with bis(triethy1-phosphine)platinum(n) chloride ; its most significant reaction is its cleavageby molecular hydrogen at room temperature and atmospheric pressure 9 9 7The evidence for, and the factors determining, the presence of metal-metal bonds in transition-metal oxides, sulphides, halides, and relatedcomplexes have been discussed. It is proposed that, when metals of highpreferred valency state are constrained to low formal oxidation states,metal-metal bonds will form to allow the metal to exercise a higher valency;it is concluded, therefore, that binary oxides and halides (excepting fluorides)of the lower oxidation states of Zr, Hf, Nb, Ta, Mo, W, Re, and a few neigh-bouring elements will display metal-metal b0nds.1~~ Metal-metal bondingwithin the three types of metal-atom cluster, fkt6x1,I9 +, [M6Xs]4f, and[M3X,,]3-, has been treated by a simple molecular-orbital method and it hasbeen shown that in this way all the general aspects of the electronic structurescan be straightforwardly accounted for.199 Compounds of the type M,IJMo30,containing MO& metal-atom clusters have been treated by a similarmolecular-orbital method, and the obtained pattern of molecular-orbitalenergies accounts satisfactorily for the strong metal-metal bonding and theabsence of unpaired electrons.200 The structural differences between mixedmetal oxides containing Sb5+, Nb5+, and Ta5+ ions can be qualitativelyunderstood if the metal-metal bonding is very effective for the Nb5+ ion,weakly effective for Ta5+, and non-erristent for Sb5+.201(Et3P)zPt(GePh,), + H, + (Et$)&(H)GePh, + PhSGeHlg7 R. J. Cross and F. Glockling, Proc. Chem. Soc., 1964, 143.lg8 J. C. Sheldon, AzcstraE. J . Chem., 1964, 17, 1191.lg9 F. A. Cotton and T. E. Haas, Inorg. Chem., 1964, 3, 10.2oo F. A. Cotton, Inorg. Chem., 1964, 3, 1217.201 G. Blasse, J . Inorg. Nuclear Chem., 1964, 26, 1191

ISSN:0365-6217    

DOI:10.1039/AR9646100113

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

ORGANIC CHEMISTRY1. INTRODUCTIONBy L. Crombie[Department of Chemhtry,University College (University of Wales), Cardifland V . Gold(Department of Chemistry, King’s College, Strand, London, W.C.2)ONLY slight changes have been made from the arrangement of last year’sReport, the most important being the inclusion of a section on organicquantum chemistry (last reviewed in the Report for 1961) in place of lastyear’s account of equilibria. A biennial report on nucleic acids replaceslast year’s corresponding section on amino-acids and peptides.In the past three years organic quantum chemistry has been applied tomany problems, but there appears to have been no major fundamentaladvance. Calculations of spectroscopic properties have received moreattention than theories of reactivity.In particular, the interpretation ofelectron spin resonance spectra on a quantum-mechanical basis is greatlyadding to the value of the rapidly increasing number of experimental studiesof stable and transient radicals and radical ions and of molecules in tripletstates.Problems of absolute configuration, energy differences between conform-ational isomers of both open-chain and ring compounds, and the bondangles in small carbocyclic ring systems continue to be explored by spectro-scopic and other optical methods. Specific deuterium-labelling is in-creasingly being used for the purpose of aiding the interpretation of massspectra of large molecules and of simplifying complicated proton resonancespectra. The rapidly growing use of carbon-13 nuclear magnetic resonancespectra is an important trend, whilst the possibility of determining tritiumresonance spectra has been demonstrated for the first time.Increasing interest in organic reaction mechanisms is notable in allsections.An unprecedented and very successful international symposiumon the subject included amongst the contributors and participants manyorganic chemists not so far associated with specialisation in this field.Carbonium-ion chemistry continues to stimulate a substantial amount ofwork. Whilst the demonstration of nuclear magnetic resonance spectra ofmany stable carbonium ions is clarifying one aspect of the subject, the prob-lem of non-classical ions as fleeting intermediates remains controversial.The simplifying elegance of the postulate that such ions exist is endangeredby reports of reactions for which the nature of the products is held to re-quire an equilibrium between several non-classical structures.The closerAbstracts, International Symposium on Reaction Mechanisms, sponsored by theChemical Society, the Institute of Chemistry of Ireland, and University College, Cork,held at Cork, Ireland, July 20-25th, 1964194 ORGANIC CHEMISTRYconcern of studies of catalysis with enzyme action is reflected both in thevolume of work on enzyme model systems and-in interest in catalysis bymacromolecular acids or in micelles. Kinetic studies of chymotrypsin andrelated enzymes assume new significance through the elucidation of theamino-acid sequence of a-chymotrypsin.Developments of preparative reactions based on ozone, such as “ amoz-onolysis ” for heterocyclic compounds and “ cyanozonolysis ” for hydroxy-acids and amino-acids, are of interest.New applications of dimethylsul-phoxonium methylide include a photochemical equivalent of the Arndt-Eistert reaction.Great interest in carbenes of many types is maintained and long-standinginvestigation of the structure of the Grignard reagent continues. Viewson the interconversion of polyacetylenes and their relatives in higher plantsare beginning to be tested by studies in vivo.Several novel ring systems have been prepared, including a “ prismane ’’derivative which is the first example of a compound known to contain theprism-like structure proposed by Ladenburg for benzene.It is formed byone of the remarkable trimerisation reactions of l-fluoro-2-t-butylacetylene.Another product from this reaction contains the ring system of Dewar’sbenzene formula. Following last year’s report of “ Dewar benzene ” itself,several derivatives based on this ring system are now known and othershave been invoked as reaction intermediates. Cubane has been synthesisedby a particularly elegant route. The previously reported supposed “ octa-phenylcubane ” has proved to be octaphenylcyclo-octatetraene. Other ringstructures of interest include bicyclobutane, tricyclohexanes, and an unusualmulti-layered p-cyclophane. The f i s t rational synthesis of a catenane isrecorded. Photochemical reactions of aromatic and alicylic compoundsare being used more generally for preparative purposes, as in the synthesisof ( + ) - thu j opsene.Structural assignments are now available for the quinonoid protoaphins.Total syntheses of kaurene, garryine, and stisine are a reminder of what asingle individual can still accomplish, and there has been other notablework in the diterpene alkaloid field.Tetrodoxin, the neurotoxin of the Japanese puffer fish, is an unusualhemilactal presenting an interesting synthetic challenge.In the corrinfield the preparation of the nickel(@ complex of (-J-)-l, 8, 8, 13, 13-penta-methyl-trans-corrin is noteworthy. Interest in the anti-tumour alkaloidsof Vinm rosea and its relatives ha.s continued and full structures for Vin-blastine and vincristine have been published. In the steroid field a verysimple total synthesis of equilin has emerged.Interest in nucleoside chemistry has been further stimulated by thediscovery of new nucleoside antibiotics.Study of nucleic acids by specialisedphysical techniques continues apace, and much effort is being devoted tosynthesis of 3’,5’-linked oligo- and poly-nucleotides. The widespread andenormous activity in nucleic acid studies is reflected in a startling estimateof the total number of papers published since the last Report two yearsago2. ORGANIC QUANTUM CHEMISTRYBy N. M. Atherton and J. N. Murrell(Department of Chernbtry, The University, Shefield, 10)IN this section are reviewed the more important developments in theapplication of quantum mechanics to organic molecules which have occurredsince the last Report on this subject.1 An account of general theory isfollowed, in more detail, by discussions of electronic spectra, electron andnuclear magnetic resonance, and reactivity.Most quantum-mechanical calculations on organic molecules are nowbased on molecular-orbital theory in its L.C.A.O.approximation. Thefree-electron approximation to molecular orbitals has been useful for aqualitative treatment of unsaturated molecules, but its mathematicaldevelopment to take account of electron interaction and the fine detail ofnuclear potentials becomes rather complicated. Valence-bond theory,which means more than the qualitative " resonance " theory used in organicchemistry, has also had only limited use because of its mathematical com-plications; it has, however, had a rather surprising success in explainingmagnetic resonance data.Also there has been a renewed examination oflinear and cyclic conjugated hydrocarbons by means of an empiricalvalence-bond theory which appears quite successful. For example, theHuckel 4n + 2 rule, which has always been taken to show the superiorityof the molecular orbital over valence-bond theories, can be derived by asimple valence-bond approach.3Most organic chemists are now familiar with the basic methods of Huckeltheory, and a considerable number of Huckel calculations occur in the recentliterature. There has also been a growing awareness of the limitations ofHuckel theory: outside the field of neutral alternant hydrocarbons the theorymust be used with caution.The appropriate parameters for hetero-atomsare now more clearly established than they were four years ago, but it isalso clear that, because of the gross approximations made in Huckel theory,the best values for these parameters depend somewhat on the nature ofthe property of the molecule which is under study.The Wheland-Mann method of varying the Coulomb integral accordingto the electron density on the atom (which Streitwieser 5 calls the cu-tech-nique) has found widespread use for aromatic ions and non-alternant hydro-carbons. This goes some way towards allowing for electron interactionin a molecular-orbital calculation, but is not enough for many problems.The Pariser-Parr-Pople method (the P-method) of introducing electroninteraction within a consistent zero-overlap approximation (see ref. 1) hasbeen extensively used for problems in which configuration interaction islR.McWeeny, Ann. Reports, 1961, 58, 137.M. Simonetta and E. Heilbronner, Theor. Chirn. Acta, 1964, 2, 228.H. Fischer and J. N. Murrell, Theor. Chim. Acta, 1963, 1, 463.G. W. Wheland and D. E. Mann, J. Chem. Phys., 1949, 17, 264.A. Streitwieser, J . Amer. Chem. SOC., 1960, 82, 4123196 ORGANIC CHEMISTRYessential to get agreement with experiment (see the sections on electronicspectra and electron spin resonance). A simplification of the P-methodhas been proposed in which only the most important two-electron integralsare retained-the one-centre and nearest-neighbour two-centre integrals.6However, insufficient work has been done with this to see whether itis a useful intermediate step between the w-technique and the fullP-method.There has been renewed interest in the molecular-orbital theory ofsaturated hydrocarbons. Although many methods had been proposedthe field suffered from the fact that the experimental data were insufficientto give a clear preference to one theory over the others.It is, however,likely that the calculation of nuclear magnetic resonance (n.m.r.) spin-spincoupling constants will provide a more critical test of these theories.*There have been two novel but controversial approaches to valencetheory. In Dewar’s split-p-orbital appr~ach,~ electrons are given a wavefunction which represents one lobe of a real p-orbital, and only one electronis allowed in each lobe.The criticism of this approach is that these wavefunctions do not have a satisfactory behaviour at the nucleus. In Linnett’snon-pairing approach lo the dominant influence on molecular structure istaken to be the repulsion between electrons of the same spin rather than thepairing of electrons of different spin. The Linnett approach is to be criticized,not on the grounds of invalid calculations, but rather on the deductionsand generalizations made from these calculations. Just because a wavefunction which is a mixture of LL simple valence bond and a simple molecular-orbital function gives a better energy than either of the two components,it does not follow that this wave function represents a non-paired electronscheme.ll Both the Dewar and the Linnett approach attempt to introduceelectron correlation into molecular calculations in a relatively simple manner.There have been several useful publications in the last four years whichgive a broad look at the methods now being followed in organic quantumchemistry. At an elementary level there is “ Notes on Molecular OrbitalCalculations ” by J.D. Roberts (Benjamin, 1962); a more advanced bookis “ Molecular Orbital Theory for Organic Chemists ’’ by A. Streitwieser(Wiley, New York, 1961). There is a Tetrahedron symposium on the statusof quantum chemistry in the interpretation of organic chemical phenomena(1963), Vol.19, Suppl. 2). There has also been a weighty book on quantumbiochemistry: B. Pullman and A. Pullman’s “ Quantum Biochemistry ”(Interscience Publ., Inc., New York, 1963).Electronic Spectra.-There have been several recent books and a reviewJ.M13 H. C. Longuet-Higgins and L. Salem, Proc. Roy. SOC., 1960, A , 257,445; E. Weltin,’ G. Klopman, Tetrahedron, 1963, 19, Suppl. 2, 14; J. A. Pople and D. P. Santry,J. A. Pople and D. P. Santry, MoZ. Phys., 1964, 8, 1.M. J. S. Dewar and N. L. Hojvat, J. Chem. Phys., 1961, 34, 1232; M. J. S. Dewarand A. L. H. Chung, ibid., 1963, 39, 1741; C. A. Coulson and C. S. Shaman, Proc.Roy. SOC., 1963, A , 272, 1.lo J. W. Linnett, The Electronic Structure of Molecules ”, Methuen, London,1964; D. M. Hirst and J.W. Linnett, J. Chem. SOC., 1962, 1035.l1 J. W. Linnett, J. Amer. Chem. SOC., 1964, 86, 2519; H. Shull, ibid., p. 1469.P. Weber, and E. Heilbronner, Theor. Chim. Acta, 1964, 2, 114.bl. Phys., 1964, 7 , 269; R. Hoffmann, J . Chem. Phys., 1963, 39, 1397ATHERTON AND MURRELL : ORGANIC QUANTUM CHEMISTRY 197dealing with the theory of electronic spectra of organic molecules.lZ Wewill mention only a few of the general developments that have occurred inthis subject.Theories which do not include the electron-interaction terms in theHamiltonian cannot provide a generally satisfactory interpretation ofelectronic spectra. In a theory based on one-electron operators, such asHiickel theory, there is no difference in energy between the Merent statesthat can arise from an open-shell configuration: there is no singlet-tripletsplitting, for example.The characteristic weak and strong bands of arom-atic hydrocarbon spectra (a and and lBb inPlatt’s nomenclature), arise from two states which are degenerate in a one-electron theory but whose degeneracy is removed by electron interaction.The one-electron theories, however, still have a useful role in correlatingthe energy of excited states within a family of related molecules, providedattention is confined to states of one particular type and provided these.states arise from non-degenerate electronic configuration^.^^A great deal of attention has been paid to the theory of weakly coupledchromophorea. Topics covered by this are the spectra of molecular crystals,14photocond~ctivity,~~ the properties of polymers and polynucleotides,15substituent effects,fa energy transfer,l7 and solvation effects.lB A generalproblem in this field is to what extent the observed phenomena are due to.energy delocalization (which does not require overlap of orbitals on different.molecules) or electron delocalization (which does).lgThere has been renewed interest in the vibrational structure of electronicabsorption bands 2o with the hope that by analysing this structure one canideduce the gebmetry of the molecule in its excited state.Some success has been achieved in explaining the optical rotatory powerof unsaturated ketones and helical molecules.This topic has been wellreviewed by Mason.2lLastly, there has been a considerable advance in our understanding ofin Clar’s nomenclature,l* S.F. Mason, Quart. Rev., 1961, 15, 287; H. H. Jaffe and M. Orchin, “ Theoryand Applications of Ultraviolet Spectroscopy ”, Wiley, New Yo&: 1962; J. N. Murrell,“The Theory of the Electronic Spectra of Organic Molecules , Methuen, London,1964; C. Sandorfy, “ Electronic Spectra and Quantum Chemistry ”, Prentice-Hall,.New York, 1964.lS E. Heilbronner and J. N. Murrell, J. Chem. Xoc., 1962, 2611; S. F. Mason, Tetra-hedron, 1963, 19, Su~pl. 2, 265.l4 D. P. Craig in Physical Processes in Radiation Biology ”, ed. L. Augenstein,R. Mason, and B. Rosenberg, Academic Press, New York, 1964; R. M. Hochstrasser,Rev. Mod. Phys., 1962, 34, 531; E. G. McRae, Awtral. J. Chem., 1963, 16, 315.l6 R.K. Nesket in “ Quantum Aspects of Polypeptides and Polynucleotides ’’+(Symposia No. 1) Biopolymers, Interscience Publ., Inc., New York, 1964; M. T. Valaand S. A. Rice, J. Chern. Phys., 1963, 39, 2348.l6 M. Godfrey and J. N. Murrell, Proc. Roy. Xoc. 1964, A , 278, 57, 64, 71; R. Grinterand E. Heilbronner, Helv. Chim. Acta, 1962, 45, 2496.l7 T. Forster in “ Comparative Effects of Radiation ”, ed. M. Burton, J. S. Kirby-Smith, and J. L. Magee, Wiley, New York, 1961.lS E. McRae, J. Phys. Chem., 1957, 61, 562; H. C. Longuet-Higgins and J. A. Pople,J . Chem. Phys., 1957, 27, 192.lo J. N. Murrell and J. Tanaka, Mol. Phys., 1964, 7, 363; S. Choi and S. A. Rice,J . Chem. Phys., 1963, 38, 366.2o E. F. McCoy and I. G. Ross, Austral.J . Chem., 1962, 15, 573.21 S. F. Mason, Quart. Rev., 1963, 17, 20198 ORGANIC CHEMISTRYthe factors governing radiationless transitions.22 The theory has not yetbeen developed to the point where one can predict fluorescence and phos-phorescence quantum yields, but this will no doubt be the next development.Electron Spin Resonance.-There has continued to be a large ouput ofpapers devoted to the interpretation of electron spin resonance (e.s.r.)spectra of aromatic radicals and radical-ions in terms of spin density.1The quantum-chemical theory underlying this work has been reviewed byCarrington 23 and by Moro~ova.~* McConnell’s equation relating protonhyperfine coupling and morbital spin density z5 has been re-derived underquite general conditions by McLachlan, Dearman, and Lefebvre.26 Theproperties of C-H bonds have also been discussed by Higuchi, who findsthat the isotropic hyperfine interaction is not strongly dependent on bondThe differences between the magnitudes of the proton splittingconstants in even-alternant cations and anions have been explained byColpa and Bolton, who show that the couplings depend on the charge densityon the ring-carbon atoms.28 However, Higuchi has commented that eventheir extended configuration-interaction treatment may be incomplete.27Molecular-orbital theory has been more widely used than the valence-bond approach, and Huckel theory successfully describes the unpaired-electron distribution in even-alternant radical-ions.23 Radicals derivedfrom substituted aromatic hydrocarbons often contain negative spin densitiesand these can be successfully, and most simply, predicted by McLachlan’sself-consistent field based treatment.29 Space does not permit the listingof all the papers dealing with different radicals, but a list of some of themolecular-orbital parameters found suitable for atoms of substituent groups(e.g., NO2, CHO, CN) has been p~blished.~O Molecular-orbital theory,including z-z configuration interaction, and valence-bond theory havenot been widely used in calculations for particular radicals, probably be-cause the treatments rapidly become very lengthy as the size of the moleculeincreases.Although valence-bond theory in its simplest form does predictnegative spin densities,23 calculations taking only Kekul6 and Dewarstructures into account tend to overestimate these.To obtain good agree-ment with the experimental results it is necessary to include ionic structures,and this feature, of course, increases the complexity of the calculations.An exception to the general tendency to favour the molecular-orbital ap-proach has been the work of Karplus and his collaborator^,^^ who haveshown how valence-bond theory may be used to describe the spin distri-butions in substituted benzenes. Valence-bond theory has also been suc-2 2 G. W. Robinson, J . Mol. Spectroscopy, 1961, 6, 58; G. W. Robinson and R. P.Frosch, J . Chem. Phya., 1962, 37, 1962; 1963, 38, 1187; M. Gouterman, ibid., 1962,36, 2846.23A. Carrington, Quart. Rev., 1963, 17, 67.24 I.D. Morozova, Rws. Chem. Rev., 1962, 31, 575.25 H. M. McConnell, J . Chem. Phys., 1956, 24, 764.26 A. D. McLachlan, H. H. Dearman, and R. Lefebvre, J . Chem. Phys., 1960, 33, 65.2 7 J. Higuchi, J . Chem. Phys., 1963, 39, 3455.28 J. P. Colpa and J. R. Bolton, Mol. Phys., 1963, 6, 273.2 9 A. D. McLachlan, MoZ. Phys., 1960, 3, 233.3O N. M. Atherton, Lab. Practice, 1964, 13, 1089.31 J. C. Schug, T. H. Brown, and M. Karplus, J . Chem. Phys., 1962, 37, 330; T. H.Brown, M. Karplus, and J. C. Schug, ibid., 1963, 38, 1749ATHERTON AND MURRELL : ORGANIC QUANTUM CHEMISTRY 199cessful in accounting for the observed spectra of vinyl and ethynyl, which area-electron radi~als.~2Hyperfine splittings from atoms in the ring ( 13C, and 14N in aza-aromatics)are expected to depend on the x spin densities on the neighbouring atomsas well as on their own spin densities.= Parameters describing 13C splittingsseem to be well established,33 but there is still some discussion as to the signof the neighbours’ contribution to 14N hyperfine splittings, although it isagreed to be small.A molecular-orbital calculation predicts a positivecontribution from the neighbours, in contrast to the 13C case.34There has been some discussion of the role of hyperconjugation in pro-ducing hyperfine splitting from substituent methyl groups. in aromaticradicals. There is compelling experimental evidence that hyperconjugationis the major mechanism,35 and a recent calculation, which predicts a muchsmaller contribution from spin polarization, supports this view.36 However,the effect of a methyl group on the distribution of n-electron spin densityin the aromatic ring can be satisfactorily accounted for in terms of an in-ductive effect.37Morton has reviewed the numerous studies of oriented radicals trapped insingle crystals.38 Analysis of the anisotropic hyperfine interaction in un-saturated radicals has demonstrated the existence of negative spin densitiesand has shown that, for a proton attached to a carbon bearing negativespin density, there is a considerable contribution to the anisotropic hyper-fine coupling from the (positive) spin density on t,he neighbouring carbonatoms.3B It has recently been confirmed that the couplings to a- and@-protons are opposite in sign.40 Radical conformations can be determinedby using the result that the isotropic coupling to a @-proton depends onthe angle between the C-C-H plane and the z-axis of the 213-orbital con-taining the unpaired electr0n.4~ Higuchi has deduced that the dependenceof the anisotropic splitting by a-protons on bond angles at the carbon atomis less than would be expected from consideration of the sp-hybridi~ation.~~The calculation of g-values of organic free radicals had received scantattention apart from the early remarks of McConnell and Robertson.43Recently, however, Stone has used molecular-orbital theory to calculateg-values of some hydrocarbon radical-ions and neutral odd-alternantradicals.44 The results agree well with the available experimental data.The e.s.r. spectra of the anions of certain hydrocarbons of D,, or D6,,32 E.L. Cochran, F. J. Adrian, and V. A. Bowers, J. Chem. Phys. 1964, 40, 213;33M. Karplus and G. K. Fraenkel, J. Chem. Phys., 1961, 35, 1312.34 J. C. M. Henning, Ph.D. Thesis, 1964, University of Amsterdam.35 J. R. Bolton, A. Carrington, and A. D. McLachlan, Mol. Phys., 1962, 5, 31.36 J. P. Colpa and E. de Boer, Mol. Phys., 1964, 7, 333.37 J. R. Bolton and A. Carrington, Mol. Phys., 1961, 4, 497.38 J. R. Morton, Chem. Rev., 1964, 64, 453.39 C. Heller and T. Cole, ‘J. Chem. Phys., 1962, 37, 243; R. J. Cook, J. R. Rowlands,40 R. J. Cook and D. H. Whiffen, Proc. Phys. SOC., 1964, 84, 845.41 W. Derbyshire, Mol. Phys., 1962, 5, 224.4 2 J. Higuchi, J .Chem. Phys., 1964, 41, 2084.4s H. M. McConnell and R. E. Robertson, J. Phys. Chem., 1957, 61, 1018.44A. J. Stone, Mol. Phys., 1963, 6, 509; 1963-64, 7, 311.F. J. Adrian and M. Karplus, ibid., 1964, 41, 56.and D. H. Whiffcn, Mol. Phys., 1964, 7, 57200 ORGANIC CHEMISTRYsymmetry (e.g., coronene and benzene) show line broadening which may beattributable to the Jahn-Teller effect.45 This observation has promptedsome theoretical investigation and the vibronic coupling problem has beenquite thoroughly discussed using molecular-orbital theory.46 In contrastto benzene and coronene the cyclo-octatetraene anion has a barrier betweenequivalent conformations, and its e.s.r. spectrum has narrow lines.47 Thespectra of radicals with near-degenerate ground states have been quali-tatively discussed;48 there are interesting effects caused by deuteriumsubstitution and temperature-variation, and it is clear that they can onlybe fully understood in terms of a complete vibronic theory.4B The low-temperature spectra of cycloheptatrienyl radicals in rigid matrices are infair accord with the predictions of Pariser-Parr and self-consistent-fieldcalculations, although it is difficult to assess properly the effects of torsionalmolecular oscillations and the crystal field in this system.50Dinegative ions with open-shell configurations are expected to havetriplet ground states, and this has been confirmed experimentally for tri-phenylbenzene and decacycline, but not for ~oronene.~~ There have beenextensive experimental studies of disubstituted carbenes and nitrenes,which also have triplet ground ~tates.~2 The spin-spin interaction in thecarbenes has received some theoretical attention from Higuchi.53 Workon the spectra of photo-excited triplet states has continued, one of the moreinteresting conclusions being that in its lowest triplet state benzene hasD,, symmetry and that tunnelling between equivalent conformationsoccurs at a rate of about 1O1O ~ e c .- l . ~ ~ Most of the better known aromatichydrocarbons have been studied and the observed zero-field splittings havebeen compared with theoretical values in some cases.55 Finally, mentionmust be made of triplet excitons, which have been investigated theoreticallyby McConnell and his collab0rators,5~ and for which there is experimentalevidence from the spectra of crystals of Wurster’s Blue perchlorate 57 andthe salts of tetracyanoquinodimethane anion.58 Photo-excited tribenzo-triptycene is believed to exhibit intramolecular exciton migration.5445 M.G. Townsend and S. I. Weissman, J. Chem. Phys., 1960, 32, 309.46 W. D. Hobey and A. D. McLachlan, J. Chem. Phys., 1960,33, 1695; C. A. Coulson47 A. D. McLachlan and L. C. Snyder, J. Chem. Phys., 1962, 36, 1159.48 J. R. Bolton, A. Carrington, A. Forman, and L. E. Orgel, MoZ. Phys., 1962,4 9 T. R. Tuttle, J. Amer. Chem. SOC., 1962, 84, 1492, 2839; R. G. Lawler, J. R.6 0 H. J. Silverstone, D. E. Wood, and H. M. McConnell, J. Chem. Phys., 1964,5 1 R. E. Jesse, P. Biloen, R. Prins, J. D.W. van Voorst, and G. J. Hoijtink, MoZ.5 2 A. M. Trozzolo, R. W. Murray, G. Smolinsky, W. A. Yager, and E. Wasserman,53 J. Higuchi, J. Chem. Phys., 1963, 38, 1237; 1963, 39, 1339.54 M. S. de Groot and J. H. van der Waals, MoZ. Phys., 1963, 6, 545.55 S. A. Boorstein and M. Gouterman, J. Chem. Phys., 1963, 39, 2443; Y. Chiu,56H. Sternlicht and H. M. McConnell, J. Chem. Phys., 1961, 35, 1793; H. M.5 7 H. M. McConnell, H. 0. GrifFith, and D. Pooley, J. Chem. Phys., 1962, 36, 2518.5 8 D. B. Chesnut and W. D. Phillips, J. Chem. Phys., 1961, 35, 1002; D. B. Chesnutand A. Golobiewski, MoZ. Phys., 1962, 5, 71.5, 43.Bolton, G. K. Fraenkel, and T. H. Brown, ibid., 1964, 86, 520.41, 2311.Phys., 1963, 6, 633.J . Arner. Chem. SOC., 1963, 85, 2526.ibid., p.2736; J. H. van der Waals and G. ter Maten, MoZ. Phys., 1964, 8, 301.McConnell and R. M. Lynden-Bell, ibid., 1962, 36, 2393, 2518.and P. Arthur, ibid., 1962, 36, 2969ATHERTON AND MURRELL : ORGANIC QUANTUM CHEMISTRY 201Nuclear Magnetic Resonance.-Experimental data in this field havecontinued to accumulate at a formidable rate. Improvements in instru-mentation have made it possible to observe resonances of 13C and otherisotopes in natural abundance quite readily. In contrast, the number ofdetailed calculations on organic molecules has been relatively small. At theFaraday Society Discussion held at Oxford in 1962 the ditriculties of makingprecise calculations of chemical shifts and spin-spin coupling constants wereunderlined. 59Fundamental work on chemical shifts has been done by Pople, whohas used rnolecular-orbital theory to show how the shift for a particularnucleus can be described in terms of contributions from atomic diamagneticcurrents.60 The theory has been further developed in parallel with ageneral theory of diamagnetism, a principal feature being the use of gauge-invariant atomic orbitals.6l The approach has been criticized by Hameka,who has also used gauge-invariant atomic orbitals in an S.C.F.calculationof diamagnetic susceptibility;62 he points out that it may be theoreticallysounder to consider the principal contributions to the susceptibility ascoming from the bonds rather than from the atoms, in a molecule.63The main quantitative successes in the calculation of chemical shiftshave been for aromatic molecules.Karplus and Pople have used molecular-orbital theory to discuss 13C shifts : the principal contributions come from then-electron density and free valence of the atom under consideration. 64Contributions to proton shifts can be divided into ring-current and localized-electron terms, and the relative magnitudes of these effects in aromatichydrocarbons have been discussed recently by Dailey. 65 From quitesimple considerations, the relative proton shifts in aromatic molecules areexpected to correlate with the n-electron densities. The results on hydro-carbons have been summarized and discussed by Schaefer and SchneiderYG6and substituted benzenes have been considered by Dailey and his co-workers,67 who discuss the validity of the correlation.For monosubstitutedbenzenes the proton shifts at the rneta- and para-positions correlate wellwith the n-electron densities, but those for the ortho-position do not. Itis now accepted that in order to describe the shift properly it is necessaryto take into account terms arising from the magnetic anisotropy of thesubstituent. 67 Similar considerations apply to the interpretation of theproton shifts in nitrogen-heteroaromatic compounds.68 The proton shiftsin substituted ethylenes have been recently discussed: the shifts of theB-protons can be adequately accounted for in terms of contributions fromn-electron density and magnetic anisotropy of the substituent s calculated59 Discuss. Faraday SOC., 1962, 34.6o J.A. Pople, Disczlss. Faraday SOC., 1962, 34, 7.61 J. A. Pople, J . Chem. Phys., 1962, 37, 53, 60; 1963, 38, 1276; 1964, 41, 2559.6 2 H. F. Hameka, Physica, 1962, 28, 908.63 H. F. Hameka, J . Chem. Phys., 1962, 37, 3008.6 4 M. Karplus and J. A. Pople, J . Chem. Phys., 1963, 38, 2803.6 5 B. P. Dailey, J . Chem. Phys., 1964, 41, 2304.67 B. P. Dailey and J. S. Martin, J . Chem. Phys., 1963, 39, 1722; T. K. Wu andB. P. Dailey, ibid., 1964, 41, 2796.6 8 B. P. Dailey, A. Gower, and W. C. Neikarn? Discuss. Faraday SOC., 1962, 34,18; V. M. 8. Gil and J. N. Murrell, Trans. Faraday SOC., 1964, 60, 248.T. Schaefer and W. G. Schneider, Canad. J . Chem., 1963, 41, 966202 ORGANIC CHEMISTRYfrom a point-dipole model; but for the a-protons the agreement is less good,suggest'ing the inadequacy of the point-dipole The shifts of 19Fnuclei in conjugated compounds have been interpreted in terms of contri-butions from the n-electron charge densities and the F-C bond ordersevaluated by simple molecular-orbital theory.70Two experimental developments should prove stimulating for work onelectron-coupled spin-spin interactions.First, there have been manymeasurements of the relative signs of coupling constants by double-reson-ance methods 71 and from the analysis of double quantum transition^.^^These methods are much more convenient than the analysis of second-orderspectra. Secondly, and perhaps more fundamentally, the absolute sign ofa coupling constant has been measured 73 by following a suggestion byBuckingham et aZ.74It has become clear that the original valence-bond theory of geminalproton couplings 75 is in error.76 The application of molecular-orbitaltheory to this problem had not been enthusiastically pursued until recentlyon account of McConnell's conclusion that a simple theory could onlygive positive coupling^.?^ This is a consequence of using an average excit-ation energy in the denominator of the perturbation expression.Pople andSantry have recently shown that, if this approximation is omitted, thernolecular-orbital theory can still be tractable and yields an excellent accountof the couplings between nuclei of the first-row elements.78 An importantresult is that H-H and H-F couplings have opposite signs. Furthermore,the theory provides a most satisfactory account of geminal proton couplings,including their dependence on H-C-H angle and the electronegativity ofsub~tituent~s.79 The results of original valence-bond theory of vicinalproton couplings have continued to be widely used in conformationalanalysis, although Karplus has stressed the limitations of the theory.80Ot'her calculations of coupling constants have generally involved onlythe contribution from the contact term, which is the principal factor. Theuse of valence-bond theory is typified by the work of Juan and Gutowskyon the dependence on substituents of the 13C-H and 29Si-H couplings inmethanes, ethylenes, and silanes.A success for molecular-orbital theoryhas been the description of the n-electron-coupled interactions in mesityleneand trisperfluoromethylbenzene. g289 T.Schaefer and T. Yonemoto, Canad. J . Chem., 1964, 42, 2318.F. Prosser and L. Goodman, J . Chem. Phys., 1963,38,374; R. W. Taft, F. Prosser,7 1 J. P. Maher and D. F. Evans, Proc. Chem. SOC., 1961, 208; R. A. Freeman and7 2 B. Dischler and 0. Englert, 2. Natzlrforsch., 1961, Ma, 1180; K. A. McLauchlan73 A. D. Buckingham and K. A. McLauchlan, Proc. Chem. SOC., 1963, 144.7 4 A. D. Buckingham and E. G. Lovering, Trans. Faraday SOC., 1962, 58, 2077.75 H. S. Gutowsky, M. Karplus, and D. M. Grant, J . Chem. Phys., 1959, 31, 1278.'6 M. Karplus, J . Amer. C h m . Soc., 1962, 84, 2458.7 7 H. M. McConnell, J . Chern. Phy8., 1956, 24, 460.78 J. A. Pople and D. P. Santry, MoE.Phys., 1964, 8, 1.?9 J. A. Pople and D. P. Srtntry, personal communication.8 0 M. Karplus, J . Amer. Chena. SOC., 1963, 85, 2870.SIC. Juan and H. S . Gutowsky, J . Chem. Phys., 1962, 37, 2198.8 2 J. V. Acrivos, Mol. Phys., 1962, 5, 1.L. Goodman, and G. T. Davies, ibid., p. 380.D. H. Whiffen, MoZ. Phys., 1961, 4, 321.and D. H. Whiffen, Proc. Chem. SOC., 1962, 144ATHERTON AND MURRELL : ORGANIC QUANTUM CHEMISTRY 203Reactivity.-The number of reactivity indices currently encountered inthe literature has remained steady over the past few years. Those mostcommonly encountered are electron density, p~larizability,~~ frontierdensity,84 superdelocalizability,~5 Z-factor,s6 localization energy,87 Dewarnurnber,s* and free valence.89A systematic studyhas been made of the ionisation and ultraviolet absorption properties ofamino- and hydroxy-pyridines; both the mono- and the di-protonation ofaminopyridines have been st~died.1~8 Pyridine, some allrylpyridines, andisoquinoline combine with dimethyl acetylenedicarboxylate at low tempera-tures to form 1:l:l molar adducts.l*g Alkylation of pyridine with mag-nesium powder and l-chlorobutane gives 57 o/o of 4-n-butylpyridine andonly a trace of the 2-isomer; in contrast, reaction of pyridine with ether-freen-butylmagnesium iodide in toluene gives 18 yo of 2-n-butylpyridine essenti-ally free from the 4-isomer.15* In the germally accepted mechanism for theconversion of 2-methylpyridine N-oxide into 2-acetoxymethylpyridine withacetic anhydride, the anhydrobase (75) is postulated as an intermediate.Reaction of 1-acetoxy-2-methylpyridinium perchlorate with triethylamineproduces 2-acetoxymethylpyridine but attempts to detect the intermediateformation of (75) failed.151 Experiments with lSO as a tracer suggest anintermolecular ionic mechanism €or the reaction of 3-methylpyricline N-oxideD.Martin, Chem. Ber., 1964, 97, 2689; D. Martin, Tetrahedroz Le:ters, 1964,Six-membered Rings.-Pyridines and piperidines.142 K. A. Jensen and A. Holm, Acta Cibem. Xcand., 196-2, 18, 826.2829.144 D. Leaver and D. M. McKinnon, Chem. and Id., 1964, 461.1*5 A. Biezais and G. Bergson, Act0 Cizern. Xcand., 1964, 18, 515.1 4 6 D. A. Usher and F. H. Westheimer, J . Amer. Chem. Soc., 1964, 86, 4732.14' F.Korte and H. Riichling, Tetrahedron Letters, 1961, 2090.148 G. B. Barlin, J. Chem. Soc., 1964, 2150.149 R. M. Acheson and A. 0. Plunket, J. Chem. Xoc., 1934, 2676.l60 n. Bryce-Smith, P. J. Xorris, and B. J. Wakefield, Chem.. and I.nd., 1964, 495.151 V. J. Traynelis and P. L. Pacini, J. Amw. (?hem. SOC., 1964, 20, 4917384 ORGANIC CHEMISTRYand acetic anhydride to give 2-acetoxy-3-methyl- and 2-acetoxy-&methyl-pyridine.152 The displacement of nitrite ion from 4-nitropyridine N-oxidewith piperidine is believed to be the first example of a light-catalysed aromaticsubstitution in heterocyclic chemistry.153 The unusual substitution reac-tions of 1 -alkoxy-, 1 -alkanoyloxy-, and 1 -arenesulphonyloxy-pyridiniumsalts with thiols have been further examined. Treatment with butane-l-thiol results in different mixtures of 2-, 3-, and 4-butylthiopyridines withchanges in the leaving 2-Alkoxypyridine N-oxides rearrange veryreadily, when heated, to the corresponding N-alkoxy-2-pyridones.155 When2-allyloxypyridine is heated in dimethylandine at 255 O, Claisen rearrange-ment occurs and a mixture of 1- and 3-allyl-2-pyridones is formed.156Pentachloropyridine, prepared in 96% yield by heating pyridine with anexcess of phosphorus pentachloride at 350",157 has been converted intopentafluoro- and chlorofl~oro-pyridines.~~~~ 158 Experiments with deuteratedpyridines, and evidence derived from product analyses, rule out a generalmechanism for the Tschitschibabin reaction involving pyridyne inter-mediates.lS9Aminations of 3- and 4-chloro-, -bromo-, and -iodo-pyridines withpotassium amide in liquid ammonia proceed by way of 3,4-pyridyneY butthe corresponding reaction of 3-fluoropyridine is anomalous.ls0 There ismuch less evidence for 2,3-pyridyne intermediates; however, the mixtureof 2- and 3-aminopyridine N-oxide obtained by treatment of 2-chloropyridineN-oxide with sodium amide in liquid ammonia suggests the intermediacyof 2,3-pyridyne N-oxide.ls19 162 2-Amino- and 2-methylamino-pyridine areoxidised a t the ring-nitrogen atom on treatment with perbenzoic acid, butoxidation occurs at the exocyclic nitrogen atom in the case of 2-dimethyl-aminopyridine.163 9 l64 The Smiles rearrangement of 3 - amino-2,2'-bipyridylsulphides and their N-acetyl derivatives can be acid-, base-, or heat-cata-1ysed.l 65Reduction of lY4-dimethyl-2-phenylpyridinium iodide with sodiumborohydride gives 1,2,3,6-tetrahydro-l,4-dimethyI-2-phenylpyridine; thisinvolves protonation of the intermediate lY2-dihydropyridine a t position3.166 1,2-Dihydropyridines are conveniently prepared by reduction ofpyridinium salts with sodium borohydride in the presence of a large excess152 S.Oae and 5. Kozuka, Tetrahedron, 1964, 20, 2961.153 R. M. Johnson and C. W. Rees, Proc. Chem. Xoc., 1964, 213.154 L. Bauer and T. E. Dickerhofe, J . Org. Chem., 1964, 29, 2183.155 F. J. Dinan and H. Tieckelmann, J . Org. Chem., 1964, 29, 1650.156 F. J. Dinan and H. Tieckelmann, J . Org. Chem., 1964, 29, 892.157R. 33. Banks, R. N. Hazeldine, J.V. Latham, and I. M. Young, Chem. and158 R. D. Chambers, J. Hutchinson, and W. K. R. Musgave, Proc. Chem. SOC.,159 R. A. Abramovitch, F. Helmer, and J. G. Saha, Tetrahedron Letters, 1964, 3445.l6O R. J. Martens, H. J. den Hertog, and M. van Ammers, Tetrahedron Letters,161 R. J. Martens and H. J. den Hartog, Rec. Traw. chim., 1964, 83, 621.162 T. Kat,o, T. Niitsuma, and N. Kusaka, J . Pharm. SOC. Japan, 1964, 84, 432.168 L. Pentimalli, Gaxxetta, 1964, 94, 458.164 J. S. Wieczorek and E. Plazek, Rec. Traw. chim., 1964, 83, 249.lcs 0. R. Rodig, R. E. Collier, and R. K. Schlatzer, J. Org. Chem., 1964, 2652.166 P. S. Andersen and R. E. Lyle, Tetrahedron Letters, 1964, 153.I n d . , 1964, 835.1964, 83.1964, 3207CHEXSEMAN : HETEROCYULIC COMPOUNDS 385of cyanide ion, followed by reaction of the resulting cyanotetrahydro-pyridines with potassium ethoxide solution.lS7 A mixture of isomeric1,Z- and 1-4-dihydro-derivatives is obtained when 3,5-dicyanopyridine istreated with methylmagnesium iodide.ls* Catalytic reduction of S-acetyl-pyridine in ethanol, and in the presence of 5t palladium-charcoal catalyst,givea mainly 3-acetyl- 1,4,5,6-tetrahydropyridhe, but use of sodium boro-hydride gives the expected 3- l'-hydroxyethylpyridineridine.lss Thermal cleavageof the bipyridyl (76) does not give 1,4-diacefyl-l,4-dihydropyridine aspreviously suggested, but 1 -4'-pyridylethyl acetate.Treatment of com-pound (76) in boiling methanolic hydroxylamine gives the mono-oxime of1,4-diacetyl- 1,4-dihydropyridine .I70 3,4,5,6-Tetrahydro-Z -t - butylpyridinehas been prepared in 75% yield by dehydrogenation of 2-t-butyl-piperidinewith mercuric acetate.l71A general ring synthesis involving a Michael alkylation is exemplifiedby the preparation of 3-acetyl-1 -benzylpiperidine from N-benzyl-3-chloro-propylamine and methyl vinyl ketone.172 Dipole-moment measurements~ M e nO N oH>Hc NAc X pN->xpN Me- - Ac N(76) (77a) X = p-CbH,CI (77b) (7 8)on 4-p-chlorophenylpiperidine and 4-p-chlorophenyl-1 -methylpiperidhe inbenzene indicate that the conformers (77a; R = H and Me) are present tothe extent of ca.88% and 94%, respectively, in the equilibrium mixtures.Thus the steric requirements of the lone pair on nitrogen are less than thoseof a hydrogen atom or a methyl gr0up.l7~9 l7* From equilibration experi-ments with methyl 1 -methyl&- 1 -azadecalin-cis-4-carboxylate and thecorresponding trans,cis-derivative under solvating and non-solvating con-ditions, it has been deduced that the steric requirement of the solvated lonepair on nitrogen is greater than that of hydrogen.lY5 A total synthesisof the antibiotic (-)-cycloheximide (78) has been achieved.176Condensed pyridines.Bromination of the quinoline-aluminium chloridecomplex gives successively 5-bromo-, 5,8-dibromo-, and 5,6,8-tribromo-quinoline. The best selectivity is obtained by adding bromine as gas ratherle7 E. M. Fry, J . Org. Ohm., 1964, 29, 1647.lea J. Kuthan, E. JaneEkova, and M. Havel, Coll. Czech. Chem.Conam., 1964,29,143lea M. Freifelder, J . Org. Chern., 1964, 29, 2895.A. T. Nielsen, D. W. Moore, J. H. Mazur, and K. H. Berry, J . Org. Chem.,171M. F. Grundon and B. E. Reynolds, J . Chem. Soc., 1964, 2445.17* J. E. Dolfini and D. M. Dolfini, Tetrahedron Letters, 1964, 2103.17a R. J. Bishop, L. E. Sutton, D. Dineen, R. A. Y. Jones, and A. R. Katritzky,174 N. L. Allinger, J. G. D. Carpenter, and F. ?A. Karkoaski, Tetrahedron Letters,K. Brown, A. R. Katritzky, and A. J. Waring, Proc. Chem. Soc., 1964, 257.176 F. Johnson, N. A. Starkovsky, A. C. Paton, and A. A. Carlson, J . Arner. Chrn.1964, 29, 2898.PTOC. Chem. Soc., 1964, 257.1964, 3345.SOC., 1964, 86, 118386 ORGANIC CHEMISTRYthan as liquid.l77 Spectroscopic evidence indicates that 2-benzamido-cinnamaldehyde is the product of the reaction between quinoline, benzoylchloride, and sodium hydr~xide.~'~ Reaction of 2-methylquinoline N-oxidewith 180-labelled benzoyl chloride gives 2-benzoyloxymethylquinoline withan equal concentration of l*O in both the ether- and the carbonyl-oxygenatom ; this indicates a free-radical solvent-cage mechanism for the decompo-sition of the intermediate anhydro-base.l'g When 4-nitroquinoline N-oxideis treated with the sodium derivative of diethyl malonate, nucleophilicsubstitution unexpectedly occurs at position 3.lSO Reaction of 2-hydroxy-quinoline l-oxide in pyridine with one equivalent of toluene-p-sulphonylchloride yields mainly 8-tosyloxy-2- quinolone .lS1 Claisen rearrangementof 4-allyloxy-2,3-dimei;hylquinoline gives 2- but -3 '-enyl-4- hydroxy-3-methyl-quinoline with only a trace of the para-rearrangement product .lS2 Isoquinol-ine and phenanthridine N-oxide form addwts with ethylene- and acetylene-carboxylic acid esters; for example, reaction of isoquinoline N-oxide with ethylacrylate and methyl propiolate gives compounds (79) and (SO), respectively.lS3A theoretical study of the H-quinolizines by the Huckel molecular-orbitalQNH d 0 H \ N /2 Br- a CH2*CH (OH)-CO,Et MeO, C-C .CHOmethod shows that the order of stability is 4H > 2H > 9aH.184 I-Hydroxy-quinolizinium salts are extremely readily bronlinated and nitrated in the%position ; t,ha diazonium salt (81) has remarkable thermal stability.l=The key step in a new isoquinuclidine synthesis is the addition of methylene-urethane to cyclohexa-l,3-diene.l*6 The structure of phomazarin (82), anorange pigment produced by the fungus, Phoma terrestis Hansen, has beendetermine~1.l~~Axines.Two unusual ring contractions of pyridazine derivatives havcbeen reported; the conversion, (83) +(84), is effected with aqueous sodiumM. Gordon and D. E. Pearson, J . Org. Cheni., 1964, 29, 329.178 I. W. Elliott, J . Org. Chem., 1964, 29, 305.179 S. Oae and S. Kozuka, Tetrahedron, 1964, 20, 2671.l a o H. J. Richter and N. E. Rustad, J . Org. Chem., 1964, 29, 3381.lS1 M. Hamana and K. Funakoshi, J . Pham. SOC. Japan, 1964, 84, 28.1 8 2 Y. Makisumi, Tetruhedron Letters, 1964, 699.185 H. Seidl and R. Huisgen, Tetrahedron Letters, 1963, 2023.184 R.M. Acheson and D. M. Goodall, J. Chm. Soc., 1964, 3225.Ia5 A. Fozard and G. Jones, J. Chem. SOC., 1964, 2760, 2763, 3030.186 M. P. Cava and C. K. Wilkins, Jr., Chem. and Ind., 1964, 1422.I B i A. J. Birch, D. N. Butler, and R. W. Rickarda, Tetrahedron Letters, 1964, 1853CHEESEMAN : HETEROCYCLIC COMPOUNDS 387hydroxide,158 and (85) +( 86) with Raney Cinnoline quaternisesa t position 2; thus the basic centre of cinnoline is N-2 rather than N-1CI P 11 phn; Ph - ;)r-JphN " N' N(8 3) (84) ( 8 5) (86)as previously assumed.lgO Benzo[c]cinnolines have been prepared byphotochemical, oxidative ring closure of azobenzenes,l91 and an analogousphenanthridine synthesis has been achieved from an aromatic Schiff base.Ig2Light is produced from the reaction of luminol (87) with alkali and oxygenin aprotic solvents such as dimethyl sulphoxide and dimethylformamide ;0the aminophthalate ion is the light-emitting species.lg3 In a new pyrimidinesynthesis, both pyrimidine-nitrogen atoms are derived from ammonia,C-2 from an aromatic aldehyde, and the remaining ring-carbon atomsfrom lY3-diketone derivatives.lg4 A systematic study of the p.m.r.spectraof pyrimidines has been made195 and a simple experimental method developedfor predicting optimum conditions for the amination of chlor~pyrimidines.~~~Transformations of biological significance are the conversion of uracil andits derivatives into pyrazolones on treatment with hydrazine and alkyl-hydrazines,lg' and the formation of stable adducts from uracil and relatedpyrimidines and benzo[a]pyrene on irradiation with ultraviolet light .198Pyrimidinylamino-acids cyclise with rearrangement on treatment withacetic anhydride; as in the Dimroth rearrangement, an exchange of exo-cyclic and ring-nitrogen occurs .l Divicine (2,4-diamino-5 ,fj-dihydroxy-pyrimidine) has been syntliesised 2oo and the structure of the blue crystallinesolid (88) formed by reaction of an excess of 2-thiobarbituric acid with1 ,I ,3,3-tetraethoxypropane has been determined.201 Tetrodotoxin, a potentlSsY. Maki and K.Obata, Chem. and Pharm. Bull. (Japan), 1964, 12, 176.189 A. Pollak and M. Tissler, Tetrahedron Letters, 1963, 253.l90 D. E. Ames and H. Z. Kucharska, J. Chem. SOC., 1964, 283.lS1 G. M. Badger, R.J. Drewer, and G. E. Lewis, Austral. J . Chem., 1963, 16,192 M. P. Cava and R. H. Schlessinger, Tetrahedrota Letters, 1964, 2109.E. H. White, 0. Zafiriou, H. H. Kagi, and J. H. M. Hill, J . Amer. Ohem. Soc.,194 F. Krohnke, E. Schmidt, and W. Zecher, Chem. Ber., 1964, 97, 1163.195 S. Gronowitz, B. Norrman, B. Gestblom, B. Mathiasson, and R. A. Hoffman,lS6 D. J. Brown and J. M. Lyall, AustraE. J . Chem., 1964, 17, 794.lo' F. Lingens and H. Schneider-Bernlohr, Angew. Chena., Internat. Edn., 1964,3,379.lS8 J. M. R,ice, J. Amer. Chem. SOC., 1964, 86, 1444.l g 9 T . Ueda and 3. J. Fox, J . Org. Chem., 1964, 29, 1762, 1770.200 J. H. Chesterfield, D. T. Hurst, J. F. W. McOmie, and M. S. Tute, J . Chem.201R.' G. Shepherd, J. Chem. SOC., 1964, 4410.1042.1964, 86, 940; E.H, White and 31. M. Bursey, ibid., p. 941.Arkiv Ke9ni, 1964, 22, 65.SOC., 1964, 1001388 ORGANIC CEBMISTRYneurotoxin isolated from the Japanese puffer fish, has an unusual hemi-lactal (orthoacid diester) structure (89).202 Pulcherrimine and pulcherri-minic acid (90) have been synthesised.203 s H H,Oe H 0- x~c,::;~x H2:<& Ho Bui[ 0 /$ >iu;O H H O(90)N( 8 8 ) HO CH1.OHH OH(8 9)Three groups of workers have prepared quinoxaline N-oxides by thecyclisation of ar-cyano-o-nitroacetanilides (and related o-nitrocarbanilideswith an activated methylene group) in an alkaline medium.2w The reactionbetween alloxan and o-sminodimethylaminobenzene gives the spiran (91)and its oxidation product the betaine (92) as a AeruginosinI3 (93), one of the red pigments produced by Pseudoomonas aerugirtosa, isthe fist example of an aromatic sulphonic acid arising from naturalsources.206 4-Hydroxy- 1,3-thiazin-6-ones have been prepared by reactionof thioamides with carbon subo~ide.~O~ Synthesis of the 3,6-dihydro-2LI- 1,3-thiazine ring system, present in the antibiotic cephalosporin C,has been achieved.208Reaction between diguanides and carbodi-imides in dimethylformamideMe203 R.B. Woodward and J. Z. Gongoutas, J . Amer. Ohem. Soc., 1964, 86, 50302osA. Ohta, Chma. and Plmrm. Bull. (Japan), 1964, 12, 125.204 G. Tennant, J . Chem. SOC., 1964, 2666; R. Fusco and S. Rossi, Gazzetta, 1964,205 J . W. Clark-Lewis, J. A. Edgar, J. S. Shannon, and M. J. Thompson, Auatral.Zo6 R.B. Herbert and F. G. Holliman, Proc. Chem. SOC., 1964, 19.207 E. Ziegler and R. Wolf, Monatsh., 1964, 95, 1061.208 D. M. Green, A. G. Long, P. J. May, and A. F. Turner, J . Chem. Soc., 1964,and references therein.94, 3; Y. Ahmad, M. S. Habib, and Ziauddin, Tetrahedron, 1964, 20, 1107.J. Chem., 1964, 17, 877.766; G. C. Barrett, S. H. Eggers, T. R. Emerson, and G. Lowe, ibid., p. 788CHEESEMAN : HETEROCYCLIC COMPOUNDS 389provides a new general route to melamine~.~o~ Thermal rearrangement of2,4-dimethoxy- lY3,5-triazine gives an appreciable quantity of the bis-triazinylidene (94).210 Methylation of the 1H-naphthotriazine (95 ; R = H)with dimethyl sulphate in methanolic sodium hydroxide gives a mixtureof the red monomethyl derivative (95; R = Me) and a blue monomethylderivative (96).2f1A new purine synthesis is exemplified by the condensation of 4-amino-1,3-dimethyl-5-nitrosouracil with benzyltrimethylammonium iodide togive 8-phenyltheophylline.212 The chemical shifts of the 2, 6, and 9 protonsof purine have been assigned by specific deuteration procedures.213 Purinemay be converted directly into 8-mercaptopurine by reaction with sulphur ;2-mercaptobenzimidazole is also prepared by this method.214 A 2-nitro-purine is obtained as a by-product from the reaction of guanosine withnitrous acid.215 Zeatin (97), isolated from sweet-corn kernels, is morepotent in inducing cell division than is kinetin; its structure was deduced byphysical measurements 216 and confirmed by The aglycone ofthe antibiotic, toyocamycin (98; R = CN), has been synthesised and thiswork has also led to an improved synthesis of the aglycone of tuberocidin(98; R = H).218 Considerable progress has been made towards the completeBtructural determination of the antibiotic, viomycin, hydrolysis of whichgives a complex mixture of peptides, including the peptide (99).219The tautomeric equilibrium between (100a) and (100b) has been ex-amined. Only the Gtrazolo-tautomer isMe Me( 1 O O a ) (1OOb)present in deuterated dimethylH209 F.Kurzer and E. D. Pitchfork, J . Chem. SOC., 1964, 3459.210 A. Piskala, Tetrahedron Letters, 1964, 2587.211 M. J. Perkins, J . Chem. SOC., 1964, 3005.212 E. C. Taylor and E. E. Garcia, J . Amer. Chem. SOC., 1964, 86, 4720.21s M.P. Schweizer, S. I. Chan, G. I(. Helmkamp, and P. C. P. Ts'o, J . Amer.214A. Giner-Sorolls, E. Thorn, and A. Bendich, J . Org. Chem., 1964, 29, 3209.216 R. Shapiro, J . Amer. Chem. Soc., 1964, 86, 2948.216 D. S. Lethm, J. S. Shannon, and I. R. McDonald, Proc. Chem. SOC., 1964, 230.217 G. Shaw and D. V. Wilson, Proc. Chem. SOC., 1964, 231.218 E. C. Taylor and R. W. Hendess, J. Arner. Chem. SOC., 1964, 86, 951.Chem. SOC., 1964, 86, 696.J. H. Bowie, D. A. Cox, A. W. Johnson, and G. Thomas, Tetrahedron Leftem,1964, 3305; J . H. Bowie, A. W. Johnson, and G. Thomas, Tetrahedron Letters, 1964, 863390 ORGANIC CHEMISTRYsulphoxide, and only the azido-tautomer in trifluoroacetic acid. In deuterio-chloroform, KT at 37" is 0-36.220 The acid-catalysed Michael-type additionof 7-hydroxy-fi-methyl- and 6-hydroxy-7-methyl-pteridine gives a racemicdipteridinylmethane (101 ), which has been resolved chromatographically.221Oxygen heterocyczes.A systematic study of the n.m.r. spectra of pyryliumsalts has been made.222 The polarographic reduction of 2,4,6-trimethyl-pyrylium salts is a one-electron process; the dimeric product, 2,2',4,4',6,6'-hexamethyl-4,4'-bi-4H-pyran, is conveniently prepared by chemical re-duction with zinc dust .223 4-Benzyl-2,4,6-triphenyl-4H-pyran, is obtainedby the reaction of 2,4,6-triphenylpyrylium perchlorate with benzylmag-nesium chloride. It has been converted into lY2,3,5-tetraphenylbenzeneand into 1,3-diphenylnaphthalene, and is photoisomerised to 4-benzyl-2,4,6-triphenyl-2H-pyr1tn.~'~ Treatment of 4-pyrone with deuterium oxidegives the 3,5-dideuterio-derivative as the major product ; the correspondingreaction with ls0-enriched water leads to the incorporation of l a 0 intoboth the carbonyl group and the heterocyclic ring.225 1,3,5,7-Tetramethyl-cyclo-octatetraene is prepared conveniently by photodimerisation of 4,6-dimethyl-2-pyrone, followed by decarboxylafion.22* The structures of+C Me*OH0 CH=CH-C,A c n 2 E r Et 0 2 C o I OH0 CH-CH-CHAcno2Et (102) CO2Et('03) (104)diethyl xanthophanic acid (102) and diethylglaucophank acid (103) havebeen determined.227 Radicin (104) is a phytotoxic metabolic product ofthe plant-pathogenic fungus, Xtemphylium radicinum.228 The mechanisms220 C.Temple, Jr., and J.A. Montgomery, J . Amer. Chem. SOC., 1964, 88, 2946.221A. Albert and E. P. Serjeant, J. Chern. Soc., 1964, 3357.222 A. T. Balaban, G. R. Bedford, and A. R. Katritzky, J. Chem. SOC., 1964, 1646.223 A. T. Balaban, C. Bratu, and C. N. Rentea, Tetrahedrort, 1964, 20, 265.224 K. Dirnroth, K. Wolf, and H. Kroke, Annalen, 1964, 678, 183, 202.2 2 5 I?. Beak and G. A. Carls, J. Org. Chem., 1964, 29, 2678.* 2 6 P. de Mayo and R. W. Yip, Proc. Chem. SOC., 1964, 84.2 2 7 L. Crombie, D. E. Games, and M. H . Knight, Tetrahedron Letters, 1964, 2313.2-28 J. F . Grove, J . Chem. SOC., 1964, 3234CHEESEMAN: HETEROCYCLIC COMPOUNDS 391for the photodimerisation of coumarin have been investigated : irradiationin ethanol with benzophenone as sensitizer gives the trans-head-to-headdimer ;22Q analogous photodimers have been obtained from 2-quinolone andits N-methyl deri~ative.2~0 Structures for three naturally occurring 4-hydroxy-3-phenylcoumarins, namely, robustic acid ( 105),231 scandenin (106),and lonchocarpic acid (107),232 have been proposed.The value of p.m.r.measurements for the characterisation of flavonoidsis illustrated in a compilation of the spectra of flavonoids in deuterateddimethyl sulphoxide.233 The structure of casticin (108) has been confirmedby synthesis ;Z3* 5-methylgenistein (109) isolated from Cytisus Zabz~rnicrnL.,235 and the structure of icht-hynone (110) determined.236"€?.o% Me0 \0(108) ' OMe ( ' 0 9 )OHReduction of chroman with an excess of lithium in ethyIamine gives5,6,7,8-tetrahydrochroman which on treatment with m-chloroperbenzoicacid gives 6-ketonoanolide dire~tly.2~' The compound (111) is the firstflavan from natural sources that does not contain an oxygen atom attachedto the heterocyclic ring.238 Acetolysis of tetra-0-methyl-(+ )-catechintoluene-p-sulphonate unexpectedly produces a mixture of acetoxy-chromanand -cournanan~ne.~~~ The absolute configuration of citrinin (1 12) hasbeen determined ; n.m.r.measurements indicate that the preferred conforma-tion is that in which the 3- and the 4-methyl group are quasiaxial.240 Ag2s G. S. Hammond, C. A. Stout, and A. A. Lamola, J . Amer. Chem. SOC., 1964,86, 3103.230 0. Buchardt, Acta Chem. Smnd., 1964, 18, 1389.231 A. P. Johnson, A. Pelter, and M.Barber, Tetrahedron Letters, 1964, 1267.232A. Pelter and A. P. Johnson, Tetrahedron Letters, 1964, 2817.233 T. J. Batterham and R. J. Highet, Austral. J . Chem., 1964, 17, 428.234 L. Horhammer, H. Wagner, E. Grd, and L. Farkas, Tetrahedron Letters, 1964,235 J. Chopin, M. Bouillant, and P. Lebreton, BuU. Soc. chim. France, 1964, 1038.236 J. S. P. Schwarz, A. I. Cohen, W. D. Ollis, E. A. Kaczka, and L. 15. Jackman,Tetrahedrm, 1964,20,1317; S. F. Dyke, W. D. Ollis, M. Sainsbury, and J. S. P. Schwarz,ibid., p. 1331.237 I. J. Borowitz and G. Gonis, Tetrahedron Letters, 1964, 1151.238 A. J. Birch and M. Salahuddin, Tetrahedron Letters, 1964, 2311.23B C. A. Anirudhan, D. W. Mathieson, and TY. B. Whalley, Proc. Chem. Soc.,240 R. K. Hill and L.A. Gardella, J . Org. Chem., 1964, 29, 766; D. W. Mathieson323.1964, 84.and W. B. Whalley, J. Chern. SOC., 1964, 4640392 ORGANICY CHEMISTRYnew synthesis of isochromans employing the condensation of 2-dimethyl-aminobenzyl-lithium with aldehydes and ketones is reported.241 A1-3,4-truns-Tetrahydrocannabinol (1 13) is the first active constituent of hashishwhose constitution is fully elucidated.242 Detailed investigations leadingMe\M e O W O M e MFG C,HII-nMe ‘\H Me(’4 (112) ( 1 13)to the determination of the structures of the protoaphins, the xanthoaphins,the chrysoaphins, and the erythoaphins and to the nature of their inter-conversions have been published.245Sulphur and other heterocycles. Cyclopenta[c]thiapyran (1 14) protonatesa t position 7 and undergoes a variety of electrophilic substitutions at positions5 and 7.244 Decomposition of the dichlorocarbene adduct of the thia-chromene (115) in hot quinoline does not give the expected benzothiepin(‘14) (‘15) (‘I 16)but gives the thiachromone (1 16).2& l-Thiachroman-4-one oxime, onreduction with lithium aluminium hydride, furnishes a mixture of 4-amho-1 -thiachroman and tetrahydroben~o[b]-1,4-thiazepine.~~~ 1,4-Dithiin hasbeen prepared in 70% yield by reaction of the &sodium salt of cis-1,2-dimercaptoethylene and cis- 1,2-dichloroethylene with sodamide in liquidTreatment of the 2-phenyl-l,3-dithian-5-ols with phosphorylchloride in pyridine causes ring contraction, and 4-chloromethyl-2-phenyl-1,3-dithiolans are formed with considerable stereo~pecificity.~~* Theconfigurations of a number of thianthrene 5,lO-dioxides have been assignedspectroscopically; the truns- are isomerised to the cis-isomers by heat.249lY3,Z-Dioxaborinium cations (117) constitute a novel aromatic system;they are formed by treating an equimolecular mixture of a 1,3-diketoneand tri-n-butyl borate with anhydrous perchloric acid.250 When an equi-24l R. L.Vaulx, F. N. Jones, and C. R. Hauser, J . Org. Chem., 1964, 29, 1387.242 Y. Gaoni and R. Mechoulam, J . Amer. Chem. SOC., 1964, 86, 1646.448 D. W. Cameron, R. I. T. Cromartie, and Lord Todd, J . Chem. SOC., 1964, 48,244 A. G. Anderson, Jr., and W. F. Harrison, J . Amer. Chem. Soc., 1964, 86, 708.245 W. E. Parham and M.D. Bhavsar, J . Org. Chem., 1964, 29, 1575.246 V. A. Zagorevskii and N. V. Dudykina, Zhur. obschei Khim., 1964, 34, 2283.247 W. Schroth and J. Perschel, 2. Chem., 1964, 4, 271.248 R. J. S. Beer, D. Harris, and D. J. Royall, Tetrahedron Letters, 1964, 1531.24s K. Mislow, P. Schneider, and A. L. Ternay, Jr., J . Amer. Chem. Soc., 1964, 86,250 A. T. Balaban, E. Barabas, and A. Arsene, Tetrahedron Letters, 1964, 2721.and succeeding papers.2957CHEESEMAN : HETEROCYCLIC COMPOUNDS 393molecular melt of 2-methylaminobiphenyl and triphenylaluminium isheated, 9-methyl-l0-phenyl-10,9-aluminazarophenanthrene (1 18) is pro-duced in associated form; this new heterocycle is isoelectronic with phen-anthrene and significantly less~henanthrene.~~~RfiR 0: 0?'(117) OBu"Seven-membered Rings andstable than the corresponding borazaro-M e (118)Ph' A]- N ,Other Heterocycles.-Reduction of ethylazepine-l-carboxylate with lithium aluminium hydride gives 1 -methyl-azepine, which is thermally unstable.The ester is rearranged by acidto N-phenylurethane; treatment with alkali and then with acid gives1H-azepine which rearranges to 3H-a~epine.~~2 The ethoxydihydroazepine(119; R = OEt) loses ethanol on gentle warming, to give the 4H-azepine(120), which is in equilibrium with its valency tautomer (121). TreatmentEt02C CO2EtMe Me M e ' K"'" N ' M e(119) H H (122)Et 0 2 " EtozC Me C02EtMe('20) (121)of the azepine (120) with bromine in carbon tetrachloride yields the di-hydropyridine (12Z).253 Reaction of compound (119; R = CN) withaqueous-ethanolic silver nitrate gives the furo[2,3-b]pyridine ( 123).254 Thedihydroazepinone (124) shows typical amide behaviour, forms an adductwith tetra~yanoethylene,~~~ and undergoes photoisomerisation to a bicyclicamide ( 125).25251 J. J. Eisch and M. E. Healey, J . Amer. Chem. Soc., 1964, 86, 4221.262 K. Hafner, Angew. Chem., Internat. Edn., 1964, 3, 165.z5sM. Anderson and A. W. Johnson, Proc. Ckem. Soc., 1964, 263.254 E. Bullock, B. Gregory, and A. W. Johnson, J . Chem. SOC., 1964, 1632.255 L. A. Paquette, J. Amer. Chem. SOC., 1964, 86, 4092, 4097; L. A. Paquette,266 L. A. Pequette, J. Amer. Chem. SOC., 1964, 88, 500; 0. L. Chapman and E. D.J . Org. Chm., 1964, 29, 3447.Hoganson, ibid., p. 498394 0 R G AN IC C H E 191 S TR YSyntheses of oxepin and 2,7-dimethyloxepin have been reported.Ox-epin, a liquid of b.p. 38"/30 mm., appears to be in equilibrium with itsvalency tautomer, benzene epo~ide.~~' An attempt to prepare benzo[b]-thiepin from its 2,3-dihydro-derivative, by successive treatment withsulphuryl chloride and sodium hydrogen carbonate, gave naphthalene andelemental sulphur.25sThe 1,2-diazepinone (126) undergoes base-catalysed rearrangement toa mixture of cc-aminopyridines after initial abstraction of a proton.259An unusual ring contraction occurs when the diazepine N-oxide (127) istreated with phosphoryl chloride with the formation of the tetrahydro-quinoxaline (128).260 Reaction of the diazepine N-oxide (129) fist withacetic anhydride and then with aqueous-methanolic alkali gives 5-chloro-3 - p hen ylindole - 2 -car baldeh y de dime t hyl a cet a1 .The perhydro thiazep -ine (130) has been formed by stereospecific synthesis from 2-N-phenyl-acetamidoacrylic acid and D-penicillamine. Treatment of this compound(130) with chlorine at -60°, followed by heating to 60°, gives in additionto the 2,3-dehydro-derivative, a mixture of two isomeric isothiazol-3-0nes.2~2The enantiomeric forms of the dibenzodiazocine (131) have been preparedand shown to have considerable optical stability.263Me Me(130) (13') ( I 32)1,6-0xido[lO]annulene (132) has the aromatic properties expected ofa plana,r 10melectron system. It is isomerised to 1-benzoxepin on attemptedchromatography on silica gel.Z6* Reaction of 1,4-dichlorobut-2-yne withinorganic sulphides gives 1,6-dithiacyclodeca-3,8-diyne (133), which under-goes base-catalysed rearrangement to the bicyclic thienothiepin ( 134).265257 E.Vogel, R. Schubart, and A. Boll, Angew. Chem., Internat. Edn., 1964, 3, 510.258 V. J. Traynelis and J. R. Livingstone, Jr., J. Org. Chem., 1964, 29, 1092.259 J. A. Moore and E. C. Zoll, J . Org. Chem., 1964, 29, 2124.260 S. C. Bell and S. J. Childress, J . Org. Chem., 1964, 29, 506.261 W. Metlesics, G. Silverman, and L. H. Sternbach, J . Org. Chenz., 1964, 29, 1621.262 N. J. Leonard and G. E. Wilson, Jr., Tetrahedron Letters, 1964, 1465, 1471.268 D. M. Hall and J. M. Insole, J . Ghenz. Soc., 1964, 2326.2s4F. Sondheimer and A. Shani, J .Amer. Chem. SOC., 1964, 86, 3168; E. Vogel,M. Biskup, W. Pretzer, and W. A. Boll, Angew. Chem., Internat. Edn., 1964, 3, 642.266 G. Eglinton, I. A. Lardy, R. A. Raphael, and G. A. Sim, J . Chem. SOC., 1964,1154CHEESEMAN : HETEROCYCLIC COMPOUNDS 395A mixture of seven- and fourteen-membered tin-containing heterocyclesis produced by treatment of o-divinylbenzene with diphenylstannane.266CH2'C=C*C\H2 K O B " ~,s - sCH2* C f C * CH;s:(133) (134) (135)[ 18]Annulene trisulphide (135) has been synthesised ; 267 molecular-orbitalcalculations indicate that it is considerably less a.romatic than [ 18]annulene,and its ultraviolet absorption is in agreement with this conclusion.2sap66 A. J. Leusink, J. C. Noltes, H. A. Budding, and G. J.M. Van Der Kerk, Rec.267 G. M. Badger, J. A. Elix, and G. E. Lewis, Proc. Chem. SOC., 1964, 81.ze8 C. A. Coulson and M. D. Poole, Proc. Chem. Soc., 1964, 220.Trav. chim., 1964, 83, 103610. ALKALOIDSBy J. D. Hobson(Department of Chemistry, The University, Edgbaston, Birmingham, 15)A BOOK dealing specially with the application of mass spectrometry toelucidation of alkaloid structures has been produced by the Stanford gr0up.lNumerous papers on this subject have appeared, including general studieson the tropane,2 lupin,3 protopine,4 ipecacuanha,5 pseudoindoxy1,a steroid,'and colchicine alkaloids. * The potentialities of bigh-resolution massspectrometry have been extended by the use of a computer, enabling thephotographic record of the entire spectrum of an organic compound to betransformed semiautomatically into a tabulation of the accurate masses, andthus the elemental composition, of all the ions prod~ced.~ The chemistryof alkaloids containing a lactone ring lo and of the aporphine bases 11 hasbeen reviewed.Biogenesk-The incorporation of [2-W]ornithine by Datura stramoniumgives hyoscyamine ( 1 ) uniquely labelled at the bridgehead position (marked)having the R-configuration.Thus, in the racemic dienamine obtained bydegradation, only the (+)-enantiomer, shown to have the absolute con-figuration (Z), possessed the label at C-1.12 The incorporation of 14C0, intonicotine by Nicotianu glutinosa gives results consistent with the hypothesisthat the pyrrolidine ring is derived from a symmetrical intermediate, originat-ing from ornithine or glutamic acid.The observed labelling pattern, how-ever, appears to require an alternative glutamate biosynthesis from carbondioxide outside the tricarboxylic acid cycle.13 Experiments with 15N-labelled lysine have revealed that the E-amino-group only is the origin ofthe piperidine N-atom of anabasine.14 Support has been obtained for theproposal that (2-4, C-5, and C-6 of the pyridine ring of the nicotine alkaloidsoriginate from glycerol or a similar precursor.15 Details have been published1 €I. Budzikiewicz, C. Djerassi, and D. H. Williams, " Structural Elucidation ofNatural Products by Mass Spectrometry, Vol. I, Alkaloids ", Holden-Day, San Fran-cisco, 1964.a J. Parello, P. Longevialle, W.Wetter, and J. A. McCloskey, Bull. SOC. chim.France, 1963, 2787.N. Neuner-Jehle, H. Nesvadba, and G. Spiteller, Monatsh., 1964, 95, 687.L. Dolejg, V. Hanug, and J. Slavdk, Coll. Czech. Chem. Comm., 1964, 29, 2479.H. Budzikiewicz, S. C. Pakrashi, and H. Vorbriiggen, Tetrahedron, 1964,20, 399.N. Finch, I. Hsiu-Chu Hsu, W. I. Taylor, H. Budzikiewicz, and C. Djerassi,H. Budzikiewicz, Tetrahedron, 1964, 20, 2267. * J. M. Wilson, M. Ohashi, H. Budzikiewicz, F. Santavy, and C. Djerassi, Tetra-K. Biemann, P. Bommer, and D. N. Desiderio, Tetrahedron Letters, 1964, 1725.J . Amer. Chem. SOC., 1964, 86, 2620.lterlron, 1963, 19, 2225.loA. R. Pinder, Chem. Rev., 1964, 64, 551.l1 M. Shamma and W. A. Slusarchyk, Chem. Rev., 1964, 64, 59.la E. Leete, Tetrahedron Letters, 1964, 1619.l3 W.L. Alworth, R. C. de Silms, and H. Rapoport, J . Amer. Chem. SOC., 1964,86, 1608; W. L. Alworth, A. A. Liebman, and H. Rapoport, ibid., p. 3375.l4 E. Leete, E. G. Gros, and T. J. Gilbertson, J . Amer. Chern. Soc., 1964, 86, 3907.l5 E. Leete and A. R. Friedman, J . Amer. Chem. SOC., 1964, 86, 1224HOBSON: ALKALOIDS 397of the work of Battersby and his colleagues on the biosynthesis of the mor-phine alkaloids ;Is the biosyntheses of hydrastine, berberine?' and cheli-donine l8 also conform to the now familiar pattern in that dopamine servesORas a precursor for only one c,-c2 unit, whereas tyrosine is capable of supply-ing two such units. A full description has also appeared of experimentsdemonstrating the elaboration of the Amaryllidaceae alkaloids from a c,-c2unit derived from tyrosine, and a C,-C, unit, possibly isovanillin, originatingfrom phenylalanine .l9In contrast to the clear-cut labelling pattern observed by Leete andGhosalY2* Battersby and his co-workers 21 have found only random scatterof activity in ajmaline produced by Rauwolfia serpentina fed with [1J4C]-acetate. Moreover, the isolation of ajmaline labelled at C-21, previouslyobserved20 as a result of the administration of [14C]formate, was not re-produced in the Liverpool group's work, in which only rather poor incorpora-tion of radioactivity was achieved with both precursors. Similar randomscattering of the label was observed in emetine and cephaeline isolated fromanalogous experiments with C.ipecacuanha. [3-14C]Tryptophan is in-corporated into ibogaine by Tabernanthe iboga with unusual efficiency(6-7%), most of the activity being confined to C-7,22 and into vindoline,vindolinine, and catharanthine by Catharanthus ro~eus.23It is now clear that, as in the Amaryllidaceae, phenylalanine and tyrosineare utilised in separate pathways in the biosynthesis of colchicine. Theformer, but not the latter, is capable of generating the ring A - C ~ porti011,2~, 25A. R. Battersby, R. Binks, R. J. Francis, D. J. McCaldin, and H. Ramuz,J. Chem. Soc., 1964, 3600; A. R. Battersby and R. J. Francis, ibid., p. 4078.17 I. Monkovic and I. D. Spenser, Proc. Chem. Xoc., 1964, 223.18 E. Leete and J. B. Murrill, Tetrahedron Letters, 1964, 147.lB A.R. Battersby, R. Binks, S. W. Breuer, H. M. Fales, W. C. Wildman, and2o Ann. Reports, 1963, 60, 399.a1 A. R. Battersby, R. Binks, W. Lawrie, G. V. Parry, and G. R. Webster, Proc.2 2 M. Yamasaki and E. Leete, Tetrahedron Letters, 1964, 1499.23 D. Groger, K. Stolle, and J. Mothes, Tetrahedron Letters, 1964, 2579.2L E. Leete, J . Amer. Chem. SOC., 1963, 85, 3666.25 A. R. Battersby and R. B. Herbert, Proc. Chem. Xoc., 1964, 260; A. R. Battersby,R. J. Highet, J . Chem. SOC., 1964, 1595.Chern. SOC., 1963, 369.R. Binks, J. J. Reynolds, and D. A. Yeowell, J . Chem. SOC., 1964, 4257398 ORGANIC CHEMISTRYwhereas incorporation of [3-W] tyrosine by Colchicum uutumnale gives col-chicine labelled exclusively at C-12. It is suggested that oxidative couplingoccurs in a precursor of the type (3), followed by ring expansion of theresulting dienolone (4).25m o l e and l?yridine Groups.-Strigosine, the major alkaloid of Helio-tropium strigosum, has been identified as the ( - )-ap-dihydroxy-p-methyl-valerate of tra~helanthamidine,~~ and jacozine as an epoxide of seneciphyl-line, into which it is reduced by reaction with potassium selenocyanate.27The tobacco alkaloid, anatabine, has been synthesised by using thedienophilic properties of the methyleneiminocarboxylate derived from (5),followed by hydrolysis of the product (6; R = C02Et).28 The structure(7) has been deduced for cassine from its mass spectrum.29 Bases isolated(ypJ Ph @ I N &HN0 Me(8)from LobeZia species appear to be of a new structural type; lobinaline,from L.cardinalis, has been formulated as (8) on the basis of physical evi-dence and chemical degradations, including especially its conversion, by de-methylation and dehydrogenation, into 5,7-diphenyl-6-2’-pyridylquinoline.30Syphilobin-A and -F, from L. syphiliticct, though not yet fully characterised,appear to have the same skeleton, but with additional substituents.31Of the two new Papilionaceous alkaloids isolated from Argyrolobiummegurhixium, both of which give (-)-sparteine on complete reduction, onehas been identified as the (-)-enantiomer (9 ; R = H) of aphyllidine, andthe other as a 2-hydroxy-derivative (9; R = OH).32 Monspessulanine,from Cytisus monspessulanw, has been formulated as (+ )-5,6-dehydro-l0-oxo-a-isosparteine (9; R = H, epimeric at C-ll),33 and virgiline and calpur-nine, from Virgilia oroboides, have been established as (-)- 13-hydroxy-aphylline, and the pyrrole-2-carboxylate of ( + ) - 13- hydroxylupanine,26A.R. Mattocks, J. Chem. SOC., 1964, 1974.27 C. C. Culvenor, Austral. J . Chem., 1964, 17, 375.28 P. M. Quan, T. K. B. Karns, and L. D. Quin, Chem. and Ind., 1964, 1553.29 R. J. Highet, J. Org. Chem., 1964, 29, 471.so M. M. Robison, W. G. Pierson, L. Dorfman, B. F. Lambert, and R. A. Lucas,31 R. Tschesche, D. Kloden, and H. W. Fehlhaber, Tetrahedron, 1964, 20, 2885.33 E. P. White, J . Chem. SOC., 1964, 4613.Tetrahedron Letters, 1964, 1513.Tsuda aDd L. Marion, Canad. J . Chem., 1964, 42, 764EOBSON: ALKALOIDS 399respectively.34 The structure of ormosanine has been revised to (10) inview of the elucidation of the structure of its formaldehyde reaction product,jamine (10 ; N-CH,-N bridge), by X-ray cry~tallography.~~ Piptanthine,an alkaloid of Piptanthus nanus, derivable from ormosanine by a remarkablyeasy isomerisation occurring under catalytic reduction conditions, has beenshown to be the 6 - e ~ i m e r .~ ~Quindine and Isoquinoline Group.-A synthesis of the Lulzasia alkaloid,lunacridine, has been rep~rted.~' The relative and absolute stereochemistryMeQMeQMe0Me0Reagents: 1, NaBM,. 2, H+. 3, CH,Cl*CO,Me-Na,NH,. 4, OH-.5, HC33COMe, NaH.of several phthalide-isoquinoline bases have been determined, includinga-narcotine, shown to have the 1R,9S-configuration.S8 Petaline (ll),34 G.C. Gerrans and J. Harley-Mason, J. Chem. Xoc., 1964, 2202.35 I. L. Karle and J. Karle, Tetrahedron Letters, 1963, 2065; P. Naegeli, W. C.36 P. Deslongchamps, J. S. Wilson, and Z. Valenta, Tetrahedron Letters, 1964, 3893.37 E. A. Clarke and Bf. F. Grundon, J. Chem. Xoc., 1964, 438, 4190.38 M. Ohta, H. Tani, S. Morozumi, S. Koidara, and K. Kuriyama, TetrahedronLetters, 1963, 1857; A. R. Battersby and H. Specer, ibid., 1964, 11; S. Safe and R. Y .Mob, Canad. J . Chem., 1964, 42, 160.Wildman, and R. A. Lloyd, ibid., p. 2069400 ORGANIC CHEMISTRYisolated from Leontice Ewnpetalum, has the rare 7,s-dioxygenated isoquinohestructure hitherto observed only in the cularine and the unusualstructure (12) has been assigned to ochotensimine, based largely on nuclearmagnetic resonance (n.m.r.) data obtained for the base and on its reductionand Emde degradation prod~cts.~OThalmelatine, another dimeric aporphine- benzylisoquinoline base ob-tained from Thalictrurn species, has been shown to be O-demethylthali-~ a r p i n e .~ ~ The gross structure of tubulosine (13; R = OH), a type ofalkaloid not previously found naturally, was established 42 by comparisonof its mass spectrum with that of the known synthetic 43 parent compound(13 ; R = H). The quaternary aporphine alkaloid, (+)-laurifoline chloride,has been obtained by ferric chloride oxidation of the methochloride of(+)-reticube (14; R = H, R‘ = Me), which itself occurs naturally inFagaro n~ranjillo.~~ Support for the hypothesis 2o that certain aporphinesare derived by rearrangement of initially formed isoquinolinedienediones hasbeen provided both by an in witro analogy, the synthesis of (&)-isothebaine(16) from the phenol (14; R = Me, R’ = H), by way of the dienone (15),45and by the discovery of additional, naturally occurring members of thisgroup.The latter include glaziovine (17; R = R” = Me, R’ = H), occur-ring in Ocotea glaxiovii together with its derived aporphine (18 ; R = R” = Me,R‘ = H, R”’ = OH),46 and stepharine (17; R = R’ = Me, R“ = H) whichaffords pronuciferine (17; R = R’ = R” = Me) on N-methylation.47 Thelast base has be3n synthesised in racemic form from 1 -ethoxycarbonylmethyl-6,7-dimethoxyisoquinoline by way of the ketone (19), and thence by thesteps i n d i ~ a t e d .~ ~The orientation of hydroxyl and methoxyl groups in crotonosine (17;R = R” = H, R‘ = Me) follows from its conversion into the known apor-phine (18 ; R = R“‘ = H, R’ = R” = Me) by successive N-methylation, boro-hydride reduction, and dienol-benzene rearrangement. Base-catalysed deu-terium-exchange experiments with both apocrotonosine (18; R = R” = H,R’ = Me, R”’ = OH) and apoglaziovine (18; R = R“ = Me, R’ = H,R”‘ = OH), showing the presence of three exchangeable hydrogen atoms(ortho to phenolic OH) in the former, compared with two in the latter, haveprovided confirmation of their structure^.^^ It has been pointed out 5O that8 9 N. J. Mecorkindale, D. S . Magrill, M. Martin-Smith, S.J. Smith, and J. B.40 S. McLean and Mei-Sie Lin, Tetrahedron Letters, 1964, 3819.4lN. M. Mollov and H. B. Dutschewska, Tetrahedron Letters, 1964, 2219.42 P. Brauchli, V. Deulofeu, H. Budzikiewicz, and C. Djerassi, J. Amer. Chem. SOC.,4a A. R. Battersby, J. C. Davidson, and J. C. Turner, J . Chem. SOC., 1961,*4 S. M. Albonico, A. M. Kuck, and V. Deulofeu, Chem. and Ind., 1964, 1580.45 A. R. Battersby and T. H. Brown, Proc. Chem. Soc., 1964, 85.46 B. Gilbert, M. E. A. Gilbert, M. M. de Oliveira, 0. Ribeiro, E. Wenkert, B.47 M. P. Cava, K. Nomura, R. H. Schlessinger, K. T. Buck, B. Douglas, R. F.M L. J. Haynes, K. L. Stuart, D. H. R. Barton, and G. W. Kirby, Proc. Chem.60 I . R. C. Bick, Experientia, 1964, 20, 362; cf. ref. 46, footnote 17.Stenlake, Tetrahedron Letters, 1964, 3841.1964, 86, 1895.3899.Wickberg, U.Hollstein, and H. Rapoport, J . Amer. Chem. Soc., 1964, 88, 694.Raffauf, and J. A. Weisbach, Chem. and Ind., 1964, 282.SOC., 1964, 261.K. Bernauer, Experientia, 1964, 20, 380HOBSON: ALKALOIDS 401an isoquinolinedienedione structure (17; R,R' = CH2, R" = Me) is alsoconsistent with the properties previously reported 51 for fugapavine.The novel structure (20) has been proposed for hasubanonine, isolatedfrom Stephania japoniuz, dif€ering from earlier structures proposed by Kondoand by Bentley, which had a morphine skeleton. The assignment restsMeOMe (20)largely on infrared and n.m.r. data obtained from the base and its degrada-tion products, one of which was shown to be enantiomeric with a product(21) obtained by successive reduction and O-methylation of dihydroindoline-codeinone.52 The last compound was previously obtained by reduction of14-bromocodeinone with sodium borohydride and was assigned the structure(22):3 though some doubt of its correctness has since been expressed.54Of the two other related bases isolated from the same source, metaphanineis formulated as (23); with hot acetic anhydride it underwent a (reductive?)transformation into (24), and was also converted into the enantiomer of(21) by WOE-Kishner and catalytic reduction.The second base, prometa-phanine, was amorphous, but afforded metaphanine (23) on mild acid-treatment ; its chemical and spectroscopic properties, including its n.m.r.spectrum in variom solvents, were in accordance with structure (25), inequilibrium with the hemiketal form (26) in solution.5551 V.A. Mnatsakanyan and S. Yu. Yunusov, DokEady Akad. Nauk, Uzbekh.S.S.R.,1961, 12, 36.53 M. Tomita, T. Ibuka,, Y . Inubushi, Y . Watanabe, and M. Matsui, TetrahedronLetters, 1964, 2037.5s S. Okuda, K. Tsuda, and S. Yamaguchi, J. Org. Chem., 1962, 27, 4121.54 K. W. Bentley, ref. 20, p. 406.5 5 M. Tomita, T. Ibuka, Y. Inubushi, and K. Tclkeda, Tetrahedron Letters, 1964,3605; M. Tomita, T. Ibuka, and Y. Inubushi, ibid., p. 3617402 ORGANIC CHEMISTRYAmaryllidacem Alkaloids.-The absolute configuration previously as-cribed to galanthamine has been confirmed by X-ray crystallography.56The mechanism of the base-catalysed rearrangement of the methiodides ofG-hydroxycrinamine (27) and its 3-epimer, haemanthidine, to give, respect-ively, criwelline (29) and tazettine , has been clarified.Deuterium-labellingprovides evidence for an intramolecular hydride shift in the intermediate(%), followed by hemiketal f~rmation.~' The use of methanol as the solventfor the initial methylation of 6-hydroxycrinamine results in interception ofthe aldehyde (28) as the acetal(30; R = OMe), acid hydrolysis and oxidationof which affords macronine (30; R = 0),57 recently isolated from Crinummacranther urnAmaryllidiiie has been formulated as (31) on the basis of the close cor-respondence of its infrared, n.m.r., and mass spectra with those of othercrinine bases.59 Narcissamine, formerly regarded as ( - )-norgalanthamine,has been shown to be a quasiracemate consisting of equimolar proportionsof ( - )-norgalanthamine and ( +)-dihydronorgalanthamine.60OH ,.- . IIndole Alkaloids.-A valuable catalogue of indole alkaloids, includingthose of incompletely determined structure, has been published, givingorigin, physical data, and classified references.s1 Chemical and spectro-scopic studies have led to revised structures for C-mavacurine [32; R = H,R' = CH,*OH,+N(b)-Me] and C-fluorocurine (33), and to the formula(32; R = CO,Me, R' = H) for pleiocarpamine.62 Two unsaturated basesfrom Rauwolfia species, deserpideine and raujemidine, have been character-ised as the 19-dehydro-derivatives of deserpidine and reserpine, respectively,6350 D.J. Williams and D. Rogers, Proc. Chem. SOC., 1964, 357.6 7 C. F. Murphy and W. C. Wildman, Tetrahedron Letter8, 1964, 3857, 3863.5 8 H. Hauth and D. Stauffacher, Helv. Chim. Acta, 1964, 47, 185.6o X. M. Laiho and H. M. Fales, J . Amer. Chem. Soc., 1964, 88, 4434.61 &I. Hesse, " Indolalkaloide in Tabellen ", Springer, Berlin, 1964.62 &I. Hesse, W. v. Philipsborn, D. Schumann, G. Spiteller, M. Spiteller-Friedman,W. I. Taylor, H. Schmid, and P. Karrer, Helv. Chim. Acta, 1964, 47, 878.e3 E. Smith, R. S. Jaret, M. Shamma, and R. J. Shine, J . Amer. Chm. SOC., 1964,56, 2083; M. Shamma and R. J. Shine, Tetrahedron Letters, 1964, 2277.A. L. B-arlingame, H. M. Fales, and R. J. Highet, J. Amer. Chm. Soc., 1964,86, 4976HOBSON: ALKALOIDS 403and isovenenatine and venenatine (from Alatonia uenenatct) as the 9-methoxy-derivatives of allo- and 3-epiall0-yohimbine.~~ Previous assignments of theR’(3 4) CHMe \ 4RAcOE t Me Et0-coEt Me(35) (3 6 ) (3 7)stereochemistry of yohimbine and reserpine have been coniirrned by applica-tion of the principles of asymmetric induction,65 and totally syntheticcorynantheine has been obtained by extension of previous work.g6Details have appeared of the determination of the structures and stereo-chemistry of rnacusine-A and -B; it third base from Xtychnos toxqera,macusine-C, has been identified as the N(b)-metho-salt of ak~amrnidine.~7Three new alkaloids from Rauwolfia vomitoria, purpeline (34; R = Me,R’,R“ = 0), mitoridine (34; R = H, R’,R” = 0), and seredamine (34;R = Me, R’ = H, R” = OH), have been characterised by chemical cor-relations and spectroscopic methods.68 Further studies on the oxidationof ajmaline derivatives have been made ; oxidation of 21-deoxyajmalineacetate with lead tetra-acetate resulted in N ( a)-demethylation, giving theindolenine (35), whereas similar treatment of 21 -deoxyajmalone afforded alactone, formulated as (37); the presumed intermediate (36) in this trans-formation was isolated when chromium trioxide-pyridine was used as theoxidant, and was converted into (37) by acid; analogous &oxygenatedproducts were obtained by oxidation of 21-deoxyajmalol-A with lead tetra-a ~ 2 t a t e . ~ ~A new 2-acylindole alkaloid, picraphylline, has been formulated as (38)on the basis of spectroscopic data and its conversion into tetrahydroalstonine(39) by borohydride reduction and acid-catalysed cyclisation to the quater-nary salt (melinonine-A), followed by pyrolytic demethylation.The occur-rence of picraphylline in Picrdiina nitida is interesting in view of Taylor’ssugzestion that the presence in the same plant of melinonine-A [39 ; +X(b)-Me],6 4 T. R. Govindachari, N. Viswanethan, B. R. Pai, and T. S. Savitri, Tetrahedron65Y. Ban and 0. Yonemitsu, Tetrahedron, 1964, 20, 2877.66 E. E. van Tamelen and I. G. Wright, Tetrahedron Letters, 1964, 295.67 A. R. Battersby and D. A. Yeowell, J . Chem. Soc., 1964, 4419.88 J. Poisson, P, R. Ulshafer, L. F. Pasxek, and W. I. Taylor, Bull. SOC. chim.69 M.I?. Bart,lett, B. I?. Lambert, and W. I. Taylor, J . Amer. Chem. Sw., 1964,Letters, 1964, 901.France, 1964, 2683.86, 729404 ORQANIC CHEMISTRYakuammigine (39; epimeric at C-3), and such 7,16-cyclised bases as picralineand pseudoakuammigine is consistent with their derivation from a commonprecursor such as de-N(b)-methylpicraphylline. 70 A laboratory method foreffecting cleavage of the C-S,N(b)-bond of indole alkaloids has been illustratedby the conversion of dihydrocorynantheic acid into the lactam (40) withQ$H H... ... Me ox(& H H'" H'" ..-H ... Me OyJ. AcO '-- CH-OMe EtMeOzC \ 0 Me02C \ 0(38) (3 9) (40) 07q o;& H0.H2C 'OZi*le oT5\ \....*. I l E' N N I 7 1 N- A' N \N O(4 I > (42) Me02C ' (43)\acetic anhydride.71 The structure of vobasine (41; R = H, R' = Me,R" = C0,Me) has been confirmed by X-ray analysis; '2 its absolute configura-tion follows from chemical correlations.73 Other new 2-acylindole basesrelated to the sarpagine group are ochropamine and ochropine, respectivelyformulated as N(a)-methylvobasine (41 ; R = R' = Me, R" = C0,Me) anditsll-methoxy-derivative,74 affinine (41; R = H, R' = Me, R" = CH,mOH),75and perivine (41; R = R' = H, R" = CO,Me).76New additions t o the class of indole bases having a 7,16-bond includeburnamine (deacetylpicraline), from Hunteriu e burnea, 77 and aspidodasy-carpine, from Aspidosperm dasycarpon, a type not encountered before inAspidospermu species. Spectroscopic and chemical evidence including theconversion of its ON-diacetyl derivative into the indole (43), support theassignment of structure (42) to the latter base; confhmation by a directcorrelation between it and picraline has been obtained.78Dependence of the rate of methiodide formation on the configuration ofthe ethyl side-chain has been observed in a series of ibogamine-type ba~es.7~7 0 J.LBvy, G. Ledouble, J. Le Men, and M.-M. Janot, Bull. SOC. chim. France,1964, 1917.71 L. J. Dolby and S. I. Sakai, J . Amer. Chem. SOC., 1964, 86, 1890.79 H. Jagger and U. Renner, Chimia (Switz.), 1964, 18, 173.T 8 G. Buchi, R. E. Manning, and S. A. Monti, J . Amer. Chem. SOC., 1964, 86, 463174 B. Douglas, J. L. Kirkpatrick, B. P. Moore, and J. A. Weisbach, Austral. J .75M. P . Cava, S. K. Talapatra, J.A. Weisbach, B. Douglas, R. F. Raffauf, and7 * M. Gorman and J. Sweeny, Tetrahedron Letters, 1964, 3105.7 7 W. I. Taylor, M. F. Bartlett, L. Olivier, J. L6vy, and J. Le Men, Bull. Soc. chim.7sM. Oh&, J. A. Joule, and C. Djerassi, Tetrahedron Letters, 1964, 3899.?@ M. Shamma and H. E. Soyster, Ezperientia, 1964, 20, 36.(see p. 4636).Chem., 1964, 17, 246.0. Ribeiro, Chem. und Ind., 1964, 1193.Frunce, 1964, 392HOBSON: ALKALOIDS 405Oxidation of dihydrocleavarnine (44; R = H) and the ester (44; R = Co,Me)by mercuric acetate has provided laboratory analogies for a key cyclisationin current theories of the biogenesis of these alkaloids. Thus, from theester (44; R = C o p e ) was obtained a mixture of coronaridine (45; R = Et,R' = H) and dihydrocatharanthine (45; R = H, R' = Et), together withthe unsaturated ester (46);SO no natural base, however, has yet been isolated;49Ec - 03Et \ /\ N(47) (48)bearing the C,-side-chain at C-7.A similar cycliaation, by controlledpermanganate oxidation of ( - )-quebrachamine (47) to ( +)-1,2-dehydro-aspidospermidine (48) has been achieved.81The stereochemistry of haplocine (49; R = H,) and related bases hasbeen established by chemical correlation with palosine ; 82 oxidation ofhaplocine with chromium trioxide-pyridine gave cimicine (49; R = 0),which has been isolated, together with its 16-methoxy-derivative, cimicidine,from Huplophyton cimicidum. 83 Four related compounds, obscurinervineco E t(50) (5 1)H (4 9 )(50; R = Et) and obscurinervidine (50; R = Me) and their 6,7-dihydro-derivatives, having the novel feature of an additional dihydro-l,4-oxazinering, have been isolated.Their structures, determined largely by spectro-scopic methods, were confirmed by synthesis of the dihydro-compounds fromdepropionylaspidoalbine and the corresponding 2-iodo-carbinols.s4 The80 J. P. Kutney and E. Piers, J . Amer. Chem. SOC., 1964, 86, 953; J. P. Kutney,B. W. Bycroft, D. Schumann, M. B. Patel, and H. Schmid, Helv. Chirn. Ada,a 2 M. P. Cava, K. Nomura, and S. K. Talapatra, Tetrahedron, 1964, 20, 581.S3 M. P. Cava, S. K. Talapatra, P. Yates, M. Rosenberger, A. G. Szabo, B. Douglas,R. T. Brown, and E. Piers, ibid., pp. 2286, 2287.1964, 47, 1147.R. F. Raffauf, E. C. Shoop, and J.A. Weisbach, Chem. and Ind., 1963, 1875.K. S. Brown and C. Djerassi, J . Amer. Chem. SOC., 1964 86, 2451406 ORGANIC CHEMISTRYepoxide structure (51) has been proposed for the Vinca alkaloid, lochnericine,and its 16-methouy-derivative, lochnerinine.85The complete structures have been deduced of vinblastine (52; R = Me)and vincristine (52; R = CHO),ss the anti-tumour properties of which havestimulated wide interest in alkaloids of Vinca rosea and related species;*'corroboration has been obtained for these structures by high-resolutionmass Details have now been reported of the elucidationof the structures of the Voacanga bis-indole alkaloids, voacamine [53 ;R = (54)] and voacorine.89 While acid-cleavage of voacamine liberatedvoacangine (53 ; R = H), the vobasinyl(54) portion was destroyed, necessitat-ing its identification in situ by n.m.r. and mass-spectroscopic studies.Con-firmation was obtained by partial synthesis from vobasinol and voacangineby acid-catdysed condensation. Voacorine was analogously derived fromvoacangarine (53 ; Et replaced by CHMe*OH) and vobasinol. Voacamidine[53; R = H, vobasinyl (54) at (2-111, and the isomeric bases conodurine andconoduramine, isolated from Voacanga africana, have been similarlycharacterised and obtained by partial synthesis.89,mN(52) X = C02Me HO C 02MeThe mass spectrum of uleine has been studied in detail,91 and the structuresof five new alkaloids of this type isolated from Aspidosperma dasycarponhave been determined by spectroscopic methods.92 Three novel bases fromVaZEesia dichotoma are (-)-apparacine (55; R,R' = 0), vallesa.mine (55;85 B.K. Moza, J. Trojhek, A. K. Bose, K. G. Das, and P. Funke, Tetra7aedron88 N. Neuss, BE. Gorman, W. Hargrove, N. J. Cone, K. Biemann, G. Biichi, andN. Keuss, I. S. Johnson, J. C. Armstrong, and C. J. Jansen, The Vinca, Alkaloids,88 P. Bommer, W. McMurray, and K. Biemann, J . Amer. Chem. SOC., 1964, $8,8 9 Ref. 73, p. 4631.$0 U. Renner and H. Fritz, Tetrahedron Letters, 1964, 283.O1 J. A. Joule and C. Djerassi, J . Chem. SOC., 1964, 2777.s 2 M. Ohashi, J. A. Joule, B. Gilbert, ar,d C. Djerassi, Experientia, 1964, 20, 363.Letters, 1964, 2561.R. E. Manning, J . Arner. Chem. SOC., 1964, $6, 1440.Adv. Chemotherapy, 1964, 1, 133.1439HOBSON: ALKALOIDS 407R = C02Me, R' = CH2*OH) and its O-acetyl derivativeYg3 possibly originat-ing biogenetically from a uleine-type precursor by cleavage a t the indole@-position and subsequent recyclisation involving t,he N ( b)-methyl group.An elegant , biogenetically patterned synthesis of ( &- )-chimonanthine hasbeen achieved by oxidative dimerisation of the iodomagnesium salt ofN( b)-methyltryptamine with ferric chloride.94Steroid Group.-The isolation and characterisation of several 3,20-diaminopregnane bases have been reported,95 and the structure of kurchilinehas been established as 2cx-hydroxy-3~-dimethylaminopregn-5-en-20-one bysynthesis.96 Funtuline, formulated as 3/I,12#?-dihydroxy~onan-5-ene,9~ andthe Kurchi alkaloids, conkurchine (ircheline) and conessidine, now amendedto (56; R = H and Me, respectively), have been prepared by padial synthesisfrom h0larrhenine.~8 Kurcholessine, also from Hokrrhena antidysenterica,has been assigned the constitution (57) on the basis of spectroscopic evidence.ggFurther studies of alkaloids of Buxus species have resulted in the isolationof additional cyclopropane-containing steroid bases,lO* including the cyclo-microphyllines-A, -B, and -C, correlated with cyclobuxine through a commonL .MeM ~ H NH (58)degradation product.101 Buxenine-G, a novel B-homo-steroid, has beenassigned the structure (58), with the alternative A1(ll)~B-diene formulationalso a possibility. lo2B8 A. Walser and C. Djerassi, Helu. Chim. Acta, 1964, 47, 2072.B p A.I. Scott, F. McCapra, and R. S. Hall, J. Amer. Chern. SOC., 1964, 86, 302.B6 M. Tomita, S. Uyeo, and T. Kikuchi, Tetrahedron Letters, 1964, 1053, 1641;T. Kikuchi, S. Uyeo, M. Ando, and A. Yamamoto, ibid., p. 1817; J. M. Kohli, A. Zaman,and A. R. Kidwai, ibid., p. 3309; W. F. Knack and T. A. Geissman, ibid., p. 1381.06 M.-M. Janot, P. Longevialle, R. Goutarel, and C. Conveur, Bull. SOC. chim.France, 1964, 2158.97 M.-M. Janot, Q. Khuong-Huu, J. Yassi, and R. Goutarel, Bull. SOC. chim. France,1964, 787.s8 Q. Khuong-Huu, L. Labler, Minh Truong-Ho, and R. Goutarel, Bull. SOC. ch6n.France, 1964, 1664.B B R. Tschesche, W. Meise, and G. Snatzke, Tetrahedron Letters, 1964, 1659.100 K. S. Brown and S. M. Kupchan, Tetrahedron Letters, 1964, 2895.101 T.Nakano and S. Terao, Tetrahedron Letters, 1964, 1035, 1045; T. Nakano and102 K. S. Brown and S. M. Kupchnn, Tetrahedron Letters, 1964, 3146.M. Hasegawa, ibid., p. 3679408 ORGANIC CHEMISTRYThe synthesis of solasodine has been accomplishedlO3 by an extensionof previous work on the elaboration of Solanurn bases from pregn-5-enederivatives. O4Lycopodium Group.-Reaction of the lactam (59), obtained by per-manganate oxidation of lycopodine, with lead tetra-acetate has yielded the7,14-epoxy-derivative (60). Ring cleavage of this ether with boron tri-fluoride and acetic anhydride, followed by hydroboronation of the resultingAl3-oleh, gave directly the alcohol (61; R = OH, R' = H), from whichO-acetylannofoline (61; R,R' = 0) was obtained by oxidation.lo5 As aresult of n.m.r.and mass-spectroscopic studies, lyconnotine has been assignedthe diene structure (62),lo6 for which additional evidence has been providedby the synthesis of its derivative (63): vigorous reaction of sn-anisidinewith 1 -bromo-3-chloropropane gave the phenol (64) which was convertedinto (63) by the stages indicated.lo7 The structure (65), having a closeMe COzMe Me??IoMe(62) (43)$4co 0 (+XJOH(44) $ (65)Reagents: 1, Raney Ni-H,. 2, MeI. 3, Me,CH*CH,Li. 4, H+. 5, LiAlH,.Io8 K. Schreiber, A. Walther, and H. Rcnsch, Tetrahedron, 1964, 20, 1939.104 K. schreiber and G. Adam, Tetrahedron, 1964, 20, 1707.105 W. A. Ayer, D. A. Law, and K. Piers, Tetrahedron Letter$, 1964, 2959.106 F. A. L. Anet, M. Z.Haq, N. H. Khan, W. A. Ayer, R. Hayatsu, S. Valverde-Lopez, P. Deslongchamps, W. Riess, M. Ternbah, Z . Valenta, and K. Wiesner, Tetra-hedron Letters, 1964, 751.10' Z. Valenta, P. Deslongchamps, R. A. Ellison, and K. Wiesner, J. Amer. Chem.SOC., 1964, 86, 2533HOBSON: ALKALOIDS 409relationship to that of lyconnotine, has been put forward as consistent withthe observed chemical and spectroscopic properties of annotine.lo8Terpene Alkaloids.-Widespread efforts to achieve the synthesis of diter-pene alkaloids have culminated in some notable successes during the yearunder review. A key intermediate in the previously reported,* synthesisof atisine has been transformed stereospecifically into the ketone (67;R = MeSO,, R' = HJ, and thence into the compound (68), from whichgarryine and veatchine are obtainable by known methods.log In anotherapproach, the tetracyclic ketone (66; R = OMe) (also available from veat-chine by degradation) was synthesised, the nitrogen-containing bridge beingintroduced subsequently by ultraviolet irradiation of the azide (66; R = N3)." COzHReduction of the ethylene ketal of the product (67; R = H, R' = 0) bylithium aluminium hydride gave the same intermediate (67; R = H,R'= H,) as was used in the fist synthesis, which was also converted,though by a different route, into (68).A multi-stage conversion of thelatter into the dicarboxylic acid (69), from which atisine has already beenobtained, completes the formal synthesis of all three alkaloids.110 Independ-ently, Wiesner and his colleagues have also developed a synthetic route tothe pentacyclic ketone (67; R = Ac, R' = H2).111The structure of the lactonic alkaloid heteratisine has been establishedby X-ray crystallography as (7O),ll2 in accord with independent interpreta-tions of infrared and n.m.r.data of the base and its transformationproducts.l13Miscellaneous.-Two novel bases, nobiline (71) and dendrobine (72), ap-parently closely related to picrotoxinin, have been isolated from DendrobiumIo8 W. A. Szarek, K. A.. H. Adams, M. hcumelli-Rodostano, and D. B. MacLean,loB W. Nagata, M. Narisadrt, T. Wakabayashi, and T. Sugastbwa, J . Amer. Chem.111 Z. Valenta, K. Wiesner, and C. M. Wong, Tetrahedron Letters, 1964, 2437.l12M. Przybylska, Canad. J.Chem., 1963, 41, 2911.llS 0. E. Edwards and C. Ferrari, Canad. J . Chem., 1964, 42, 172; R. Aneja andCanad. J . Chem., 1964, 42, 2585.SOC., 1964, 86, 929.S. Masamune, J . Amer. Chem. Soc., 1964, 86, 288, 289, 290, 291.S. W. Pelletier, Tetrahedron Letters, 1964, 669410 ORGANIC CHEMISTRYnobile, their structures being deduced from chemical and spectroscopicdata. The relative configuration of dendrobine follows from the readyformation of an internal quaternary salt by the derived diol (73), and thefact that the isopropyl group occupies the thermodynamically more stableconfiguration in the corresponding y-leto-ester, in which the six-memberedring takes up the boat conformation. Assignment of the absolute configura-H HCH2. OH1(71)Pr i Pri(73)(74) (75) (76)tion was made by application of the lact'one and octant rules, and coincideswith that of picrotoxinin.l14 The structure and absolute configuration ofsecurinine has been confirmed by X-ray ana1ysis,ll5 and other related baseshave been isolated.ll* Halfordine, from HaEfordia.scleroxyla (Rutaceae),has been shown to be the oxazole derivative (74);l17 and from a comparisonof the mass spectra of thiobinupharidine and neothiobinupharidine withthat of deoxynupharidine, it has been concluded that the two former basesare stereoisomers (75).llS The absolute stereochemistry of the aromaticerythrina alkaloids and the erythroidines, all having the same configurationat the spiro-carbon atom, have been determined,llg and a total synthesis oferysotrine (76), the completely methylated derivative of the natural phenolicbases, has been accomplished.120114 S.Yamamura and Y. Hirata, Tetrahedron Letters, 1964, 79; Y. Inubushi,Y. Sasaki, Y. Tsuda, B. Yasui, T. Konita, J. Matsumoto, E. Katarao, and J. Nakano,Tetrahedron, 1964, 20, 2007; Y. Inubushi, E. Katarao, Y. Tsuda, and B. Yasui, Chem.and Ind., 1964, 1689.116s. Imado and M. Shiro, Chem. and Ind., 1964, 1691.116 S. Ssito, T. Iwamoto, T. Tanaka, C. Matsumura, N. Sugimoto, Z. Horii, andY. Tamura, Chem. and Ind., 1964, 1263.117 W. D. Crow and J. H. Hodgkin, AuJral. J . Chem., 1964, 17, 119.118 0. Achmatowicz, H. Banazek, G. Spiteller, and J. T. Wr6be1, Tetrahedron Letters,1964, 927.119 V. Boekelheide and M. Y. Chang, J .Org. Chem., 1964, 29, 1303; V. Boekelheideand G. R. Wenziger, ibid., 1964, 29, 1307; U. Weiss and H. Zeffer, Experientia, 1963,19, 660.1 2 o A . Mondon and H. J. Nestler, Angew. Chern., 1964, 76, 65111. STEROIDSBy J. S. Whitehurst(Department of Chemistry, The University, Exeter)A B o o K on nuclear magnetic resonance spect'roscopy with special referenceto steroids has been published.1Physical Mea,surements.-2a- and 2p-Isopropyl and 2a- and 2p-t-butyl-cholestan-3-ones have been synthesised,2s and in each case at equilibriumabout 95y0 of the a-compounds are present. The conformation of ring Ain the 2p-t-butyl compound is thought to be the twist form * (1) (C-3,C-10'' points " 5 , of the C-2,C-5(prow-stern) boat. The rotatory contributionI '2+66 7 HRTd Heq$-H a , R(1) (2) (3)[optical rotatory dispersion (o.r.d.)] of an equatorially oriented t-butyl groupadjacent to a carbonyl group in a cyclohexane ring (chair conformation) isestimated to be 33-39 units of amplitude.For an isopropyl group it is15-41 units and for a methyl group about 9 units.6 The energy differencebetween conformers bearing axial and equatorial isopropyl groups adjacentto carbonyl groups is almost certainly less than 1 kcal./mole.2pCircular dichroism (c.d.1 measurements * on steroid ketones at -192"reveal that the vibrational fine structure developed is fairly specific for thelocation of the carbonyl group and is thus analogous to the backgroundrotational effects in 0.r.d. The ll-carbonyl group is particularly easy todetect.Similar low-temperature measurements of the ultraviolet absorptionspectrum for the n+n* transition are not as useful. The reversal of thec.d. curve for 5a-androstan-ll-one found earlier 9 is not general 10 for otherll-keto-compounds, but the curves do change in the direction expected fort'he formal enantiomer. It is considered10 that the change is broughtN. S. Bhacca and D. H. Williams, " Applications of NMR Spectroscopy inOrganic Chemistry ", Holden-Day Press, San Francisco, 1964.C. Djerassi, P. A. Hart, and C. Beard. J. Anzer. C,5em. SOC., 1964, 86, 85.C. Djerassi, I?. A. Hart, and E. J. Wamwara, J . Amer. Chem. SOC., 1964, 86, 78.W. S. Johnson, V. J. Bauer, J. L. Blnrgrzve, &I. A. Frisch, L. H. Dreger, andC . Djerassi and W.Klyne, Proc. Nut. Acad. Sci. U.S.A., 1962, 48, 1093.C . Beard, C. Djerassi, J. Sicher, F. &PO&, and M. Tichf, Tetrahedron, 1963,N. L. Allinger and H. M. Blatter, J . -4mer. Chem. SOC., 1961,83, 994; B. Rickborn,K. M. Wellman, R. Records, E. Bunnenberg, and C . Djerassi, J . Amer. Chem.* K. M. Wellman, E. Bunnenberg, and C. Djerassi, J . Amer. Chem. SOC., 1963,W. N. Hubbard, J . Amer. Chem. Soc., 1981, 83, 606.19, 919.ibid., 1962, 84, 2414.SOC., 1964, 86, 492.85, 1870.lo G. Snatzke and D. Becher, Tetrahedron, 1964, 20, 1921.412 ORGANIC CHEMISTRYabout by a conformational change, not in ring A but in ring c, the oxygenatom of the carbonyl group presumably taking up a position below themedian plane of ring c l1 at room temperature.In the c.d. curves inversionis found lo in 5a-A2-1 -keto-steroids and also in 7a-chloro-7~-nitro-5a-choles-tane.12 Studies of 0.r.d. and c.d. have been carried out on pregnanones, 13, 14steroidal N-phthal~ylamines,~~ and aromatic conjugated ketones ; l 6 and areview l 7 has appeared.The coupling constant of axial and equatorial protons has the normalvalue (5.5 & 1.0 c./sec.) in the system (2; R = OH or OAc), but in (3) itis much reduced (2-5-3.2 c./sec.), a finding of considerable importance.For the proton sharing the substituted carbon atom in systems such as (2)and (3), the half-width of the band due to that proton is 5-10 c./sec. if it isequatorial and 15-30 c./sec. if it is a ~ i a l . 1 ~ Often, visual inspection of thespectrum is sufficient to make a decision.The orientation of the cyano-groups in a pair of epimers can be decided20 by measuring the extinctioncoefficient of the C=N stretching band in the infrared spectrum, that for theequatorial isomer always being the greater. Often the stretching frequencyfor the equatorial isomer is higher also.Unlike the fragmentationpattern of saturated ketones, that of unsaturated ketones, steroid amines,and ethylene ketals is fairly characteristic. Deuterium exchange with aA1-3-ketone occurs at the 2-, 4a-, and 4p-positions only. In saturated11 Ring c cannot beoome a formal C-l1,C-14 boat because of the trans-B/c junction;a C-8,C-12 boat is equally impossible because of the trans-c/D junction.l2 G. Snatzke, D.Becher, and J. R. Bull, Tetrahedron, 1964, 20, 2443.lS G. Snatzke, H. Pieper, and R. Tschesche, Tetrahedron, 1964, 20, 107.l4 P. CrabbB, F. McCapra, F. Comer, and A. I. Scott, Tetrahedron, 1964, 20, 2455.l5 H. Wolf, E. Bunnenberg, and C . Djerassi, Chem. Ber., 1964, 97, 533.l* R. C. Cambie, L. N. Mander, A. K. Bose, and M. S . Mmhas, Tetrahedron, 1964,1'P. CrabbB, Tetrahedron, 1964, 20, 1211.18 D. H. Williams and N. S . Bhacca, J . Amer. Chem. SOC., 1964, 86, 2742; ref. 1,Mass spectrometry continues to flourish.21-3220, 409.pp. 81, 135.1964, 3133.1964, 86, 269.SOC., 1964, 06, 2623.and C. Djerassi, J . Amer. Chem. SOC., 1964, 86, 2532.A. Hassner and C. Heathcock, J . Org. Chem., 1964, 29, 1350.2o W. Nagata, M. Yoshioka, M. Narisada, and H.Watanabe, Tetrahedron Letters,$1 C . Beard, J. M. Wilson, H. Budzikiewicz, and C . Djerassi, J . Amer. Chern. SOC.,22 H. Powell, D. H. Williams, K. Budzikiewicz, and C . Djerassj, J . Amer. Chem.2s R. Beugelmans, R. H. Shapiro, L. J. Durham, D. H. Williams, H. Budzikiewicz,2 4 R . H. Shapiro and C . Djerassi, J . Acmer. Chem. SOC., 1964, 86, 2825.2 5 R. H. Shapiro, D. H. Williams, H. Budzikiewicz, and C. Djerassi, J . Amer.26 Z. Pelah, D. H. Williams, H. Budzikiewicz, and C. Djerassi, J . Amer. Chem.17 H. Audier, J. Bottin, A. Diara, M. Ft?tizon, P. Foy, M. Golfier, and W. Vetter,28 N. S. Wulfson, V. I. Zaretskii, V. G. Zaikin, G. M. Segal, I. V. Torgov, and29R. H. Shapiro and C. Djerassi, Tetrahedron, 1964, 20, 1987.8 0 H. Budzikiewicz, Tetrahedron, 1964, 20, 2267.81 M.von Ardenne, K. Steinfelder, R. Tiimmler, and K. Schreiber, Experientia,1963,19,178; M. von Ardenne, R. Tiimmler, E. Weiss, and T. Reichstein, HeZv. Chim.Acta, 1964, 47, 1032.82 H. Audier, M. FBtizon, and W. Vetter, Bull. SOC. chirn. France, 1964, 415.Chem. SOC., 1964, 86, 2537.SOC., 1964, 86, 3722.Bull. SOC. chim. France, 1964, 2292,.T. P. Fradkina, Tetrahedron Letters, 1964, 3015WHITEHURST 1 STEROIDS 4135a-androstan-7-ones two deuterium atoms can be introduced 23 at (3-6 beforethe third a t C-8 (cf. the ll-CO group). Enolisation of a A*-3-ketone understrongly basic or weakly acidic conditions involves33 prior loss of the Zp-proton ; the thermodynamically stable enol is, of course, the A3,5-compound.Electron spin resonance is already 34 making its contribution to the studyof ring conformation.B-Nor-steroids.-Since the carbonyl group in 6-keto-~-nor-steroids isadjacent to two bridgehead carbon atoms four configurations are possibleand three of these, vix., SccSP-, SB,Sp- and 5/3,8a-, are kn0wn.~~9 36 Mildacid-treatment or, better, chromatography on neutral alumina 35 of the5a,Sb-compounds (4) brings about epimerisation at C-5 alone (5).In these5~,8#l-compounds ring A is usually a (twist) boat. The 5p,8p-ketonesundergo further epimerisation in alkaline solution to the 5/3,8a-isomers(6) (ring A invariably a boat) except when C-3 is a carbonyl group in whichcase the 5&8b-configuration is stable. The changes, 5% --+ 5/3 and 8/3 --+ 8a,are accompanied by marked l~vorotation.~~ The 6-carbonyl group in the5,!l,8%-series is extremely unrea~tive.~~ However, reduction can be broughtabout with lithium aluminium hydride 36 and yields 6@-hydroxy-5/3,8cc-compounds.The 65-hydroxyl group is not a ~ y l a b l e , ~ ~ in contrast 35 to the6%-group in the same 5~,8cc-~tereochemical series. In 3p,6p-dihydroxy-5p,8cc-compounds the 6p-hydroxyl group can be preferentially oxidised withchromic acid.General Reactions.--Rings A and B. The epimeric sulphoxides (7 and8 ; R as for cholesterol) behave 37 differeatly when heated, the former yieldingexclusively the A4-olefin and the latt,er mainly the As-isomer. The fluoro-hydrin (9) reacts with acetic anhydride-perchloric acid to yield 38 in part the33 S.K. Malhotra and H. J. Ringold, J . Amer. Chem. Soc., 1964, 86, 1997.34 G. A. Russell and E. T. Strom, J . Amer. Chem. Soc., 1964, 86, 744; 0. A. Russell35 J. Fajkog, J. Joska, and F. Born, Coll. Czech. Chem. Comm., 1964, 29, 652 and36 Y. Morisawa, Chem. and Pham. Bull. (Japan), 1964,12,1060, 1066; Y. Morisawa,38 J. W. Blunt, M. P. Hartshorn, and D. N. Kirk, J. Chem. Soc., 1964, 1073.and E. R. TaIaty, ibid., p. 5345.previous articles.Y. Kishida, and K. Tanabe, ibid., 1963, 11, 686.D. N. Jones and M. A. Saeed, Proc. Chem. Soc., 1964, 81414 ORGANIC CHEMISTRYperchlorate of the ion (10). 4,5-Epoxy-3-ketones react with methanol andthe boron trifluoride-ether complex to give,39 surprisingly, their 3-dimethylketals in which the oxide ring is stable to lithium aluminium hydride. InAcO(9)IMe (10)general, the reaction of 4,5-epoxy-4-methyl compounds in the cholesterolseries with boron trifluoride-ether yields complex mixtures.40 3p-Acetoxy-4~,5-epoxides with Grignard reagents furnish 4@-alkyl-3/?-hydroxy-5a-steroids,4l offering a means of monoalkylation at (2-4.Use of vinylmag-nesium bromide, followed by oxidation and epoxidation, yields the compound(11) 42 which with boron trifluoride gives the furan (12), structurally relatedto a number of natural products. Treatment 43 of the @-epoxide (13) withpolyphosphoric acid in acetic acid yields as sole and abnormal product thecompound (14). With both cx- and 6-oxides ethanethiol yields 4-ethylthio-A4-3-0nes.~3, 44 The compound (15) with methylmagnesium iodide givesthe two epimers (16) and a little of the compound (17).45 Al-3-Ketones withs9 D.J. Collins and J. J. Hobbs, Chem. and Ind., 1964, 1063.40 J. M. Coxon, M. P. Hartshorn, and D. N. Kirk, Tetrahedron, 1964, 20, 2531,2547.*l S. Julia, B. Decouvelaere, J.-P. Lavaux, C. Montonnier, and P. Simon, Bull.SOC. chim. France, 1963, 1221, 1223; S. Julia and C. Montonnier, Bull. SOC. chim. France,1964, 321, 331.S. Julia and C. Montonnier, BuZl. SOC. chim. France, 1964, 979.4* M. Tomoeda, M. Ishizaki, H. Kobayashi, S. Kanatomo, T. Koga, M. Inuzuka,and T. Furata, Chem. and Pharm. Bull. (Japafh), 1964, 12, 383.4 4 M. Tomoeda, M. Inuzuka, and T. Furata, Tetrahedron Letters, 1964, 1233;J. 31. KrBmer, K. Briickner, K. Irmscher, and K.-H.Bork, Chem. Ber., 1963, 96, 2803.45 P. N. Rao and J. C. Uroda, Tetrahedron Letters, 1964, 1117; B. G. Christensen,R. G. Strachan, N. R. Trenner, B. H. Arison, R. Hirschmann, and J. M. Chemerda,J . Anaer. Chem. SOC., 1960, 82, 3995WHITEHURST : STEROIDS 415diazomet,hane in the presence of aluminium chloride undergo expansion 46of ring A. Normal addition 47 yields pymzolines (18), which by heat or onadsorption undergo rearrangement to Al-l-methyl compounds (19) and,as minor product, la,2-cyclopropane-ketones (20). A1,496-3-Ketones, onthe other hand, give isomeric pyrazolines of structure (18a) which, whenheated, give mainly the cyclopropane-ketones (20 ; A4s6). Al-3-Ketones inboth the 5a- and the 5p-series undergo conjugate addition of methyl-Grignardreagent to give la-methyl compounds.48H(18) (18a) (19) (20)Acid-catalysed cyclopropane ring fission 49 of compounds (21; R' = Meor Ph) proceeds according to Markownikow's rule, giving 2-methyl-A2-enes.Solvolysis 5 0 of the A-nor-steroid (22) follows a path almost identical withthat of cholesteryl toluene-p-sulphonate, whereas the 3-epimer of (22) yieldsas the principal compound (23).3x-Hydroxy-5cc-steroids are 51 nowreadily available by hydroboronation of A3-5a-compounds, themselves avail-able from A4-3-ones. A study 52 of the hydroboronation of steroid monoenesand dienes has shown that, in general, attack of the reagent occurs from thecc-face and that with disubstituted monoenes (e.g., A2) both positional isomersare formed (cf.A3; ref. 51). The A9(11)-bond is inert in 5p- 53 but not in5a-compo~nds.~~ The boron trifluoride-ether complex in acetic anhydridereacts with 3-keto-5a-steroids 54 and their ketals 55 to introduce an acetylgroup at position 2. The Vilsmeier reagent readily introduces an aldehydegroup into en01 ether~,~G ethylene ketals,57 and pyrrolidine enamines.5846 E. Miiller, B. Zeeh, and R. Heischkel, Annalen, 1964, 67'7, 47.47 R. MTiechert, 2. Naturforsch., 1964, 19b, 945.48 W. J. Wechter, J. Org. Chem., 1964, 29, 163; H. Mori, Chem. and Pharsn. Bull.49 R. C. Cookson, D. P. G. Hamon, and J. Hudec, J . Chem. SOC., 1963, 5782.(2. H. Whitham and J. A. F. Wickramasinghe, J . Chem. Soc., 1964, 1655.51 L. Cagliotti, G. Cainelli, G. Maine, and A.Selva, Tetrahedron, 1964, 20, 957;6 a M. Nussim, Y. Mazur, and F. Sondheimer, J . Org. Chem., 1964, 29, 1120.64 G. I. Fujimoto and R. W. Ledeen, J . Org. Chem., 1964, 29, 2059.66 R. D. Youssefyeh, J . Amer. Chem. SOC., 1963, 85, 3901.66 D. Burn, G. Cooley, J. W. Ducker, B. Ellis, D. N. Kirk, and V. Petrow, Tetra-6 7 R. D. Youssefyeh, Tetrahedron Letters, 1964, 2161.6 8 R. Sciaky and U. Pellini, Tetrahedron Letters, 1964, 1839.(Japan), 1962, 10, 386.Gazzetta, 1962, 92, 309.W. J. Wechter, Chem. and Ind., 1959, 294.hedron Letters, 1964, 733416 ORGANIC CHEMISTRYThe carbonyl group must be protected,58 otherwise chlorine is introduced.In the case of A3s5-enol ethers,59 the aldehyde group enters at position 6and can be transformed into a methyl group.The action of boron trifluoride-acetic anhydride on A3s5-3-enol acetates furnishes 6-acetyl- and 2,6-diacetyl-A4-3-ket ones. 60In the reaction between A4-3-hydroxy-steroids and 2,3-dichloro-5,6-dicyano-l,4-benzoquinone, equatorial alcohols 61 are oxidised faster thanaxial ones, the kinetics suggesting a slow hydride transfer followed by rapidproton loss. The same reagents acting on 3-ethoxy-A3a5-dienes in aqueousacetone yield A4r6-dien-3-ones, but in anhydrous acetone or benzene yieldA1,4s6-trien-3-ones. 62 Potassium t-butoxide in dimethyl sulphoxide is asufficiently strong base to deconjugate the A4-bond in A1y4-diene-3-ket0nes.6~The action of hydriodic acid on ring A diosphenols furnishes 64 saturatedketones ; the benzilic acid rearrangement of one such ketone proceededstereospecifically.65 l/Nyanocholestan-3-one is isomerised by mild ethan-olic potassium hydroxide to the la-epimer.6g With the same reagent the1-methyl compound (24; R as for androstan-17#l-ol) undergoes a retroaldolchange to produce a mixture of the original compound and the isomer (25).67The 19-nor derivative of (24) undergoes a similar change.The 19-nor compound (26) has been converted into androst-4-ene-3,17-dione by addition of dibromocarbene to the double bond, followed by reduc-tion and ring opening.68 Epoxidation 69 of the A5(10)-bond of the diketoneparent of compound (26) also occurs from the #l-face and, after reduction ofthe carbonyl groups, either acid-hydrolysis or the action of methyl-Grignardreagent yields l0~-hydroxy-5a-compounds.or-Epoxides in this system canbe formed by addition of hypobromous acid (lO/?-brorno-5a-hydroxy) at69 D. Burn, Gr. Cooley, M. T. Davies, J. W. Ducker, B. Ellis, P. Feather, A. K.Hiscock, D. N. Kirk, A. P. Leftwick, V. Petrow, and D. M. Williamson, Tetrahedron,1964, 20, 597.R. Youssefyeh, M. Gorodetsky, E. Levy, and Y. Mazur, I.U.P.A.C. Congress,1963, Abstract A, 341; B. C. Elmes, M. P. Hartshorn, and D. N. Kirk, J . Chern. Soc.,1964, 2285.61 S. H. Burstein and H. J. Ringold, J . Amer. Chem. SOC., 1964, 86, 4952.62 S. K. Pradhan and H. J. Ringold, J . Org. Chern., 1964, 29, 601.ea E. L. Shapiro, T. Legatt, L. Weber, and E. P. Oliveto, Steroids, 1964, 3, 183;H. J. Ringold and S. K. Malhotra, Tetrahedron Letters, 1962, 669.64 W.Reusch and R. Le Mahieu, J. Amer. Chem. SOC., 1964, 86, 3068.66H. R. Nace and D. H. Nelmder, J . Org. Chem., 1964, 29, 1677.66A. T. Glen and J. McLean, Tetrahedron Letters, 1964, 1387.6 7 F. Bohlmann and C. Rufer, Chem. Ber., 1964, 97, 1770.68 A. J. Birch, J. M. Brown, and G. S. R. Subba Rao, J . Chem. SOC., 1964, 3309.6g A. D. Cross, E. Denot, R. Acevedo, R. Urquizza, and A. Bowers, J . Org. Chem.,1964, 29, 2195WHITEHURST : STEROIDS 417the 5,lO-bond and treatment with base. Solvolysis 70 of the toluene-p-adphonate of the alcohol (27) yields a mixture of dienes, the epimeric alcohol,0and the IO#l-hydroxy-30c,5-cyclo-steroid (28). The 3-epimer of compound(27) gave the same diene mixture, compound (27), and a 3#l,5-cyclo-steroidanalogous to (28), the configuration of the 10-hydroxyl group not yet havingbeen settled.'lLithium and biphenyl in boiling tetrahydrofuran converts the compound(29) into Gestrone in high yield, the methyl group being expelled as its anion ; 72n0 .=-+C02Menone of the B-seco-product (30) appeared to be formed.Treatment ofthe ester (31) (from deoxycholic acid) with zinc and dimethylformamidealso brings about smooth ar0matisation.7~ When compounds such as(32 ; X = halogen, Y = halogen or OH) are treated with dimethylformamide,aromatisation to equilenin derivatives occurs.74 The combiried action ofacetyl bromide and a-bromopropionic acid on androst-4-ene-3,17-dione yieldsthe compound (33). 75 A4-3-Keto-steroids react with phosphorus halidesand other acid halides to form 3-halogen0-A~~~-dienes.7~ A1s4-Dien-3-onesand oxalyl halides give compounds of type (34; X = halogen).777 0 W.F. Johns, J. Org. Chem., 1964, 29, 1490.71 cf. S. G. Levine, N. H. Eudy, andE. C. Farthing, Tetrahedron Lettert?, 1963,1517.H. L. Dryden, G. M. Webber, and J. J. Wieczorek, J . Amer. Chem. Xoc., 1964,86. 742.73 K. Tsuda, S. Nozoe, and K. Ohata, Chem. and Pharm. Ball. (Japan), 1963, 11,1265.l4 M. Heller, R. H. Lenhard, and S. Bernstein, J . Amer. Chem. SOC., 1964, 88,7s J. Schmitt, J. J. Panouse, P. J. Cornu, A. HaUot, H. Pluchet, and P. Comoy,J. A. Ross and M. D. Martz, J . Org. Chem., 1964, 29, 2784 and references there7 7 G. W. Moersch, W. A. Neuklis, T. P. Culbertson, D. F. Morrow, and M.E.2309.Cmpt. Tend., 1964, 259, 1652.cited.Butler, J . Org. Chem., 1964, 29, 249541 8 ORGANIC CHEMISTRYThe compound (35) undergoes normal dienone-phenol-type rearrange-ment to form compounds evidently derived from the intermediate (36).780Esters of structure (37; R' = acyl) undergo rearrangement in trifluoroaceticanhydride to yield the compounds (38) by a 1,2-di~placement.~D WithIR' = alkyl a slower reaction ensues, both the ethers (39) and (40) beingproduced, a finding of some significance in the mechanism of the dienone-phenol rearrangement.Cholesteryl acetate reacts with nitrosyl chloride to give the 6p-nitro-5a-chloro-derivative,80 the reaction being catalysed by nitrogen dioxide ; molarproportions of reactants furnish the nitro-chloride and unchanged material.The Westphalen rearrangement 81 is not found s2# 83 with 5/?-hydroxy-steroids; moreover, even with 5a-hydroxy-steroids it does not occur if thisgroup is alkylated or acetylated.84 A thorough investigation 83 on theoriginal compound (41; R as for cholesterol) has revealed that, besides theAcO @ '' OAc( 4 ' )AcO & OAcAcO(42) OAcAcO4 4)AcO LJ?j OAc(43)(45)'8 R.Villotti, A. Cervantes, and A. D. Cross, J . Chem. SOC., 1964, 3621.'BE. Hecker, Chenz. Ber., 1964, 97, 1940.K. Tanabe and R. Hayashi, Chem. and Pharm. Bull. (Japan), 1962, 10, 1177;W. A. Harrison, Sir Ewart Jones, G. D. Meakins, and P . A. Wilkinson, J . Chem. Soe.,1964, 3210; A. Hassner and C. Heathcock, J . Org. Chem., 1964, 29, 1350.T.Westphalen and A. Windaus, Ber., 1915, 48, 1064; H. Lettre and E. Miiller,Ber., 1937, 70, 1947; V. A. Petrow, J . Chem. SOC., 1937, 1077 and subsequent papers.8aA. T. Rowland, J . Org. Chem., 1964, 29, 222.G. Snatzke and H.-W. Fehlhaber, Annulen, 1964, 676, 188, 203.a4 J. W. Blunt, M. P. Hartshorn, F. W. Jones, and D. N. Kirk, Tetrahedyon Letters,1964, 1399WHITEHURST : STEROIDS 419normal product (as), the compounds (43),85 (44) and (45) are formed.Though the authors s3 invoke a non-classical carbonium ion for this re-arrangement, this does not seem to explain its extreme particularitmy to thenature and stereochemistry of the 6-substituent.Attempts 86 to obtain a A5,7-system in 6- and 7-methyl steroids have sofar proved abortive, trans-dime systems being formed preferentially.Neither the oxidation of 6-methylcholesteryl benzoate nor that of its 7ct-hydroxy-derivative yielded the 7-ketone.86 A5,7-Dienes (46 ; R as forcholesterol, ergosterol) with the normal 9x,lOP-stereochemistry react 87 withmethyl azodicarboxylate to yield the products (47) (cf. maleic anhydride),which on pyrolysis afford the compounds (48) and (49); compound (47;R as for cholesterol), on treatment with acid, undergoes an anthrasteroidrearrangement to give the same products as are formed from 3/3-acetoxy-cholestane-5,7,9( 1 l)-triene,s8 suggesting a common pathway for the tworeactions. Hydrogenation (palladium-calcium carbonate) 89 of the com-pound (50 ; R as for 17~-acetoxyaiidrostane) yields the Ga-hydroxy-com-pound (50; no Br, ~X-OH), which is surprising as the 6~-hydroxy-compoundAcO IHO (50)(50; no Br) is not epimerised under the same conditions.Exposure ofdehydroisoandrosterone to tritium gas gives, by trans-addition to the 5,6-bond, the saturated 6/?,5a-ditritio-cornpo~nd.~~Ring C.-Chromous acetate in dimet,hyl sulphoxide srnoot>hly removes 91the bromine atom from 9a-bromo-1 I/?-hydroxy-compounds [e.g., (a)] in thepresence of a donor of hydrogen radicals (e.g., BunSH). In the absence ofthe thiol, then depending on conditions 5,9-cyclo-steroids (52) or A9W-olehs are produced. Arenesulphonyl chlorides, normally poor reagents forthe dehydration of Ilp-alcohols, become highly effective in the presence of8 5 H. Aebli, C.A. Grob, and E. Schumacher, Helv. Chim. Acta, 1958, 41, 774;V. Petrow, 0. Rosenheim, and W. W. Starling, J. Chem. SOC., 1938, 677.86 R. K. Callow and G. A. Thompson, J. Chem. SOC., 1964, 3106. *' A. van der Gen, 3. Lakeman, M. A. M. P. Gras, and H. 0. Huisman, Tetrahedron,1964, 20, 2521.8 8 K. Tsuda, R. Hayatsu, J. A. Steele, 0. Tanaka, and E. Mosettig, J . Amer.Chem. SOC., 1963, 85, 1126.8D 0. Wintersteiner, M. Moore, and A. J. Cohen, J . Org. Chem., 1964, 29, 1335.S. Baba, H. J. Brodie, M. Hayano, G. Kwass, atnd M. Gut, J. Org. Chem., 1964,29, 2751; K. E. Wilzbach, J. Amer. Chem. Soc., 1957, 79, 1013.91 D. H. R. Barton and N. K. BILSU, Tetrahedron Letters, 1964, 3151; 0. Gnoi,E. P. Oliveto, C. H. Robinson, and D. H. R. Barton, Proc. Chenz. Soc., 1961, 207;J.Fried and E. F. Sabo, J. Amer. Chem. Xoc., 1957, 79, 1130420 ORGANIC CHEMISTRYa trace of sulphur di0xide.~2 5,6-Dihydroergosteryl acetate gives, withbromine, a compound which on chromatography yields a 12-methyl (ring caromatic) ster0id.9~ The somewhat conflicting views g4, g5 on the stabilitiesof 12-hydroxy-steroids possessing an unanchored 17-side-chain may perhapsbe rationalised by the suggestion S5 that reduction of the 12-carbonyl groupby metal-alcohol or metal-ammonia to the dianion is slow relative to thesubsequent protonation.Ring D.-Treatment of the toluene-p-sulphonylhydrazones of 17-ketoneswith sodium borohydride in dioxan brings about complete reduction to17-CH2 compounds,96 and the reaction appears to be general. The cyano-compound (53) is reduced to the corresponding aldehyde by lithium alu-minium hydride in ether, but in tetrahydrofuran it yields a 13-hydroxy-compound.97 A similar reaction involving a la-cyano-group has beenreported.98 trans-Perhydroindan-3a-ylmethylamine (54), when treated withnitrous acid, yields 99 the compound (55) in 74% yield and this reaction hasbeen carried over into steroid chemistry.A15- 17-Ketones react withmethanol in the presence of potassium hydroxide to furnish 15b-methoxy-17-ketones by addition of methanol to the 15,16-b0nd.~~~ 16J7-Diketonesof 13a-configuration (c~s-c/D) are completely enolised.lOl The conversion9 2 G. G. Hazen and D. W. Rosenburg, J . Org. Chem., 1964, 29, 1930.Qa T. N. Margulis, C. F. Hammer, and R. Stevenson, J.Chem. SOC., 1964, 4396.Q 4 M. Alauddin and M. Martin-Smith, J. Org. Chem., 1963, 28, 886.Q6 J. W. Huffman, D. M. Alabran, and T. W. Bethea, J. Org. Chem., 1962, 27,3381; J. W. Huf€man, D. M. Alabran, T. W. Bethea, and A. C. Ruggles, ibid., 1964,29, 2963.96 L. Cagliotti and P. Graselli, Chem. and Ind., 1964, 153; L. Cagliotti and M. Magi,Tetrahedron, 1963, 19, 1127.97 M.-M. Janot, X. Lusinchi, and R. Goutarel, Compt- rend., 1964, 258, 4780.S. Julia, H. Linarks, and P. Simon, Bull. SOC. chim. Frame, 1963, 2471.Qs W. G. Dauben and P. Laugg, Tetrahedron, 1964, 20, 1259.loo W. S. Johnson and W. F. Johns, J. Amer. Chem. SOC., 1957, 79, 2005; E. W.lo1 L. J. Chinn, J . Org. Chem., 1964, 29, 3304.Cantrall, R. Littel, and S.Bernstein, J. Org. Chem., 1964, 29, 64, 214WHITEHURST: STEROIDS 421of ethynyl compounds (56) into D-homo-materials (57) lo2 proceeds by aWagner shift, a t least when R = H. 15-Keto-steroids have been syn-HOthesised.lo3 The C-17 side-chain of eburicoic acid has been degraded lo4 tothat of corticosterone without disturbing tihe nuclear double bond.Intramolecular Radicd Transfers.-The mechanism of the Bartonreaction lo5 (sterically constrained systems) (58) has been studiedcase X- =NO. The low quantum yield indicates the first stepr .X 7 OXin theto be(3Hreversible,l06 and new evidence 107 involving isotope-labelling shows thatthis step occurs within a solvent cage. After the hydrogen-radical t r a d e rthe nitric oxide molecule becomes free.Under unusual conditions, suchas the presence of t-butyl nitrite, even the first step is to some extent un-caged. Other radicals can compete with nitric oxide for the final recom-bination. Thus, the photolysis of nitrites, in the presence of iodine orbromotrichloromethane, yields iodohydrins or bromohydrins (58 ; X = Ior Br).10* Mercuric oxide-iodine (with illumination) 109 is a powerful com-petitor to lead tetra-acetate-iodine for these radical transfers. t-Butylhypohalites are also effective, particularly the hypochlorite. The combina-tion silver oxide-bromine (without illumination) has also been used 111 (ontertiary alcohols) and it is considered that the initially formed hypobromitesare decomposed catalytically by silver ion.Both epimers of cholestan-1-01 undergo 1 ,lO-bond cleavage with leadlo* E.Hardegger and C. Scholz, Helw. Chim. Acta, 1945, 28, 1355; J. Canceill,M. Dvolaitzky, and J. Jacques, Bull. Soc. chim. France, 1963, 336; C . Ouannes, M.Dvolaitsky, and J. Jacques, ibid., 1964, 776.lo3 C. Djerassi and G. von Mutzenbecher, Proc. Chem. SOC., 1963, 377.lo4 D. Rosenthal, P. Grabowich, E. F. Sabo, and J. Fried, J . Amer. Chem. SOC.,1963, 85, 3971.lo6 D. H. R. Barton, J. M. Beaton, L. E. Geller, and M. M. Pechet, J. Amer. Chem.SOC., 1960, 82, 2640; D. H. R. Barton and J. M. Beaton, ibid., p. 2641; A. L.Nussbaum and C. H. Robinson, Tetrahedron, 1962, 17, 35.lo6 P. Kabasakalian and E. R. Townley, J. Amer. Chem. SOC., 1962, 84, 2711.l o p M. Akhtar and M. M. Pechet, J .Amer. Chem. SOC., 1964, 86, 265.lo* BI. Akhtar, D. H. R. Barton, and P. G. Sammes, J. Amer. Chem. SOC., 1964,86, 3394.1°9M. Akhtar and D. H. R. Barton, J . Amer. Chem. Soc., 1964, 86, 1528.C. Meystre, K. Heusler, J. Kalvoda, P. Wieland, G. h e r , and A. Wettstein,Experientia, 1961, 10, 474 and subsequent papers; for a review see K. Heualer andJ. Kalvoda, Angew. Chem., Internat. Edn., 1964, 3, 525.ll1R. A. Sneen and N. P. Matheny, J. Arner. Chern. Soc., 1964, 86, 3905422 ORGANIC CHEMISTRYtetra-ace t a t e to give 1 -aldehydes 3B-Ace t oxycholes tan-5cc-01 with eitherlead tetra-acetate or mercuric oxide-iodine gives 5-ketones derived from5JO-bond fi~si0n.l'~ Oxidation of the compounds (59) and (60; R = ethyl-ene ketal or /?-benzoate) by lead tetra-acetate proceeds 11* smoothly asshown.By contrast,l15 the 5a- and 5/?-compounds (60; 5,6-dihydro-,R = ethylene ketal) yield complex mixtures of compounds. Evidently theOAcpresence of a homoallylic double bond assists fragmentation. The etherspresent in the mixtures were derived from attack of the alkoxyl radical atpositions 8 and 11 and not at other positions. The implications of all thesehdings have been fully discussed.115Photochemktry.-Most purely photochemical studies on steroids arecarried out on their ketones and the transformations which occur includeepimerisation, double-bond migration, decarbonylation (with aldehydes),addition including dimerisation (with conjugated ketones), ring fission, andring formation. A particular photochemical reaction may involve severalof these processes.4,6-Dien-3-ones and 3,5-dien-7-ones undergo dimerisation on irradiation.ll6112 M.Stefanovid, 31. GaBi6, L. Lorenc, and M. L. Mihailovi6, Tetrahedron, 1964,20, 2289.118 M. L. Mihailovi6, M. Stefanovi6, L. Lorenc, and M. GsSi6, Tetrahedron Letters,1964, 1867; M. Akhtar and 8. Marsh, ibid., p. 2475.114 &I. Amorosa, L. Cagliotti, G. Cainelli, H. Immer, J. Keller, H. Wehrli, M. L.Mihailovid, K. Schaffner, D. Arigoni, and 0. Jeger, Helv. Chim. Acta, 1962, 45, 2674.116 D. Hauser, K. Heusler, J. Kalvoda, K. Schaffner, and 0. Jeger, Helv. China.Acta, 1964, 47, 1961.116 M. €3. Rubin, G. E. Hipps, and D. Glover, J. Org. Chenz., 1964, 29, 68; Tetra-hedron Letters, 1964, 1075WHITEHTJRST: STEROIDS 423A 12-oxo-steroid (hecogenin acetate) undergoes 12,13-bond fission to formthe compound of structure (61), which on further irradiation undergoesrecyclisation to form a 12cc,14-0xide.~~~ A c-nor-1 l-keto-steroid furnisheda compound with structure similar to that of (61 ; CHO instead of CH,*CHO).llBQuinkert et a1.l19 reported ring fission in saturated 3-, 6-, 7-, 12-, and 17-keto-steroids.Deuterium-labelling has established the course of the hydro-gen transfers in some of these reactions.1 -Dehydro-B-nortestosterone acetate (62) yields a single isomer (63) (68 %conversion) on irradiation ;I20 1 -dehydro-2-methyltesOosterone acetate,121 likethat of l-dehydrotestosterone acetate itself,122 gives a complex mixture.In contrast, introduction of a 4-alkyl group 123 into these systems simplifiestheir photochemistry quite remarkably.124 Irradiation of 4,5-epoxy-3-ketones gives the almost completely enolic A-nor-B-homodiketones (64) .125The stereochemistry at position 10 is retained in this transformation;4-methyl-4aY5- and -4/3,5-epoxides yield isomeric products (64 ; 4-Me) differingin configuration at the 4-bridgehead.Synthesis.-An extremely simple and totally chemical synthesis ofequilin has been announced126 (Chart l), the starting material (65) beingavailable by a radical transfer.0 nO WCHART 1 .Reagents : 1, Ac,O-AcCl-C,H,W.2, NaHC0,-MeOH.3, 2,3 -Dichloro- 5,6-dicyano- 1,4- benzoquinone-diouan. 4, NaOH-MeOH.11' P. Bladon, W. McMeekin, and I. A. Williams, J .Chem. SOC., 1963, 5727.118 J. Iriarte, K. Schaffner, and 0. Jeger, Helw. Chim. Acta, 1964, 47, 1255.llB G. Quinkert, B. Wegemund, F. Homburg, and G. Cimbollek, Chenz. Ber., 1964,lZo G. Bozzato, H. P. Throndsen, K. Schaffner, and 0. Jeger, J . Amer. Chem. Soc.,C . Ganter, F. Greuther, D. Kiigi, K. Schaffner, and 0. Jeger, Hclw. China. Acta,122 H. Dutler, H. Bosshard, and 0. Jeger, HeZu. Chim. Acta, 1957, 40, 494.12* K. Weinberg, E. C. Utzinger, D. Arigoni, and 0. Jeger, Helw. Chim. Acta, 1960,lZ4 See also P. J. Kropp, J . Amer. Chem. SOC., 1963, 85, 3779.125 H. Wehrli, C. Lehman, K. Schaffner, and 0. Jeger, Helw. Chim. Acta, 1964, 47,126 J. F. Bagli, P. F. Morand, K. Wiesner, and R. Gaudry, Tetrahedron Letters,97, 958; G. Quinkert, E. Blanke, and F.Homburg, ibid., p, 1799.1964, 86, 2073.1964, 47, 627.43, 236.1336; 1962, 45, 2420.1964, 387424 ORGANIC CHEMISTRYThe synthesis of digitoxigenin (66) I27 (Chart 2) has been succeeded byAnother synthesis of digitoxigenin 128b one of periplogenin (67) 128u (Chart 3).AcO eH HMeIHO - C - C E C. OEtAcOCHART 2.Reagents: 1, LiMe. 2, LiEC*OEt. 3, MeOH-H,SO,; Ac,O-C,H,N.4, SeO,; HCl-MeOH.CHZsOHIAcOCH~*OACc=oOH' 0LHOOH /@ OH (67)CHART 3.Reagents : 1, LiAlH,; Ac,O-C,H,N. 2, HOBr; MeOH-KOH. 3, Me,CO-GUS04.4, LiAlH,. 5, H+. 6, Ac,O-C,H,N. 7, Cr0,-Me,N'CHO. 8, LiCEC'OEt; H+.l2lN. Danieli, Y. Mazur, and F. Sondheimer, J . Amer. Ch SOC., 1962, 84,12* (a) R. Deghengi, A. Phillip, and R. Gaudry, Tetrahedron Letters, 1963, 2045;875.(b) C.R. Engel and G. Bach, Steroids, 1964, 3, 593WHITEHURST : STEROIDS 425defers the introduction of the 14;B-hydroxyl function until after the 17b-cardenolide side chain has been elaborated (Chart 4).AcOHReagents :HCHART 4.3, Raney Ni; hydrolysis.1, HOBr ; dehydrobromination by chromatography.(66)2, HC1- -CHCl,.Related Natural Products.-Cucurbitacin A has the structure (68) ;lmother cucurbitacins are similarly constituted. Isojervine is now known 130-132to have structure (69). The unusual ultraviolet light absorption of thissubstance (virtually “end” absorption) is caused by the presence of theisoIated 5,6-ethylenic b0nd.1~~ The chemistry of pseudo-strophanthidin hasbeen errp10red.l~~ The stereochemistry of the B/c/D-ring junctions ofla9 W.T. de Kock, P. R. Ens&, K. B. Norton, D. H. R. Barton, B. Sklarz, andA. A. Bothner-By, J. Chem. SOC., 1963, 3828; D. Lavie, Y. Shvo, 0. R. Gottlieb,and E. Glotter, J. Org. Chem., 1963, 28, 1790.lSo 0. Wintersteiner and M. Moore, J . Org. Chem., 1964, 29, 262.lS1 T. Masamune, M. Takasugi, M. Gohda, H. Suzuki, S. Kawahara, and T. Irie,J . Org. Chem., 1964, 29, 2282.la3 W. G. Dauben, W. W. Epstein, M. Tanabe, and B. Weinstein, J . Org. Chena.,1963, 28, 293.1x4 E. A. Braude, E. R. H. Jones, F. Sondheimer, and J. B. Toogood, J . Chem. SOC.,1949, 607; E. R. H. Jones, G. H. Mansfield, and M. C. Whiting, J . Chem. SOC., 1956,4073.ls4T. Kubota and M. Ehrenstein, J . Org. Chem., 1964, 29, 342426 ORGANIC CHEMISTRYfusidic acid is thought t o be trans-anti-trans.The dried roots ofAsclepias glaucophylla Schlechter are a rich source of sarc08tin.l~~ Structureshave been proposed for tornentogenin 137 and meta~1exigenin.l~~ Thedigipurpurogenins 139 are now considered to be 17#?-acetyl-l4~-hydroxy-compounds. The simple steroid, 5a-androstane-3~,16a,l7a-triol occurs inAplupappus 7~eterophyZZus.l~~ Veratramine has been related 141 to hecogenin,thus proving its 9aH-configuration, and nuclear magnetic resonance studieshave confirmed the 27P-methyl configuration.142The steroids and the pentacyclic triterpenes have been related by con-version of lupeol (70) into the %methyl enantio-steroid (71), and comparisonof the latter with the (synthesised) natural extensive use ofgas-liquid chromatography was made in this study.bonds of both lanosterol and agnosterol can be hydrogenated.144The nuclearP I -\'7 3 ) --.w HdoubleSteroidal alkaloids have b~rge0ned.l~~~ 146 In the case of Buxus alka-loids (72) a welcome rationalisation of nomenclature has been proposed,145136 D.Arigoni, W. von Daehne, W. 0. Godtfredson, A. Melera, and S . Vangedaal,Experientia, 1964, 20, 344; R. Bucourt, M. Legrand, H. Vignau, J. Tessier, and V.Delaroff, Compt. rend., 1963, 257, 2679.136 J. M. do Nascimento, C. T a m , H. Jiiger, and T. Reichstein, Helv. Chim. Acta,1964, 47, 1775.13' H. Mitsuhashi, T. Sato, T. Nomum, and I. Takemori, Chem. and Pharm. Ball.(Japan), 1964, 12, 981.13a H. Mitsuhashi and T. Nomura, Chem.and Phurm. Bull. (Japan), 1963, 11, 1333.139 T. Tschosche, G. Briigmann, and G. Sniitzke, Tetrahedron Letters, 1964, 473;H. Mitsuhashi and T. Nomura, Steroids, 1964, 3, 271.I4O L. H. Zalkow, N. I. Burke, and G. Keen, Tetrahedron Letters, 1964, 217.141 H. Mitsuhashi and K. Shibata, Tetrahedron Letters, 1964, 2281.142 S. Ito, J. B. Stothers, and S . M. Kupchan, Tetrahedron, 1964, 20, 913.143 G. V. Baddeley, T. G. Halsall, and Sir Ewart Jones, J . Chem. Soc., 1964, 1173;S. Binns, J. S. G. Cox, Sir Ewart Jones, and B. G. Ketcheson, J . Chem. Soc., 1964,1161.144 J. D. Chanley and T. Mezzetti, J . Org. Chem., 1964, 29, 228; L. F. Fieser andM. Fieser, " Steroids ", Reinhold Publ. Co., New York, 1959, p. 368.14B K. S. Brown and S . M. Kupchan, Tetrahedron Letters, 1964, 2895.T.Nakano and S . Terao, Tetrahedron Letters, 1964, 1035, 1045; S. M. Kupchanand W. L. Asbun, ibid., p. 3145; J. P. Calame and D. Arigoni, Chimda (Switz.), 1964,18, 183; T. Nakano and M. Hasegawa, Tetrahedron Letters, 1964, 3679; D. Stauffacher,Helv. Chim. Acta, 1964, 47, 968; P.-L. Chien, W. E. McEwen, A. W. Burgstahler, andN. T. Iyer, J . Org. Chena., 1964, 29, 315; W. F. Knaack and T. A. Goissman, TetrahedronLetters, 1964, 1381 ; L. Labler and F. Sorm, Coll. Czech. Chem. Comm., 1963, 28, 2315;M. Tomita, S . Uyeo, and T. Kikuchi, Tetrahedron Letters, 1964, 1053, 1641, 1817;J. M. Kohli, A. Zaman, and A. R. Kidwai, ibid., p. 3309; M.-M. Janot, P. Longevialle,C. Conrew, and R. Goutarel, Bull. Xoc. chim. France, 1964, 2158; R.Tschesche, W.Meise, and G. Snatzke, Tetrahedron Letters, 19G4, 1659; R. Tschesche and H. Ockenfells,Chem. Ber., 1964, 97, 2316, 2326; M.-M. Janot, F.-X. Jarreau, 31. Truong-Ho, Q.Khuong-Huu, and R. Goutarel, Compt. rend., 1964,258,2089; 35.-35. Janot, Q. Khuong-Huu, J. Yassi, and R. Goutarel, Bull. Xoc. chim. France, 1964, 787, 2169; V. cernyWHITEEURST: STEROIDS 427based on the substitution pattern a t the nitrogen atoms.of ring systems, apart from the sapogenin alkaloids, a.re (72)-(75).review of Apocyanuceae alkaloids has been ~ub1ished.l~'The main typesAorH OHUThe structures assigned 14* to diginin and digifolein are correct, but theether ring is not cleaved by lithium aluminium hydride;149 reduction occursat the 11- and 15-carbonyl groups.Ring c in these compounds is con-sidered to be an 8,12(prow-stern)-boat. Compound (76) (from digifolein)MeI0-C-H. I . .shows normal carbonyl absorption with a strong intramolecular hydrogenbridge from the 15-hydroxyl group. The A596-parent compound, on theother hand, shows virtually no carbonyl absorption and exists a.s the 11,15-hemiketal-an interesting example of the Barton effect.L. Dolejg, and F. sorm, Con. Czech. G h n . Conwn., 1964, 29, 1591; P. Potier, C. Kan,and J. Le Men, Tetrahedron Letters, 1964, 1671; A. CavB, P. Potier, A. Cavk, andJ. Le Men, Bull. SOC. chirn. France, 1964, 2415.147 R. Goutarel, BulE. SOC. chim. France, 1964, 1665.148 C. W. Shoppee, R. E. Lack, and A. V. Robertson, J . Chem.SOC., 1962, 3610;ibid., 1963, 3281.llS R. Tschesche and G. Brugmann, Tetrahedron, 1964, 20, 1469428 ORGANIC CHEMISTRYRacemic mevalonic acid 5-phosphate and 5-pyrophosphate have beensynthesised.150 The cardenolide ring is formed 151 biochemically from apregnane unit and acetic acid. A number of microbiological transformationsof steroids have been reported.152lS0 H. Machleidt, E. Cohnen, and R. Tschesche, Annalen, 1964, 672, 215; 1962,655, 70.161 J. von Euw and T. Reichstein, Helv. Chim. Acta, 1964, 47, 711.lS2 A. I. Laskin, P. Grabowich, B. Junta, C. de L. Meyers, and J. Fried, J . Org.Chem., 1964, 29, 1333; V. Schwarz, M. Ulrich, and K. Syhora, Steroids, 1964, 4, 645;C. Coronelli, D. Kluepfel, and P. Semi, Experientia, 1964, 20, 208; E.L. Patterson,W. W. Andres, and R. E. Hartman, ibid., p. 256; T. Okumura, Y. Nozaki, and D. Satoh,Chem. and Pharm. Bull. (Japan), 1963, 11, 1340; Y. Sato, T. Tanaka, M. Kato, andK. Tsuda, ibid., p. 1579; R. C. Tweit, E. A. Brown, S. Kraychy, S. Mizuba, and R. D.Muir, ibid., p. 859; 0. el-Tayeb, S. G. Knight, and C. J. Sih, Biochim. Biophys. Acta,1964, 93, 402, 41112. CARBOHYDRATESBy D. H. Hutson and D. J. Manners(Chemistry Department, The University, West Mains Road, Edinburgh, 9)A MAJOR scientific event in 1964 was the Sixth International Congress ofBiochemistry, at which 146 papers covering the chemistry and biochemistryof carbohydrates were presented.1 Highlights included a Congress lectureby L. F. Leloir 2 on the biosynthesis of polysaccharides and a report of theenzymic synthesis of cellulose by W.Z. Hassid.3The following topics have been reviewed recently : photochemistry andpaper electrophoresis 5 of carbohydrates ; osotriazoles 6 and thio-sugars ;7trehaloses ; 8 naturally occurring C-glycosyl compounds ;9 amino-sugarsderived from antibiotics ;lo biosynthesis of carbohydrates from sugar nucleo-tides ;I1 physical properties of polysaccharide solutions ;12 the applicationof instrumental techniques to the structural analysis of monosaccharides ;13the molecular structure of polysaccharides from plants,14 and algz ;Isand the chemical technology of carbohydrate oxidations.17 A comprehensivemonograph on monosaccharide chemistry,lS a revised edition of a standardtext-book,lg and a fourth volume 2o of ‘‘ Methods in Carbohydrate Chemistry(Starch) ” have also been published.General Methods.-Thin-layer chromatography is continuing to be animportant technique for the analysis of sugar derivatives.21 Of particularinterest is the use of starch 22 and microcrystalline cellulose 23 as supports,1 Abs.Sixth Internat. Congress of Biochemistry, I.U.B., 1964, 32, Section VI.2 L. F. Leloir, Plenary Sessions, Sixth Internat. Congress of Biochemistry, I.U.B.,8 W. Z. Hassid, G. A. Barber, and A. D. Elbein, in ref. 1, S.7; see also A. D.1964, 33, 15.Elbein, G. A. Barber, and W. Z. Hassid, J . Arner. Chem. SOC., 1964, 86, 309.G. 0. Phillips, Adv. Carbohydrate Chem., 1963, 18, 9.H. Weigel, Adv. Carbohydrate Chem., 1963, 18, 61.H.El Khadem, Adv. Carbohydrate Chem., 1963, 18, 99.D. Horton and D. H. Hutson, Adv. Carbohydrate Chem., 1963, 18, 123.G. G. Birch, Adv. Carbohydrate Chew., 1963, 18, 201.L. J. Haynes, Adv. Carbohydrate Chern., 1963, 18, 227.lo J. D. Dutcher, Adv. Carbohydrate Chem., 1963, 18, 259.l1 E. F. Neufeld and W. Z . Hassid, Adv. Carbohydrate Chem., 1963, 18, 309.W. Banks and C. T. Greenwood, Adv. Carbohydrate Chern., 1963, 18, 357.l3 R. J. Ferrier and N. R. Williams, Chem. and Id., 1964, 1696.l4 D. H. Northcote, Ann. Rev. Biochern., 1964, 33, 51.l6 G. A. Adams, Pulp Paper Mag. Canada, 1964, 65, T.13.l6 E. Percival, Proc. Fourth Internat. Seaweed Symposium, Biarritz, 1961, ed.A. D. de Virville and F. Feldman, Pergamon Press, Oxford, 1964, p. 18.l7 C.L. Mehltretter, Starke, 1963, 15, 313.l8 J. Stanek, M. Cerny, J. Kocourek, and J. Pacak, “ Monosaccharides ”, AcademicPress, New York, and Publishing House of the Czechoslovak Academy of Sciences,Prague, 1963.R. D. Guthrie and J. Honeyman, “ An Introduction to the Chemistry of Carbo-hydrates ”, Oxford Univ. Press, 1964.2o “ Methods in Carbohydrate Chemistry ”, Vol. N, ed. R. L. Whistler, AcademicPress, New York, 1964.21H. Grasshof, J . Chromatog., 1964, 14, 513; B. D. Modi, J. R. Patil, and 5. L.Bose, Indian J . Chem., 1964, 2, 32; J. P. Tore, A m l y t . Biochem., 1964, 7, 123.22 B. Shasha and R. L. Whistler, J . Chromatog., 1964, 14, 532.23 M. L. Wolfrom, D. L. Patin, and R. M. de Lederkremer, Chem. and Id., 1964,1065430 ORGANIC CHEMISTRYso that paper-chromatographic methods can be translated directly into thin-layer chromatography, with saving of time and increased sensitivity.Gas-liquid chromatography (g.1.c.) has been used for the determination andcharacterization of amino-sugars 24 and the trimethylsilyl derivatives ofsugar phosphate^.^^ Partition chromatography of sugars on fine-mesh basicion-exchange resins under pressure has been reported.2s Ionophoresis inbisulphite solution,27 and absorption on the bisulphite form of a basic ion-exchange resin, followed by elution with acetone,2* have been developed forthe analysis of mixtures of keto-sugars.The kechnique of molybdate iono-phoresis has been extended to the tungstate i0n.29 Sugars have been detectedon paper chromatograms with complex cuprates 30 and with quaternarysalts .31The stereochemistry of a number of monosaccharide derivatives has beenelucidated by nuclear magnetic resonance (n.m.r.) spectroscopy, and the tech-nique is clearly becoming very important.Among the compounds studiedare aminodeo~yheptulosans,~2 1,2-0-alkylidenepyranose derivatives,33 “ di-fructose anh~dride,”~* 4-deoxyuronic acids,35 and D-glucal triacetate.36Acyclic structures can be detected by means of the signal from the l-formylprotons.37 The structure of sugar osazones has been re-e~amined.~~Hydroxyl protons of sugars in dimethyl sulphoxide solution have beenstudied.39 It is possible to distinguish ring-size, position of deoxy-groups,position of unprotected hydroxyl groups in partially methylated sugars, andaldoses from ketoses by the use of mass specfr~metry.~O Studies of carbo-hydrates by means of optical rotatory dispersion have been reported.41Useful crystalline derivatives of sugars include thiosemicarbazones 42 and2 4 M.B. Perry, Canad. J . Biochem., 1964, 42, 451.25 W. W. Wells, T. Katagi, R. Bentley, and C . C. Smeeley, Biochim. Biophys. Acta,2 6 J. Dahlberg and 0. Samuelson, Acta Chem. Scand., 1963, 17, 2136.27 A. Assarsson and 0. Theander, Acta Chem. Scand., 1964, 18, 727.? * K. Heyns, A. L. Baron, and H. Paulsen, Chem. Ber., 1964, 9’7, 921.29 H. J. F. Angus, E. J. Bourne, F. Searle, and H. Weigel, Tetrahedron Letters,30 J. Kocourek, M. Ticha, J. Kostir, and L. Jensovsky, J . Chromatog., 1964,14,228.3IW.A. Rosenthal, S. Spaner, and K. D. Brown, J . Chronaatog., 1964, 13, 152.3 2 H. H. Baer, L. D. Hall, and F. Kienzle, J . Org. Chem., 1964, 29, 2014.33 B. Coxon and L. D. Hall, Tetrahedron, 1964, 20, 1685.s4R. U. Lemieux and R. Nagarajan, Canad. J . Chem., 1964, 42, 1270.s5 H. W. H. Schmidt and H. Neukom, Tetrahedron Letters, 1964, 2063.ssL. D. Hall and L. F. Johnson, Tetrahedron, 1964, 20, 883. *’ M. L. Wolfrom, G. Fraenkel, D. R. Lineback, and F. Komitsky, J . Org. Chem.,3 8 L. Mester and E. Moczar, J . Org. Chem., 1964, 29, 247.39 B. Casu, M. Reggiani, G. G. Gallo, and A. Vigevani, Tetrahedron Letters, 1964,2839.40D. C. DeJongh, J . Amer. Chem. SOC., 1964, 86, 3149; D. C. DeJongh and K.Biemann, J . Amer. Chem. SOC., 1964, 86, 67; P. A. Finan, R.I. Reed, W. Snedden,and J. M. Wilson, J . Chem. SOC., 1963, 5945; N. K. Kochetkov and 0. S . Chizhov,Biochim. Biophys. Acta, 1964,83, 134; N. K. Kochetkov, N. S . Wulfson, 0. S. Chizhov,and B. M. Zolotarev, Tetrahedron, 1963, 19, 2209; M. Venugopalan and C . B. Anderson,Chem. and Ind., 1964, 370.41 N. E. Franks, Dws. Ah., 1964, 24, 2687; T. Okuda, S. Harigaya, and A. Kiyo-moto, Chern. and Pharm. BuU. (Japan), 1964, 12, 604; N. Pace, C. Tanford, and E. A.Davidson, J . Amer. Chem. SOC., 1964, 86, 3160; Y. Tsuzuki, K. Tanabe, M. Akagi, andS . Tejima, Bull. Chem. SOC. Japan, 1964, 37, 162.1964, 82, 408.1964, 55.1964, 29, 457.4 2 J. R. Holker, Chem. and Ind., 1964, 546HUTSON AND MANNERS : CARBOHYDRATES 431p - benzamidobenzoic esters.43 The latter, though requiring a three-stagesynthesis, are excellent crystalline compounds ; in addition, the ester groupwill not migrate. F'rom a study of the optical rotations of phenylosotri-azoles 44 the following generalization has been made: if the 3-hydroxyl groupin an unsubstituted reducing sugar lies to the left in the Fischer projectionformula, the derived phenylosotriazole is lzevorotatory for the sodium-D linein pyridine.Monosaccharides.-Oxi&lttion. The oxidation of a-D-glUCOSe by bromineproceeds mainly by anomerization to p-D-glucose 45 and this appears tohold for a number of pentoses and hexoses; the '' direct " oxidation ofa-D-glUCOSe is much less important than hitherto supposed;46 in fact, bromineis even more selective towards a- and p-D-glucose than is the enzyme,glucose oxidase.The mechanism proposed for the reaction involves electro-philic attack by bromine on the glycosidic oxygen atom to form the hypo-bromite conjugate acid; this is greatly facilitated by participation of thering-oxygen atom which can only occur in p-D-glucose (1). Bromine oxida-tion of L-sorbose, ~-glucitol, or D-fructose at 50" in the presence of strontiumcarbonate leads to the formation of 2,5-~-threo-diketohexose.~~ The oxida-tion of aldoses to aldonic acids cannot be effected with bromine whenhydroxyl groups are protected by benzylation ; the use of N-bromocarbamideeffects this change with high yield and selecti~ity.~s The introduction ofketo-groups into sugar rings after protection of the 1-hydroxyl group hasbeen effected with nitrogen dioxide,49 platinum+xygen,28 and chromiumtri~xide.~* The usual solvent for chromium trioxide-pyridine-can leadto isomerization of oxidation products.51 Recently, oxidation with ruth-enium tetroxide in carbon tetrachloride has been reported.This reagentleads to higher yields than are obtained with the above reagents. 1,2 : 5,6-Di-O-isopropylidene-a-r,-glucofuranose, containing a 3-hydroxyl group whichis normally very resistant to oxidation, is cleanly oxidized to give 1,2 : 5,6-di-O-isopropylidene-or-~-r~bo-3-hexulofuranose in 80% yield.52 This reaction,followed by may be the best route to D-allose.The y-ray decomposition of solid glycosides is retarded Degradution.43 J. Kiss, Chem. and Ind., 1964, 32.4 4 J.A. Mills, Austral. J . Chem., 1964, 17, 275.45 I. R. L. Barker, W. G. Overend, and C. W. Rees, J . Chem. SOC., 1964, 3254.4 7 G. C. Whiting and R. A. Coggins, Chem. and Ind., 1964, 1925.48 J. Kiss, Chem. and Ind., 1964, 73.4B A. Assarsson and 0. Theander, Acta Chem. Scand., 1964, 18, 553.so A. Assarsson and 0. Theander, Acta Chem. Scand., 1964,18, 727; 1963, 17, 1751.s1 A. F. Krasso, E. Weiss, and T. Reichstein, Helv. Chim. Acta, 1063, 46, 2538.6a P. J. Beynon, P. BI. Collins, and W. G. Overend, Proc. Chem. SOC., 1964, 342.s3 F. P. Phelps and F. Bates, J . Arner. Chew?,. SOC., 1934, 56, 1250.H. S. Isbell and W. Pigman, J . Res. Nut. Bur. Stand., 1933, 10, 337432 ORGANIC CHEMISTRYor prevented by the introduction of aromatic groups into the molecule;5*thus, phenyl a-D-glucopyranoside is much more stable than the methylglycoside, in contrast to their stability in acid; benzoylation of the glyconesimilarly confers stability.Hexose formation is the main reaction in thesensitized photo-oxidation of ~-glucitol,~5 hexonic acid being produced moreslowly. A similar degradation is effected by y-radiation.56 D- Arabhose isobtained in almost quantitative yield by treatment of t-butyl 2,3,4,6-tetra-O-acetyl- 1 -peroxy-p-D-glucopyranoside with dilute sodium methoxide atroom temperature for three days; this new method of degradation is capableof general application to sugars.57 The four isomeric 2,4-di-O-methyl-tetroses have been prepared by the periodate oxidation of suitably methylatedpentoses and hex0ses.~8Esters.The phosphates of 4-keto- 59 and 2-amino-s~gars,~~ and also2-deoxy-D-arabino-hexonic acid 6-phosphate and trehalose 6-pho~phate,~~have been synthesized. Carbohydrate esters show a complex series ofreactions in liquid hydrogen fluoride, including deacetylation, Waldeninversion, and ring cleavage. 63 Met hylation of 1 ,Z-O-isopropylidene-a-D-glucofuranose 5,6-thionocarbonate (2) yields, not the expected 3-O-methylether, but it unique orthoester, 1,2-0-isopropy~idene-a-~-g~ucofuranose3,5,6-(S-methyl monothio-orthocarbonate) (3).64 The synthesis of the 2,3-,O - CHI 2 0 -CH2MeS-C4 'kO$ s=c, IMel- ~O-CHAg2OHH O-CMe2 H O-CMe2(2) (3)carbonate from 6-0-trityl-D-mannose forces the ring into the furanose formand consequently permits the synthesis of either of the anomeric methylmmannofuranosides through 5,6-di-O-acetyl-a-~-mannofuranosyl bromide2,3-~arbonate.~~ Condensation of phenylboronic acid with the methylxylopyranosides leads to the formation of 2,4-cyclic esters.66 Phenylboronicacid may be removed non-destructively by the addition of propane-1,3-dioland extraction of the resulting ester with light petroleum.The cyclic64 G. 0. Phillips, F. A. Blouin, and J. C . Arthur, Nature, 1964, 202, 1328.6 6 G. 0. Phillips, P. Barber, and T. Rickards, J . Chem. SOC., 1964, 3443.66 G. 0. Phillips and K. W. Davies, J . Chem. SOC., 1964, 3981.6 7 M. Schultz and H. Steinmans, Angew. Chem., Internat. Edn., 1963, 2, 623.6* G. G. S. Dutton and K.N. Slessor, Canad. J . Chem., 1964, 42, 614.6 9 D. B. E. Stroud and W. Z . Hassid, Biochem. Biophys. Res. Comm., 1964, 15, 65.60 D. M. Carlson, A. L. Swanson, and 8. Roseman, Biochemistry, 1964, 3, 403;6 2 D. L. MacDonald and R. Y . K. Wong, Biochim. Biophys. Acta, 1964, 86, 390.6 3 E . J. Hedgley and H. G. Fletcher, J . Amer. Chem. SOC., 1964, 86, 1576; C.64 B. S. Shasha, W. M. Doane, C. R. Russel, and C . E. Rist, Nature, 1964,204, 186;6sA. S. Perlin, Canad. J . Chem., 1964, 42, 1365.66 R. 3. Ferrier, D. Prasad, A. Rudowski, and I. Sangster, J . Chem. Soc., 1964,P. J. O'Brien, Biochirn. Biophys. Acta, 1964, 86, 628.N. E. Franks, Diss. A h . , 1964, 24, 2687.Pedersen, Acta Chem. Scand., 1964, 18, 60.cf. J. C. P. Schwarz, J . Chem.SOC., 1954, 2644.3330; R. J. Ferrier, D. Prasad, and A. Rudowski, Chem. and Ind., 1964, 1260HUTSON AND MANNERS : CARBOHYDRATES 433complexes between molybdate and tungstate and polyhydroxy-compoundshave been examined by potentiometric titration and paper electrophoresis ;dimolybdate and ditungstate ions are probably the complex-forming agents.67The readily prepared ally1 ethers of carbohydrates should proveto be useful synthetic intermediates. While the ally1 ether group (4) is stableto both acid and alkali, it is readily rearranged by potassium t-butoxidein dimethyl sulphoxide t o the acid-labile prop-1-enyl ether (5).6* Alkalinepermanganate affords an alternative, completely basic method of removal(see below). Part,ial cyanoethylation of tetrahydropyran-2-yl glucosidesEthers.B ~ O K H+RO*CH,-CH-CH, R O - C H S H M e -+ R O HI ( 5 ) 4 Me,SO (4)KJln04J +NaOH I[RO*CH( OH)-CHMe-OH]indicates that the 6-position is most reactive, followed by the 2-p0sition.6~An apparent displacement of a methanesulphonyl group by alkoxide indimethyl sulphoxide, t o form an ether with retention of conJig~ration,~~ isan unusual feature; studies with l 8 0 showed that the C-0 bond is not brokenin this reaction.N-Trimethylsilylacetamide has been used for the formationof silyl ethers of glucose, and a synthesis of gentiobiose was accomplishedby using this readily removable blocking gr0up.7~Methyl 2,3 - anhydro - 4 - 0- methyl- a-D - allop yranoside (6)is converted into methyl 3,6- anhydro-4- 0-met hyl-a- D -gIucop yranoside (7) inAn h ydro - s ugars .H2C ' 0CH2 OHMe0 +OM: M e 0 OH(6) (7)hot, dilute alkaL72 The mechanism of the reaction is clear if the epoxideassumes the half-chair conformation (6), the 6-hydroxyl group attacks theepoxide ring from the rear, and the subsequent ring opening obeys theFiirst-Plattner rule.67 H.J. F. Angus and H. Weigel, J . Chem. Soc., 1964, 3994.6 8 J. Cunningham, R. Gigg, and C. D. Warren, Tetrahedron Letters, 1964, 1191.69 P. J. Garegg and J. Kubo, Acta Chem. Scum?., 1964, 18, 207; P. J. Garegg,'O D. H. Ball, E. D. M. Eades, and L. Long, J . dmer. Chem. Soc., 1964, 86, 3679.7e P. Chang and Chan-Ming Hu, Sci. Sinica, 1964, 13, 441.J. Kubo, and B. Lindberg, ibid., 1963, 17, 1761.L. Birkofer, A.Ritter, and F. Bentz, Chm. Ber., 1964, 97, 2196434 ORGANIC CHEMISTRY3,5-Anhydrofuranoses have been synthesized by the alkali-treatment of5,6-anhydrof~ranoses.7~ The presence of a 6-O-acetyl group in derivativesof methyl 3,4-anhydro-6c-~-altropyranoside (8) leads to t'he formation ofD-idose derivatives (10) on acid hydrolysis;74 a cation (9) having a six-membered ring is postulated as an intermediate.A route to 2,5-anhydro-sugars has been found in the reaction of methyl2-deoxy-2-iodo-~-~-glucopyranoside triacetate (1 1) 75 with a large excess ofbromine and silver acetate as illustrated.76 The resultant anomeric mixtureReagent : 1, Br,AgOAc-KOAc-AcOH.of 1,3,4,6-tetra-O-acetyl-2,5-anhydro-l-methoxy-~-ma~oses is formed inalmost quantitative yield.2,5-Anhydro-~-talose has been prepared bydeamination of D-galactosamine with nitrous acid.77 Condensation ofnitromethane with pentoses, reduction, and the action of nitrous acid onthe resultant l-aminohexitol lead to 1,4-anhydrohexitols.7* 1,6-Anhydro-@-D-glucofuranose has been detected in the products of thermal degradationD-fiCOSamine has been isolated from the cell-wall poly-saccharides of various Bacillus species,g* and L-fucosamine from the muco-polysaccharide of Enteric bacteria.81 The last of the eight possible Z-amino-2-deoxypentoses, 2-amino-2-deoxy-~-xylose, has been synthesized byepimerization of the L-lyxose derivative.*2 A new approach to the synthesisof 2-amino-2-deoxy-sugars has been initiated by two groups of workers.*3Nitrosyl chloride reacts smoothly with 3,4,6-tri-O-acetyl-~-glucal to form acrystalline adduct, 3,4,6-tr~-~-acety~-2-deoxy-2-~troso-~-~-g~ucop~chloride (12); reaction with silver acetate followed by reduction with azinc-copper couple in glacial acetic acid affords the D-glucosamine derivative ;the intermediate (12) should be useful in the preparation of glycosides andnucleosides. The two anomers of benzyl 2-amino-N-benzyloxycarbonyl-2-deoxy-D-glucopyranoside were prepared by direct glycosidation and wereof P-D -glucose.'gAmdno-sugars.73 J.G. Buchanan and E. M. Oakes, Tetrahedron Letters, 1964, 2013.7 4 J. G. Buchanan and R. M. Saunders, J. Chem. Soc., 1964, 1791.7 6 R. U. Lemieux and B. Fraser-Reid, Canad. J . Chem., 1964, 42, 539.70 R.. U.Lemieux and B. Fraser-Reid, Canad. J. Chem., 1964, 42, 547.7 7 J. Defaye, Bull. Soc. chim. France, 1964, 999.78R. Barker, J. Org. Chem., 1964, 29, 869.N. M. Merlis, E. A. Andrievskaya, 2. V. Volodina, and 0. P. Golova, Zhur.obshchei Khirn., 1964, 34, 334.so R. Wheat, E. L. Rollins, and J. Leatherwood, Nature, 1964,202, 492; N. Sharon,I. Shif, and U. Zehavi, Biochem. J., 1964, 93, 210.81 G. T. Barry and E. Roark, Nature, 1964, 202, 493.M. L. Wolfrom, D. Horton, and A. Bockmann, J. Org. Chem., 1964, 29, 1479.83 W. J. Serfontain, J. H. Jordaan, and J. Whitme, Tetrahedron Letters, 1964, 1069;R. U. Lemieux, T. L. Nagabhushan, and I. K. O'Neill, Tetrahedron Letters, 1964, 1909HUTSON AND MANNERS : CARBOHYDRATES 435separated by ~rystallization.8~ Halogen, and thence nucleoside, derivativescontaining an acyclic D-glucosamine structure have been synthesized.85The reaction of isothiocyanates with 2-amino-sugars yields the acyclictetrahydroxybutylt,hioimidazoles, and not the hitherto expected cyclicphenylthiocarbamyl derivatives.86 N - Alkylation 87 and N-deacetylation 88studies have been reported, the latter leading to the first crystalline sampleof the free base, methyl , 2-amino-2 -deoxy-cc-~ -glucopyranoside . N - Ace tyl-2-amino-2-deoxy-~-mannose has been synthesized from 1 -deoxy-1 -nitro-D-mannitol penta-a~etate.8~ The reduction of D-fructose oxime affords2-amino-2-deoxy-~-mannito~.~~ The search for synthetic nucleosides andfor synthetic antibiotic constituents has led to extensions of the alreadyimportant neighbouring-group displacement reactions.Baker and Neilson 91report a series of studies on the nitroguanidine (13), thiourea (14), urea (15),and guanidine (16) neighbouring groups as agents for the synthesis of cis-2,3-diamino-sugars. In the first three cases, when the starting material\ /1/ :MeOC y Msy Acid.accept orN NH t ” / YI IIt NH H,N-C:= Y H2N C=Y(13) Y : N*N02 (15) Y = 0(14) Y = S (16) .Y = NHwas converted into a.n anion by sodium methoxide, ring closure t o anaziridino(2,3-imino)-sugar occurred. In the presence of an acid-acceptor(e.g., pyridine), closure to a 5-membered ring resulted except with compounds(13) and (16). However, the use of the l-phenylguanidine group leads tothe required structure.The opening of a 2,3-aziridine with azide ion leadsto trans-diamino-sugnr~.~~ The neighbouring-group opening of an epoxidering is a stereospecific method of conversion of one amino-sugar into another.Thus, the N-benzyloxycarbonyl-D-galactosamine derivative (1 7) can be8 4 P. H. Gross and H. K. Zimmer,man, Annalen, 1964, 674, 211.85 M. L. WoLfrom, H. G. Garg, and D. Horton, J. Org. Chem., 1964, 29, 3280.86 J. E. Scott, Biochem. J., 1964, 92, 57P.8 7 V. I. Veksler, L. N. Kovalenko, and A. V. Markovich, Zhw. obshchei Khim.,8 8 R. D. Guthrie and G. P. B. Mutter, J . Chenz. SOC., 1964, 1614; M. Fujinaga andC. Satoh and A. Kiyomoto, Chem. and Pharm. Bull. (Japan), 1964, 12, 615.W. Roth, W. Pigman, and I. Da.nishefsky, Tetrahedron, 1964, 20, 1675.91 B.R. Baker and T. Neilson, J. Org. Chem., 1964, 29, 1047, 1051, 1057, 1063.9a W. Meyer zu Reckendorf, Chem. Ber., 1964, 97, 325.1964, 34, 704.Y. Matsushims, Bull. Chem. SOC. Japan, 1964, 3’9, 468436 ORGANIC CHEMISTRYconverted into a D-gulosamine derivative by way of an oxazolidone deriva-tive (18).93Reported syntheses using these or established methods include those of:NH\ /(1 91oc' ' ( I 7) '0 * CH2 Ph CO (18)2 - amino - 2 - deoxy - L - rhamnose ;94 4 - amino - 4,6 - dideoxy - D - glucose (vios-amine) ;95 4 - amino - 4,6 - dideoxy- D -galactose ;gs 3,4,6 - trideoxy- 3 -dimethyl-amino-D-glucose (desosamine) ;97 2,6-diamino-2,6-dideoxy-~-idose (paromose,from paromomycin) ;98 2,3-diamino-2,3-dideoxy-derivatives of D-auOSe andD-glucose;99 and a triaminoallose.D9 Methyl 2,6-dideoxy-2,6-imino-3,4-0-isopropylidene-a-D-talopyranoside (19), the fist imino-sugar involving asix-membered ring, has been synthesized by the hydrazinolysis and hydro-genation of methyl 3,4-0-isopropylidene-2,6-di-0-toluene-~-sulphonyl-~-~-galact opyranoside .looInterest in sugars containing nitrogen as the heteroatom lol continuesand the first synthesis of a nitrogen-containing furanose ring has beenachieved.102 Spectroscopic (n.m.r.) studies indicate that there is hinderedinternal rotation in carbohydrates containing nitrogen in either a furanoseor a pyranose ring.103 The structure lo4 and mechanism of hydrolysis lo5 ofglycosylamines have been studied and secondary N-glucosides have beenreported.lo6 The action of nitrous acid on osazone acetates has afforded anew synthesis of osotriazoles.107Photocatalysed addition of thioacetic acid to an exocyclicdouble bond leads to a 6-thiohexose derivative.lO8 The thiobenzoate ionhas been used for the nucleophilic introduction of sulphur into carbo-Thio-sugars.O3 P.H. Gross, K. Brendel, and H. K. Zimmerman, Angew. Chem., Internat. Edn.,1964, 3, 379.gq J. S. Brimacombe and M. C. Cook, J . Chem. Soc., 1964, 2663.96 C. L. Stevens, P. Blumbergs, I?. A. Daniher, 5. L. Strominger, M. Matsuhashi,D. N. Dietzler, S. Suzuki, T. Okazaki, K. Sugimoto, and R. Okazaki, J . Amer. Chem.Soc., 1964, 86, 2939.96 C. L. Stevens, P. Blumbergs, D. H. Otterbach, J. L. Strominger, M. Matsuhashi,and D. N.Dietzler, J . Amer. Chem. Soc., 1964, 86, 2937.97 H. Newman, J . Org. Chem., 1964, 29, 1461.98 W. Meyer zu Reckendorf, Tetrahedron, 1963, 19, 2033.09 W. Meyer zu Reckendorf, Chem. Ber., 1964, 97, 1275.l o o A . Zobacova and J. Jaw, Coll. Czech. Chem. Comm., 1964, 29, 2042.lol H. Paulsen, Annalen, 1963, 670, 121; H. Paulsen, Tetrahedron Letters, 1964, 451;Io2 W. A. Szarek and J. K. N. Jones, Canad. J . Chem., 1964, 42, 20.lo3 W. A. Szarek, S. Wolfe, and J. K. N. Jones, Tetrahedron Letters, 1964, 2743.lo4 B. Capon and B. E. Connett, Tetrahedron Letters, 1964, 1391; J . Sokolowski,1O5 B. Capon and B. E. Connett, Tetrahedron Letters, 1964, 1395.l06 J. Sokolowski and S. Kolka, Roczniki Chem., 1964, 38, 939.lo' M. L. Wolfrom, H. El Khadem, and H.Alfes, J . Org. Chem., 1964, 29, 2072.108 D. Horton and W. N. Turner, Chem. and Ind., 1964, 76.R. L. Whistler and R. E. Gramera, J . Org. Chem., 1964, 29, 2609.Roczniki Chem., 1964, 38, 889HUTSON AND MANNERS : CARBOHYDRATES 437hydrates.lO@ Syntheses of derivatives of 1 -thio-p-D-ribopyranose and-mannopyranose,llo and of 1 - and 6-thio-cc-~-sorbofuranose,~~~ have beenreported. 8- (3,4,6-Tri -0 -acetyl-2 -amino -2 -deoxy -/f? -D -galactopyranosyl)-thioisourea dihydrobromide (20) rearranges at neutral pH to a 2-deoxy-2-guanidino- 1 -thio-derivative (2 1) .l12The ring opening of methyl 2,3-anhydro-~-~-lyxofuranoside by sodiumbenzyl sulphide proceeds predominantly by attack at C-2; this is contraryto all previous experience, even the cr-isomer opening by attack a t C-3.llSVarious pyranose derivatives containing sulphur as the heteroatom havebeen synthesized.l14Deaxy-sugars.Hydroboronation of an exocyclic double bond of a hexo-furanoside leads to a 5-deoxyhexose.ll6 Reduction of aldose and ketosetosylhydrazones with potassium borohydride is a general reaction, leadingto 1 - and 2-deoxyalditols, respectively.116 The structures of several natur-ally occurring deoxy-sugars have been confirmed by synthesis, includingthose of 2,3,6- trideoxy-D-erythro-aldohexose (amicetose) ,117 2,6-dideoxy-4- 0-methyl-D-galactose (chromose A),ll* 5-deoxy-~-aUose (homoribo~e),~~~ and6-deoxy-2,3-di-O-methyl-~-allose (mycinose).120 5-Deoxy-~-ribose has beensynthesized from 5-deoxy-~-xylose by inversion by an anchimericallyassisted displacement.121 Also, syntheses of 2-deoxy-~-allose,~~~ Ei-deoxy-~-glucose,123 and 3,6-dideoxy-~-galactoseThe trans-diol group of methyl 4,6-O-benzylidene-a-D-glucopyranoside was converted into the alk-2-ene by direct reaction ofhave been reported.Unsaturated sugars.loo J.Kocourek, CoZZ. Czech. Chem. Comm., 1964,29,316; J. Kocourek and V. Jiracek,S. Tejima, T. Maki, and M. Akagi, Chem. and Pharm. BUZZ. (Japan), 1964,12,528.l l 1 K . Tokuyama and M. Kiyokawa, J. Org. Chem., 1964, 29, 1475.112 M. L. Wolfrom, W. A. Cramp, and D. Horton, J . Org. Chem., 1964, 29, 2302.11* G. Casini and L. Goodman, J . Amer. Chem. SOC., 1964, 86, 1427.lI4R. L. Whistler and R. M. Rowell, J . Org. Chem., 1964, 29, 1259; T. van Esand R.L. Whistler, ibid., p. 1087; L. Goodman and J. E. Christensen, ibid., p. 1787.115 M. L. Wolfrom, K. Matsuda, F. Komitsky, and T. E. Whiteley, J . Org. Chem.,1963, 28, 3551.llti A. N. de Belder and H. Weigel, Chem. and Ind., 1964, 1689.11' C. L. Stevens, P. Blumbergs, and D. L. Wood, J . Amer. Chem. SOC., 1964, 86,3592.118 J. S. Brimacombe, D. Portsmouth, and M. Stacey, Chem. and Ind., 1964, 1758.ll0 K. J. Ryan, H. Arzoumanian, E. M. Acton, and L. Goodman, J. Amer. Chem.120 J. S. Brimacombe, M. Stacey, and L. C. N. Tucker, Proc. Chem. SOC., 1964, 83.lal K. J. Ryan, H. Arzoumanian, E. &I. Acton, and L. Goodman, J . Amer. Chem.122 W. Werner Zorbach and A. P. Ollapally, J . Org. Chm., 1964, 29, 1790.123 R. E. Gramera, T. R. Ingle, and R.L. Whistler, J . Org. Chem., 1964, 29, 2074.lZ4 K. Antonakis, Compt. rend., 1964, 258, 5911.Angew. Chem., Internat. Edn., 1964, 3, 62.SOC., 1964, 86, 2503.Soc., 1964, 86, 2497438 ORGANIC CHEMISTRYthe 2,3-di-O-rnethylsulphonate with potassium ethyl anth hate.^^^ A trans-2-0-tosyl-3-deoxy-3-iodo-grouping in a pentopyranoside has also been readilyconverted into an alk-2-ene group.126 Conversion of the 5,6-diol group of1,2-O-isopropy~idene-a-~-g~ucofuranose into the alk-5-ene was achieved byway of the 5,6-thiono~arbonate,l~~ and this reaction may be applicable tocis-diols in pyranose and furanose rings. An exocyclic double bond is formedby the reaction of a 6-0-benzyl-5-0-tosylhexofuranose with a base, a 6-0-benzyl-5-deoxyhexofuran-5-enose being the product .127 A similar reaction,but with a 6-deoxy-analogue, resulted in a furanose propenyl ether (22),hydroboronation of which yielded a gulose derivative.lZ8Me*cHQoMe0 0\ /(22) CMezBranched and higher sugars.Apiose has been identified as a constituentof the marine algz, Zostera marina, and synthesized by a new route.l2OBranched amino-sugars may be prepared by the condensation of dialdehydes(e.q., 23) with nitroethane, followed by reduction,ls* as formulated. A con-OHC koyMe NaOMe E t N 3 2 \ "'QMe + KOOHCMe NO2 Me NH2 (23)figurational correlation of hamamelose and " 01 "-D-ghcosaccharho1actonehas been established.131 The synthesis of noviose, acylnoviosyl halides, andnovobiocin has been reported.132 D-Erythrose undergoes a mixed aldolcondensation with 1,3-dihydroxypropan-2-one, to give D-allo-, D-altro, and~-gluco-heptdoses.~~~ The alkaline epberization of ~-manno-3-heptdoseproceeds via both a 2,3- and a 3,4-enedio1.lS4 Successive reduction anddeamination of 2,3,4,6-tetra-O-acefyl-~-~-ga~sctopyranosyl cyanide yields1 -deoxy-~-gaZacto- heptu10se.l~~GZycosides.Acetylated monosaccharide 1,2-alkyl orthoacetates react126 D. Horton and W. N. Turner, Tetrahedron Letters, 1964, 2531.126 N. F. Taylor and G. M. Riggs, J. Chem. Soc., 1963, 5600.lZ7 R. E. Gramera, T. R. Ingle, and €3. L. Whistler, J. Org. Chem., 1964, 29, 878.12* H. Arzoumanian, E. M. Acton, and L. Goodman, J. Amer. Chem. SOC., 1964,129 D. T. Williams and J. K. N. Jones, Canad. J . Chem., 1964, 42, 69.l30 S.W. Gunner, W. G. Overend, and N. R. Williams, Chem.. and Im?., 1964, 1523.l31A. B. Foster, T. D. Inch, J. Lehmann, and J. M. Webber, J. Chem. SOC., 1964,948.132 B. P. Vaterlaus, J. Kiss, and H. Spiegelberg, HeZv. Chim. Acta, 1964, 47, 381;B. P. Vaterlaus, K. Doebel, J. Kiss, A. I. Rachlin, and H. Spiegelberg, ibirE., p. 390;J. Kiss and H. Spiegelberg, ibid., p. 398; B. P. Vaterlaus and H. Spiegelberg, ibid.,p. 508.88, 74.133 R. Schaffer, J. Org. Chem., 1964, 29, 1471.134 R. Schaffer, J. Org. Chem., 1964, 29, 1473.135 B. Coxon and H. G. Fletcher, J . Anzer. Chem. SOC., 1964, 86, 922HUTSON AND MANNERS: CARBOHYDRATES 439with alcohols in the presence of catalytic amounts of mercuric bromide andtoluene-p-sulphonic acid, giving good yields of the 1,2-trans-glyco~ides.~~~Acetylated glycosyl perchlorates react smoothly with alcohols to giveglycosides.137 Kinetic measurements have confirmed that solvolysis ofglycosyl halides in which a 2-acetoxy-group and a l-halogen atom are cis-related proceeds by an SN1 mechanism; if there is a trans-arrangement ofthese groups, solvolysis involves neighbouring-group participation.An 5,2mechanism operates in reactions with thiophenoxide Condensationof glycofuranose acetates with phenol in the presence of toluene-p-sulphonicacid yields phenyl glycofura,nosides.l39 Glycosidation of N-acyl-D-glucos-amines has been effected by condensation with alcohols in the presence ofboron trifl~oride.1~0 In studies of the acid hydrolysis of glycosides, moreattention has been paid to the effect of various 5-sub~tituents.~~~ Thestabilization effect of a 5-carboxyl group is due to an inductive effect.Electron-attracting substituents in the aglycone have little influence on therate of hydrolysis since the two effects they cause (lowering the equilibriumconcentration of conjugate acid and facilitating heterolysis of the C-0 bond)tend to ~ance1.l~~ The instability of 6-aldehydo-glycosides is probably dueto steric factors caused, in turn, by intramolecular hemiacetal formation.142The reaction of mercury salts of carboxylic acids with l-thioglycosidesaffords a route to 1-0-a~ylaldoses.~~~Complex Glycosides, and Di- and Oligo-saccharides.-“ Hydrol,” themother-liquor of acid hydrolysates of starch remaining after the separationof D-glUCOSe, contains a mixture of oligosaccharides including the tri-saccharides, isomaltotriose, 3-O-isomaltosyl-~-glucose, panose, ‘‘ isopanose,”and a trisaccharide containing both an oc-1,2- and a-1,6-h1kage.l~~ Apolymer-homologous series of methyl p-D-glycosides has been prepared fromcellulose, and the relation between physical properties and degree of poly-merization examined.145 Certain species of gentian contain gentiobiose insuch amounts that acetylation of aqueous-ethanolic extracts readily affordscrystalline gentiobiose octa-acetate ;lac the occurrence of sophorose andrelated oligosaccharides in various species of Sophora has been investigated.l4713* N.K. Kochetlrov, A. J. Khorlin, and A. F. Bochkov, Tetrahedron Letters, 1964,289.13’ Yu.A. Zhdanov, G. A. Korol’chenko, G. N. Dorofeenko, and G. I. Zhungietu,Doklady Akad. hTauk S.S.S.R., 1964, 154, 861.lS8 B. Capon, P. M. Collins, A. A. Levy, and W. G. Overend, J. Chem. Soc., 1964,3242.Is@ H. Borjeson, P. Jerkeman, and B. Lindberg, Acta Chem. Scand., 1963, 17, 170s’;P. Jerkeman and B. Lindberg, ibid., p. 1709.IP0 J. Yoshimura, H. Ando, Y. Takahashi, H. Ono, and T. Sato, J . Chem. SOC.Japan, 1964, 85, 142.141 L. K. Semke, N. S. Thompson, and D. G. Williams, J. Org. Chem., 1964, 29,1041; T. E. Timell, Canad. J. Chem., 1964, 42, 1456; T. E. Timell, Chem. and Ind.,1964, 503.142 0. Theander, Acta Chem. Scand., 1964, 18, 1297.143 H. B. Wood, B. Coxon, H. W. Diehl, and H. G. Fletcher, J.Org. Chem., 1964,29, 461.144 A. Sat0 and H. Ono, Reports Ferna. Res. Imt., Japan, 1963, 147.145 M. L. Wolfrom and S. Haq, TAPPI, 1964, 47, 183.147 R. W. Bailey, Arch. Biochem. Bioplays., 1964, 107, 355.N. Badenhuizen, R. J. Bose, S. Kirkwood, B. A. Lewis, and F. Smith, J. Org.Chern., 1964, 29, 2079440 ORGANIC CHEMISTaYThe condensation products of methyl 4,6-0-benzylidene-a-~-glucopyranosidewith acetobromoglucose include derivatives of sophorose and lamina-ribiose.l** A derivative of a sulphur-containing analogue of gentiobiose [themethyl glycoside of 6-~-~-~-g~ucopyranosy~-6-thio-or-~-g~ucopyranosidehepta-acetate (24)] has been synthesized ;149 the product of deacetylationis an inhibitor of a p-glucosidase.(24) ' OAcNewly synthesized oligosaccharides include: 4,6-di-o-(a-~-glucopyran-OSy1)-D-glUCOpyranOSe (the branch point of glycogen and amylopectin) ;laothe hydrochloride of maltosamine (4- 0-or -D -glucopyranosyl-2-amino-2 -deoxy-a-D-glucopyranose, a hydrolytic fragment of carboxyl-reduced heparin) ;Is1the a- and p-anomers of 2-o-D-g~ucosy~g~ycero~ and 4-O-D-glucosyl-~-ribitol(degradation products of various teichoic acids) ;152 p-D-ribofuranosyl-p-D-ribofuranose;153 maltobiouronic acid (4-0-a-D-g~ucopyranosy~uronic acid-D-glucopyranose) ;154 and pseudocellobiouronic acid (4-O-/?-~-glucopyranosyl-~-glucuronic acid).156 The last derivative is hydrolysed by acid a t about thesame rate as cellobiose.The enzymic transfer of monosaccharide residues from certain donorsubstrates to various acceptors leads to new oligosaccharides or glycosides,e.g. : 6-O-or-ma~tosy~-~-g~ucopyranose from cyclomaltohexaose and isomaltoseby use of Bacillus m e r u n s transglucosylase ;156 a-D-galactosyl-( 1 +6)-trehalose from phenyl a-D-galactoside, trehalose, and a plant-seed extract ;ls7galactosyl-lactose and galactobiosyl-lactose from lactose by an enzymesystem in a growing yeast ;15* various glucosylpentose disaccharides fromphenyl or-D-glucoside, D-xylose, D-ribose, D-Iyxose, or D-arabinose and aprotozoal extract ;159 m-hydroxyphenyl p-D-galactoside or B-D-fucoside fromlactose or o-nitrophenyl p-D-fucoside, resorcinol and E.coli ,6-galactosidase,160148N. Yamoaka, T. Fujita, M. Kusaka, and K. Aso, J . Agric. Chem. Soe. Japan,149 D. H.Hutson, Chem. and Ind., 1964, 750.150 R. de Souza and I. J. Goldstein, Tetrahedron Letters, 1964, 1215.151M. L. Wolfrom, H. El Khadem, and J. R. Vercellotti, Chern. and Id., 1964,152 P. W. Austin, F. E. Hardy, J. G. Buchanan, and J. Baddiley, J . Chem. Soc.,153 J. A. Zderic, Experientia, 1964, 20, 48.154 G. 0. S. Dutton and K. N. Slessor, Canad. J . Chem., 1964, 42, 1110.166 I. Johansson, B. Lindberg, and 0. Theander, Acta Chem. Scand., 1963, 17, 2019.156 D. French, P. M. Taylor, and W. J. Whelan, Biochem. J., 1964, 90, 616.16' E. Guilloux and F. Percheron, Compt. rend., 1963, 257, 545; F. Percheron andE. Guilloux, Bull. SOC. China. b i d , 1964, 46, 543.168 P. A. J. Gorin, J. F. T. Spencer, and H. J. Phaff, Canad. J . Chem., 1964, 42,1341.lSB D.J. Manners and J. R. Stark in ref. 1, p. 518.160 J. B. Pridham and K. Wallenfels, Nature, 1964, 202, 488.1964, 38, 5.645.1964, 2128HUTSON AND MANNERS : CARBOHYDRATES 441and p-hydroxyphenyl p-D-fructofuranoside from sucrose, qubol, and a yeastextract.lsl The action of dextransucrase on sucrose and D-[l~]fructoseyields sucrose labelled in the fructose part, and other [14C]fructose-containingoligosaccharides.162 The enzymic oxidation of sucrose yields /?-D-fmcto-furanosyl-a-~-ribohexopyranoside-3-ulose (ketosucr~se).~~~The isolation of oligosaccharides from partial acidic or enzymic hydro-lysates of polysaccharides continues to provide new information on thestructure of the native polymer. Amongst recent examples are the isola-tion of carrobiose (3,6-anhydro-4-~-~-~-ga~actopyranosy~-~-ga~actose) fromthe methanolysate of an algal polysaccharide,la4 of O-p-D-glucopyranosyl-(1 4)-0-/3-D-glucopyranosyl-( 1 +3)-~-glucose from enzymic hydrolysates oflichenin,l65 of 6-O-~-D-ga~actofuranosy~-D-galactose from a galactan fromMycoplmrna rnycoides,166 and of a serologically active, L-fucose-containingtrisaccharide from human blood-group Lea substance.167Complex glycosides that have been investigated include : Z-acetamido- 1 -p-(~-/?-aspartamido)-l,2-dideoxy-~-glucose from a, partial hydrolysate of anovalbumin glycopeptide preparation ;I68 a rnyoinisitol mannoside from aglycolipid from Mycobacterium tuberculosis ; 169 a phytoglycolipid from avariety of seed phosphatides which on degradation gives a glucosaminyl-glucuronyl-inositol trisaccharide ;I70 ustilagic acid, a fungal glycolipid (shownto be a mixture of di-0-acyl-p-cellobiosides of di- and tri-hydroxyhexa-decanoic acids) ; l 7 l and various mannitol glycosides from Peltigera (lichen)species.172 The glycosides from Peltigera horixontulis contain an uncommonD-galactofuranose residue.Cytolipin-H (N-lignoceroyl-l-sphingosyl-lacto-side) has been synthesized from acetobromolactose.173Polgsaccharides.--GEucans. Studies on the molecular structure ofnaturally occurring glucans have been continued. The cellulose of greencoffee beans has been characterized,l74 and the procedure for acetolysis top-cellobiose octa-acetate improved. Various samples of purified laminarincontain, in addition to #?-1,3-linked D-glucose residues, 2-3% of mannitolwhich is monosubstituted, and a small proportion of /?-1,6-glucosidic inter-chain linkages ; D-mannose is not a component sugar ;I75 the soluble form of161 S.Nakamura and T. Miwa, Nature, 1964, 202, 291.162 E. J. Bourne, J. Peters, and H. Weigel, J . Chem. SOC., 1964, 4605.163 E. E. Grebner, R. Durbin, and D. S. Feingold, Nature, 1964, 201, 419.164 T. J. Painter, J . Chem. SOC., 1964, 1396.165 W. L. Cunningham and D. J. Manners, Biochrn. J., 1964, 90, 596.166 P. Plackett and S. H. Buttery, Biochem. J., 1964, 90, 201.167 V. P. Rege, T. J. Painter, W. 31. Watkins, and W. T. J. Morgan, Nature, 1964,168 H. Tsukamoto, A. Yamamoto, and C . Miyashita, Biochem. Biophys. Res. Comm.,lbS C .E. Ballou and Y . C . Lee, Biochemistry, 1964, 3, 682; Y. C. Lee and C. E.170 H. E. Carter, S . Brooks, R. H. Gigg, D. R. Strobach, and T. Suami, J . Biol.D. E. Eveleigh, C. P. Dateo, and E. T. Reese, J . Biol. Chem., 1964, 239, 839.17% B. Lindberg, B. G. Silvander, and C. A. Wachtmeister, Acta Chem. Scad., 1964,17s D. Shapiro and E. S. Rachaman, Nature, 1964, 201, 878.174 M. L. Wolfrom and D. L. Patin, Agric. Pood Chem., 1964, 12, 376.175 W. D. Annan, Sir Edmund Hirst, and D. J. Manners, J. Chem. Xoc., 1965, 220,204, 740.1964, 15, 151.Ballou, J . Biol. Chem., 1964, 239, 1316.Chern., 1964, 239, 743.18, 213.885; M. Fleming and D. J. Manners, Biochem. J., 1965, 94, 17P442 ORGANIC CHEMISTRYlaminarin has a higher degree of branching than the insoluble form.l75 Man-goes contain an a-glucan for which the partial structure (25) has beenproposed, although this is not compatible with the observed resistance todiastase.176 Polyporus giganticus synthesizes a mixture of polysaccharidesincluding an cc-glucan of the glycogen type.177-[4 Gp 119-4 @ 1-61I ( 2 5 )GP 1-r3 GP19Methods for the fractionation of amylomaize starch by forming acomplex of the amylose with fatty acids and alc~hols,l'~ and of potato starchby using hydrophobic compounds such as hydrocarbons and halogenatedhydrocarbons, have been studied,l79 and conditions for the large-scalepreparation of Schardinger dextrins have been devised.180Several derivatives of amylose and cellulose have been prepared, includingamylose containing amino-groups at position 2 or 6,l8l or entirely at position6 ,l 82 6 - deox yam ylose - 6 - sulp honic acid , 83 and 6 - deoxy- 6 - hy dr azino - am ylit 01and -~ellulose.~~~ The oxidation of cellulose analogues by alkaline hypo-chlorite has been studied kineti~al1y.l~~ Various esters of cotton cellulosewere prepared by esterification with acid chlorides in dioxan at 80" inpresence of varying amounts of pyridine.186A critical physicochemical study has shown that the degradation ofamylose by /&amylase and phosphorylase proceeds by multi-chain action.ls'Enzymically synthesized amylose is more stable in aqueous solution thanis natural amylose, and also differs in heterogeneity and in rate of changeof degree of polymerization on enzymic degradation.l8s In solution, theconformation of amylose has been approximated to '' a relatively stiff worm-like coil consisting of an imperfect or deformed helical backbone."183 Micro-methods for the enzymic determination of glycogen have been devised.lgOAmylopectin is converted into a polysaccharide of glycogen type by branch-ing enzyme preparations from Arthrobacter globifornzis lS1 and sweet corn(Zea mays).192176A. Das and C.V. N. Rao, TAPPI, 1964, 47, 339.17' V. P. Bhavanandan, H. 0. Bouveng, and B. Lindberg, Acta Chem. Scad., 1964,178 R. A. Anderson, C. Vojnovich, and G. Soedomo, Starke, 1963, 15, 355.1 7 9 D. French, A. 0. Pulley, and W. J. Whelan, Sturke, 1963, 15, 349.la0 D. French, A. 0. Pulley, and W. J.Whelan, Stiirke, 1963, 15, 280.lal M. L. Wolfrom, M. I. Taha, and D. Horton, J. Org. Chem., 1963, 28, 3553.la3 R. L. Whistler and D. G. Medcalf, Arch. Biochem. Biophys., 1964, 105, 1.185 M. L. Wolfrom and W. E. Lucke, TAPPI, 1964, 47, 189.l a 6 R. Riemschneider and J. Sickfeld, Monatsh., 1964, 95, 194.lS7 E. Husemann and B. Pfannemiller, Makromol. Chem., 1963, 69, 75.E. Husemann, W. Burchard, and B. Pfannemiiller, Starke, 1964, 16, 143.V. S. R. Rao and J. F. Foster, Biopolymers, 1963, 1, 527.lgo E. Bueding and J. T. Hawkins, Analyt. Biochem., 1964, '4, 26.lgl L. P. T. M. Zevenhuizen, Biochinz. Biophys. Acta, 1964, 81, 608.lsa N. Lavintman and C. R. Krisman, Biochim. Biophys. Acta, 1964, 89, 193;18, 504.R. L. Whistler and D. G. Medcalf, Arch.Biochem. Biophy8., 1964, 104, 150.R. 1;. Whistler and B. Shasha, J. Org. Chem., 1964, 29, 880.D. J. Manners and J. J. M. Rowe, Chem. and Ind., 1964, 1834HUTSON AND MANNERS: CARBOHYDRATES 443The products of the partial acetolysis of certain dextrans,lg3 and particu-larly those with serotype A reactivity,lg4 include kojibiose, thus providingdefinite evidence for its containing a proportion of a-l,2-glucosidic linkages.These linkages are absent from serotype B dextrans.lg4 The kinetics of theacid hydrolysis of one dextran sample approximated to that of the randomsplitting of a statistically branched p01ymer.l~~Synthetic glucans prepared by thermal polymerization of glucose underacidic conditions are highly branched polymers lg6 containing both pyranoseand furanose residues.197 In the absence of a catalyst, a mixture of eightglucose disaccharides, 1,6-anhydroglucose, panose, and isomaltotriose isproduced.138HemiceZZuZoses.Most xylans consist of a main chain of /l-1,4-linkedD-xylopyranose residues to which various side chains are attached. In thexylan from pea-skin (Pisum sativum), single L-arabinofuranose residues areattached at position 3 as side chains.lg9 The tropical pasture grass GiantStar (Cynodort plectostachyus) contains a xylan with side chains of L-arabino-furanose or aldobiouronic acid residues.200 The xylan from bagasse resemblesthat from esparto grass in having a branched main chain, with a single 1,3-xylosidic inter-chain linkage.201Centrosema seeds synthesize a polysaccharide containing D-galactose(93%) and L-arabinose (7%) and having a complex branched structure witha preponderance of 1,4-linkages ;20z PoZyporus giganticus produces a /l-1,6-galactan with side chains of 3-O-~-~-mannopyranosyl-~-~-fucopyranose.~~~Bluebell seeds (ScyZZa nonscripta L.) contain a glucomannan which is a linearpolymer of /I- 1,4-1inked D-glUCOpyELnOSe and D-mannopyranose residues inthe ratio 1 : 1.3.203 The galactomannan of white-clover seeds ( TrifoZiumwpens L.) consists of a main chain of p-1,4-linked D-mannose residues towhich are attached, at position 6, single cc-D-galactopyranose residues.204The reserve polysaccharide of huacra pona palm seeds is also a p-1,4-linkedmannan, but it contains small amounts of D-galactose, and probably 1,6-linkages.205 A p-1,4-linked mannan has been isolated from the green sea-weed, Codiurn fragile, where it is accompanied by a water-soluble sulphatedpolysaccharide composed mainly of L-arabinose, D-galaCt,OSe, and galactose4- and 6-mono~ulphate.~~~A glucomannan has been isolated and purified from white spruce pulp;the nitrate ester had a degree of polymerization of 70.207 Oxidation of thelg3 M.Torii, E. A. Kabat, and S. Beychok, Arch. Biochem. Biophys., 1963, 103, 283.194 H. Suzuki and E. J. Hehre, Arch. Biochem. Biophys., 1964, 104, 305.lg5 E. Antonini, L. Bellelli, M. L. Bonacci, M. R. Bruzzesi, A. Caputo, E. Chiancone,lg6 P. S. O’ColIa and E. E. Lee, J. Chem. SOC., 1964, 2351.19’ G. G. S. Dutton and A. M. Unrau, Canad. J.Chem., 1964, 42, 2048.lg8 H. Sugisawa and H. Edo, Chem. and Iiz-d., 1964, 892.lgg N. Banerji and C. V. N. Rao, Austral. J . Chem., 1964, 17, 1059.2oo R. J. McIlroy, J. Chem. Soc., 1963, 6067.201 B. C. Banerjee, S. Bose, and S. Mukherjee, J. Indian Chem. Soc., 1964, 41, 323.*02A. &.I. Gnrau, Canad. J. Chem., 1964, 42, 916.203 J. L. Thompson and J. K. N. Jones, Canad. J. Chem., 1964, 42, 1088.204 K. F. Horvei and A. Wickstrom, Acta Chenz-. Xcand., 1964, 18, 533.205 W. Sow& and J. K. N. Jones, Canad. J. Chem., 1964, 42, 1751.206 J. Love and E. Percival, J. Chem. SOC., 1964, 3338, 3345.207 J. M. Vaughan and E. E. Dickey, TAPPI, 1964, 47, 142.and A. Rossi-Fanelli, Biopolymers, 1964, 2, 35.444 ORGANIC CHEMISTRYglucomannan with lead tetra-acetate, followed by mild acid hydrolysis, gaveD-mannose, D-glucose, cellobiose, and 4-0-~-~-glucopymnosyl-~-mannose.A polysaccharide from the xylem sap of white birch contains D-mannOfUranOSeresidues, a- 1,3-linked D-mannopyranose residues, and 1,3-1inked D-galaCtO-pyranose residues, together with D-ghcopyranose and D-glUCUrOniC acid non-reducing e n d - g r o ~ p s .~ ~ ~ Sugar maple (Acer saccharum) sapwood containsa mixture of a water-soluble glucomannan, a 4-O-methylglucuronoxylan,and an arabinogalactan.210 From the bark of Engelmann spruce (Piceaengelmanni) a mixture of a branched B-1,4-glucan, an arabino-4-O-methyl-glucuronoxylan, and an alkali-soluble galactoglucomannan has beenisolated.211 Pollen grains of mountain pine (Pinus mugo Turra) contain amixture of polysaccharides including a #?-l,S-glucan, a polymer of D-xyloseand D-galacturonic acid, and a heteropolysaccharide composed of L-arab-hose (80%) with smaller amounts of glucuronic acid, D-galactose, andL-rhamnose.2lZPolyuronides. Studies of the component sugars of several plant gums havebeen reported, including Jeol gum,213 and the gums from Carapa procera,214Albixzia procera,215 Commiphora muku1,216 and Chloroxylon ~wieteina.2~7Full details of a partial acid-hydrolysis study of reduced alginic acid haveappeared; the term '' alginic acid " should be used to describe a family ofpolymers containing varying proportions of D-mannuronic and L-guluronicacid.2l8 Solutions of alginate are unstable in the presence of reducing agents,e.g., ascorbic acid, the intrinsic viscosity decreasing rapidly even at 20" andpH 6.219 In certain algze, e.g., Ascophyllum nodosum, alginate may bebound to an acidic polysaccharide (ascophyllan),220 but can be separated byfree- boundary electrophoresis.221 A pathogenic Pseudomonas micro-organism produces a polyuronide containing both mannuronic and guluronicacid and very similar to alginic acid.Z22Substantial progress on the structural analysis of the major mucopoly-saccharides of animal tissues has been made, after difliculties due to thepresence of both uronic acid and sulphate ester groups had been overcome.Partial acid hydrolysis and methylation studies of desulphated, carboxyl-reduced heparin show the presence of an alternating sequence of 1,4-linkedD-glUCUrOniC acid and 2-amino-2-deoxy-~-glucose 224 Methano-208 J.M. Vaughan and E. E. Dickey, J . Org. Chem., 1964, 29, 715.209 B. Urbas, G. A. Adams, and C. T. Bishop, Canad. J . Chem., 1964, 42, 2093.210 G. A. Adams, Svensk Papperstidn., 1964, 67, 82.211 K. V. Ramalingam and T. Timell, Svensk Papperstidn., 1964, 67, 512.212 H. 0. Bouveng, Ph,ytochemistry, 1964, 2, 341.21s A. K. Bhattacharyya and C. V. N. Rao, Canad. J . Chem., 1964, 42, 107.214 I. Cole, Nature, 1964, 202, 1109.215 M. I. H. Farooqi and K. N. Kaul, Indian. J . Chem., 1963, 1, 542.216 S. Bose and K. C. Gupta, Indian J. Chem., 1964, 2, 57, 156.217 S. Bose, N. N. Mody, and S. Mukherjee, J . Indian Chem. SOC., 1964, 41, 173.218 E. L. Hirst, E. Percival, and J.K. Wold, J. Chm. Soc., 1964, 1493.21B 0. Smidsrod, A. Haiig, and B. Larsen, Actu Chem. Scand., 1963, 17, 2628.220 A. Haiig and B. Larsen, Actu Chem. Scand., 1963, 17, 1653.221 B. Larsen and A. Haug, Actu Chem. Scand., 1963, 17, 1646.222 A. Linker and R. S. Jones, Nature, 1964, 204, 187.228 M. L. Wolfrom, J. R. Vercellotti, and G. H. S. Thomas, J . Org. Chem., 1964,29, 536; M. L. Wolfrom, J. R. Vercellotti, and D. Horton, ibid., pp. 540, 547.A. B. Foster and J. M. Webber, Biochem. J., 1964, 91, 1PHUTSON AND MANNERS : CARBOHYDRATES 445lysis of hyaluronic acid yields a derivative of 2-amino-2-deoxy-3-0-B-~-glucuronosyl-cc- D - glucopyranose ,225 which has been synthesized ; 22 this,together with previous evidence, establishes the presence of an alternatingsequence of D-g~ucuronic acid and N-acetyl-D-glucosamine linked at positions4 and 3, respectively.A 1,4-1inked 2-amino-2-deoxy-D-galactoside di-saccharide has been isolated from the hydrolysate of N-deacetylated,carboxyl-reduced chondroitin, prepared from chondroitin sulphate C.227225 R. W. Jeanloz and D. A. Jeanloz, Biochemistry, 1964, 3, 121.226 H. M. Flowers and R. W. Jeanloz, Biochemistry, 1964, 3, 123.227 K. Onodera, T. Komano, and S. Hirano, Biochim. Biophys. Acta, 1964, 83, 2013. NUCLEIC ACIDSBy T. L. V. Ulbricht(Twyford Laboratories, Elveden Road, London, N . W.10)IN the indices of Chemical Abstracts for 1963 there are some 3,400 entriesfor nucleic acids under general headings alone (such as “nucleic acids,”“ nucleotides,” etc.) and there is little doubt that well over 10,000 papershave been published in this field since the last review in these Reports.1During that time, there has been a notable revival of interest in the chemistryof nucleosides, partly stimulated by the discovery of new nucleoside anti-biotics; much effort has been devoted to the synthesis of 3‘,5’-linked oligo-and poly-nucleotides and valuable information has been derived from furtherstudies of nucleic acids and their derivatives by specialized physical methods.Tremendous activity on the biochemical side has clarified our understa.ndingof the biosynthesis of the nucleic acids and of proteins.A welcome feature,at a time when new journals continually appear, has been the concentrationof the most important biochemical papers in a very few journals.2 A newseries of occasional reviews has been la~nched.~ The chemistry of nucleicacids has been discussed in a comprehensive monograph,* more briefly aspart of a series on biochemistry,6 and in a short introductory book forstudents ;g the first book exclusively devoted to nucleohistones has appeared.’It was, however, an eminent authority of an older generation who producedthe most critical, amusing, and provocative book.*Bases.-In further studies of the effects of ultraviolet radiation onnucleic acid bases, it has been shown that reversible formation of thyminedimers occurs between adjacent residues in dithymidylic and polythymidylicacid,g indicating that dimer formation in DNAlO probably occurs betweenadjacent residues in one polynucleotide strand. In radiation-resistantstrains of Escherichia coli, thymine dimers disappear from the acid-insoluble(i.e., polynucleotide) cell-fraction and appear in the acid-soluble fraction,1 T.L. V. Ulbricht, Ann. Reports, 1962, 59, 371.J . Mol. Biol., Proc. Nut. Acad. Sci. U.S.A., and the specialized issues of Biochinz.Biophys. Acta.3 “ Progress in Nucleic Acid Research ”, ed. W. E. Cohn and J. N. Davidson,Vol. I (1963), Vol. I1 (1964), Academic Press, New York.4 A. M. Michelson, “ The Chemistry of Nucleosides and Nucleotides ”, AcademicPress, New York, 1963.6 D. M. Brown and T. L. V. Ulbricht, “ Nucleic Acids ”, in “ ComprehensiveBiochemistry ”, ed. by M. Florkin and E.H. Stotz, Vol. VIII, Elsevier, Amsterdam,1963.13 T. L. V. Ulbricht, “ Purines, Pyrimidines and Nucleotides ”, Pergamon Press,Oxford, 1964. ’ “ Nucleohistones ”, ed. J. Bonner and P. Ts’o, Holden-Day, San Francisco, 1964. * E. Chargaff, “ Essays on Nucleic Acids ”, Elsevier, Amsterdam, 1963 (see reviewby T. L. V. Ulbricht, Chem. and Ind., 1964, 640).R. A. Deering and R. B. Setlow, Biochem. Biophys. Acta, 1963, 68, 526.10 Abbreviations : DNA, deoxyribonucleic acid; RNA, ribonucleic acid; s-RNA,soluble (transfer) RNA; m-RNA, messenger RNA; A, adenylic acid; C, cytidylic acid;G, guanylic acid; U, uridylic acid; similarly polyA, polyUULBRICHT: NUCLEIC ACIDS 447whereas they remain in the acid-insoluble fraction in radiation-sensitivestrains.11 Thus, the enzymic removal of ‘‘ injured ” bases, including dimers,and the reconstruction of the DNA from information in the complementarystrand, appear to be the basis of resistance to radiation and may be animportant biological mechanism for the preservation of DNA.Ultra-violet radiation causes significant deamination of cytosine to uracil inaqueous solution.12 Photochemical addition (at wavelengths above 320 mp)of benzopyrene to nucleic acid pyrimidines-probably at the 4,5-doublebond-and to guanine has been reported.13 Similarly, a covalent linkagebetween benzopyrene and DNA is generated by irradiation at the absorptionband of ben~0pyrene.l~The Bacillus subtilus phage PBS2 contains deoxyuridine in place ofthymidine in its DNA15 and also contains glucose, associated with thedeoxycytidine and deoxyguanosine fractions, but the structure of theglucosylated nucleosides is not yet knomn.16 Another B.subtilis phage,$e, contains 5-hydroxymethyluracil in place of thy1nine.l‘ Additionalbases found in yeast s-RNA are 1 -methyluracil, 1 -methylcytosine, hypo-xanthine, l-methylhypoxanthine, and N6-arninoacyladenines.l8Many studies have appeared of the alkylation of nucleic acid bases andtheir derivatives.lg-z6 Jones and Robins 21 showed that, in the absence ofalkali, guanosine, 2’-deoxyguanosine, inosine, and xanthosine are all alkyl-ated at N-7 and adenosine at N-1, and they related these results to evidenceconcerning the site of protonation in these nucleosides. Imidazole ring-opening in N7N9-disubstituted purines, and the instability of 7-substitutedguanosines in particular, have been reported by several workers.lg~ 21 Inthe presence of alkali, however, inosine,21, 22 guanosine, and 2’-deoxyguanos-ine 23 are alkylated at N-1.It has also been shown 23 that “ l-methyl-2’-deoxyguanosine ” 24 is the 1,7-dimethyl compound, and that thel1 R. B. Setlow and W. L. Carrier, Proc. Nut. Acad. Sci. U.S.A., 1964, 51, 226;R. P. Boyce and P. Howard-Flanders, ibid., p. 293.l2 M. Daniels and A. Grimison, Biochem. Biophys. Res. Comm., 1964, 16, 428.la J. M. Ryce, J . Anaer. Chem. SOC., 1964, 86, 1444.l4 P. 0. P. Ts’o and P. Lee, Proc. Nut. Acad. Sci. U.S.A., 1964, 51, 272.l5 I. Takahashi and J. Marmur, Nature, 1963, 197, 794.l6 I. Takahashi and J.Marmur, Biochem. Biophys. Res. Comm., 1963, 10, 289.l7 D. H. Roscoe and R. G. Tucker, Biochem. Biophys. Res. Comm., 1964, 16, 106.R. H. Hall, Biochem. Biophys. Res. Comm., 1963, 12, 361; 1963, 13, 394; idem,Biochemistry, 1964, 3, 769.lS J. A. Haines, C. B. Reese. and Lord Todd, J . Chem. SOC., 1962, 5381; E. Kriekand P. Emmelot, Biochemistry, 1963, 2, 733; P. D. Lawley and P. Brookes, Biochem. J..1963, 89, 138.2o T. C. Myers and L. Zeleznick, J . Org. Chem., 1963, 28, 2087; B. C. Pal andC. A. Horton, J . Chem. SOC., 1964, 400; P. N. Magee and K. Y . Lee, Biochem. J., 1964,91, 35; J. A. Haines, C. B. Reese, ar,d Lord Todd, J . Chem. SOC., 1964, 1406; E. Kriekand P. Emmelot, Biochim. Biophys. Acta, 1964, 91, 59; M. Adler and A. B. Gutman,Nature, 1964, 204, 681.*l J.W. Jones and R. K. Robins, J . Amer. Chem. SOC., 1963,85,193; L. B. Townsendand R. I<. Robins, ibid., p. 242.32 E. Shaw, J . Amer. Ckem. SOC., 1958, 80, 3899; 1961, 83, 4770.23 A. D. Broom, L. B. Townsend, J. W. Jones, and R. K. Robins, Biochemistry,1964, 3, 494.24 0. M. Friedman, G. N. Mahapatra, and R. Stevenson, Biochirn. Biophys. Actu,1963, 68, 144.25 P. Brookes and P. D. Lawley, J. Chem. SOC., 1960, 563.z 6 P. D. Lawley and P. Brookes, Biochem. J . , 1964, 92, 19C448 ORGANIC CHEMISTRY" 1,3-dimethyladenine " of Brookes and Lawley 25 is the 3,7-isomer. Thelatter workers 26 have reported that alkylated DNA at neutral pH splits off,not only 7-methylguanine and 3-methyladenine, but also 7-methyladenine.Another reaction which has been studied with derivatives of the bases,including RNA, is hal~genation.~' On using bromine water, it was foundthat the reaction of the free bases and of their nucleotides in s-RNA issimilar: uracil and cytosine react readily, guanine less readily, and adeninenot at all.At a bromination level at which approximately one uraciland one cytosine per s-RNA chain are brominated, the inhibitory effecton the formation of phenylalanine-s-RNA is 67%, suggesting that thesequence responsible for recognition by phe-s-RNA synthetase contains atleast one bromine-sensitive residue, and therefore cannot be AAA as hadbeen suggested.28Nuc1eosides.-The reaction of the chloromercuri-derivative of 6-ethoxy-2-hydroxypyrimidine (1) with acetobromoglucose, reported to give theN-gluc~side,~~ has been shown to give the O-glucoside,3° which can berearranged to the N-glucoside with mercuric bromide.This confirms thesuggestion31 that salts such as (1) are O-derivatives and give N-glucosidesand N-ribosides by rearrangement, as has now been demonstrated in anumber of cases.32, 33 Reactions with glycosyl halides derived from 2-deoxy-~ugars,~3, on the other hand, indicate that O-deoqribosides arevery unstable and that N-deoxyribosides cannot be formed by rearrange-ment, in agreement with the fact that the latter derivatives are onlyobtainedwhen a different kind of heavy-metal salt is used.31E t 3 S i . 0 SiEt3 yy" N ?ClHgO fi Et,Si*O \ NSiEt3 ('1 (2)The fact that adenine, in the absence of alkali, is alkylated at N-3, hasbeen exploited in nucleoside synthesis.Thus, from the reaction of adeninewith tri-0-benzoylribofuranosyl bromide one obtains 25 yo of the N3-nucleo-side, and also lSYo of adenosine;35 3-benzyladenine is an intermediate in thefirst synthesis of the nucleoside from pseudovitamin B12, 7-a-ribofuranosyl-adenine .3627 K. W. Brammer, Biochim. Biophys. Ada, 1963,72,217; D. Lipkin, F. B. Howard,D. Nowotny, and M. Sano, J . Biol. Chem., 1963, 238, PC 2249; R. E. Holmes andR. K. Robins, J . Amer. Chem. SOC., 1964, 86, 1242.a * C. Yu and P. C. Zamecnik, Biochim. Biophys. A&, 1963, 76, 209.2e J. J. Fox, N. Yung, I. Wempen, and I. L. Doerr, J . Amer. Chem. SOC., 1957,79, 5060.3O T. Ukita, H. Hayatsu, Y .Tomita, Chem. and Pharm. Bull. (Japan), 1963,11,1068.31 T. L. V. Ulbricht, Angew. Chem., 1962, 74, 767.32 T. L. V. Ulbricht, Proc. Chem. SOC., 1962, 298, G. Wagner and H. Pischel, Arch.Phurm., 1962, 295, 373; G. Wagner and D. Heller, Naturwiss., 1963, 50, 497; T. Ukita,R. Funakoshi, and Y. Hirose, Chem. and Pharm. Bull. (Japan), 1964, 12, 828.a3 T. L. V. Ulbricht, Abs. I.U.P.A.C. Symposium on Natural Products, 1964.3 4 M. Hoffer, Chem. Ber., 1960, 93, 2777; W. W. Zorbach and G. J. Durr, Jr.,J . Org. Chem., 1962, 27, 1474.35 N. J. Leonard and R. A. Laursen, J . Amer. Chem. SOC., 1963, 85, 2026.36 J. A. Montgomery and H. J. Thomas, J . Amer. Chem. SOC., 1963, 85, 2672ULBRICHT: NUCLEIC ACIDS 449A new method of nucleoside synthesis, which consists of fusing a fullyacetylated sugar with the heterocyclic base and an acid catalyst, is mostsuccessful with purines and is supposed to yield p-nucleosides;37 from theconditions of the reaction, however, one might expect both anomers to beformed, as later found in some cases.38 Both anomers are obtained in asimilar reaction when using acetylated glycals,39 and also in the Hilbert-Johnson reaction 4O which had previously been believed to be stereospecific.Since syntheses from 2-deoxy-sugars also yield anomeric mixtures,31 it hasbecome increasingly important to be able to distinguish between u- andp-anomers : this can readily be done by using optical rotatory dispersion (seebelow), use of which has also clarified the applicability of Hudson’s isorota-tion rules to nucle~sides.~~A second new method of nucleoside synthesis is an extension of Birkofer’swork on heterocyclic trimethylsilyl derivatives 42 and the synthesis of thenatural nucleoside, uric acid 3-riboside, from tetrakistriethylsilyluric acid(2) 43 (this nucleoside has also been synthesized by an unambiguous but muchmore complex route 4”).In general, trimethylsilyl derivatives of purines andpyrimidines are treated with the glycosyl halide with or without solvent;the silyl protecting groups are removed by treatment with aqueous alcoholand good yields of nucleosides are claimed, both anomers being obtained insome cases.45The synthesis of 2’-deoxyadenosine using polyphosphate ester 46 hasbeen shown to give a mixture of at least six products and to lack stereo-specificity,*‘ as would be expected on mechanistic grounds.31 The firstsyntheses of 2’-deoxy-5-hydroxymethylcytidine 48 and of a 9-glycoside oftheophylline 49 have been reported.A new glycosyl halide, 2,3,5-tri-O-benzyl-D-arabinofuranosyl chloride, promises to be useful for the synthesisof ~-arabinofi~anosides,~~ which are of interest because of their biologicalactivity (for example, cytosine arabinoside inhibits the growth of DNAviruses and of tumours; it appears to interfere with the metabolic conversion57 Y. Ishido and T. Sato, Bull. Chenz. Soc. Japan, 1961, 34, 1347; T. Shimidate,Y. Ishido, and T. Sato, Nippon Kagaku Zmshi, 1961, 82, 938 (Chem. Abs., 1962, 57,15216); T. Shimidate, ibid., p. 1268 (Chem.A h . , 1962, 57, 16726).s8 W. W. Lee, A. P. Martinez, G. L. Tong, and L. Goodman, Chem. and Ind.,1963, 2007.s9 W. A. Bowles and R. K. Robins, J. Amer. Chem. SOC., 1964, 86, 1252.40 J. Farkas, L. Kaplan, and J. J. Fox, J . Org. Chem., 1964, 29, 1469.41T. R. Emerson and T. L. V. Ulbricht, Chem. and Ind., 1964, 2129.42 L. Birkofer and A. Ritter, Angew. Chem., 1959, 71, 372; L. Birkofer, P. Richter,and A. Ritter, Chem. Ber., 1960, 93, 2804; L. Birkofer, H. P. Kiihltau, and A. Ritter,ibid., p. 2810.43 L. Birkofer, A. Ritter, and H. P. Kiihltau, Chem. Ber., 1964, 97, 934.c* R. Lohrmann, J. M. Lagowski, and H. S. Forrest, J. Chem. SOL, 1964,451.45 T. Nishhura, B Shimizu, and I. Iwai, Chem. an& Pharm. Bull. (Jupan), 1963,11, 1470; T. Nishimura and I.Iwai, ibid., 1964, 12, 352; T. Nishimura and I. Iwai,ibid., p. 357; T. Nishimura and B. Shimizu, Agric. Biol. Chem., 1964,28,224; E. Witten-burg, 2. Chem., 1964, 4, 303.48 G. Schramm, H. Grotsch, and W. Pollmann, Angew. Chem., Internat. Edn.,1962, 1, 1.4 7 J. A. Carbon, Chem. and Ind., 1963, 529.48 R. Brossmer and E. R o b , Angew. Chem., Internat. Edn., 1963, 2, 742.E. Biihler and W. Pfleiderer, Angew. Chem., Internat. Edn., 1964, 3, 638.C. P. J. Glaudemans and H. G. Fletcher, Jr., J. Org. Chem., 1963, 28, 3004450 ORGANIC CHEMISTRYof cytidine into 2'-deoxycytidine 5l). A number of 2',3'-dideoxynucleosideshave been ~ynthesized.~~ Interest in these compounds has undoubtedlybeen stimulated by the discovery that the antibiotic, amicetin, is a 2',3'-dideoxynucleoside derivative 53 and that the long-known antibiotic, cordy-~ e p i n , ~ ~ is in fact S'-deo~yadenosine~~ which had previously been syn-thesized 56 and may also be prepared from 3-deo~yribose.~' Cordycepinis biosynthesized from adenosine 58 and is converted into the triphosphate,which inhibits purine biosynthesis de novo 59 and also RNA synthesis.60Other nucleoside antibiotics include tubercidin (3; R = H) (the P-D-ribofbranoside of a 7-dea~apurine),~l and its cyano-derivative, toyocamycin 62(3; R = CN).Angustmycin A and decoyinine have been shown 63 to be thesame compound (4), and angustmycin C is identical with psicofuranine.64(3) HO OH HO OH (4)Several cytosine-containing nucleoside antibiotics, blasticidin S, cyto-mycin,66 and g~ugerotin,~' have also been reported.Two naturally occurring51 J. S. Evans, L. Bostwick, and G. D. Mengel, Biochem. Pharm., 1964, 13, 983;J. S . Evans and G. D. Mengel, ibid., p. 989.5 2 C. L. Stevens, N. A. Nielsen, and P. Blumbergs, J . Amer. Chem. SOC., 1964, 86,1894; J. P. Hurwitz, J. Chua, I. L. Klundt, M. A. Dmooge, and M. Noel, &id., p. 1896;M. J. Robins and R. K. Robins, ibid., p. 3585.53 C. L. Stevens, P. Blumbergs, and F. A. Daniher, J . Amer. Chem. Soe., 1963,85, 1552.5 4 H. R. Bentley, K. G. Cunningham, and F. S. Spring, J . Chem. SOC., 1951, 2301.55 E. A. Kaczka, N. R. Trenner, B. Arison, R. W. Walker, and K. Folkers, Biochem.Biophys. Res. Comm., 1964, 14, 456.56 Sir Alexander Todd and T. L. V.Ulbricht, J . Chem. Soc., 1960, 3275; W. W. Leo,A. Benitez, C. D. Anderson, L. Goodman, and B. R. Baker, J . Amer. Chem. SOC., 1961,83, 1906.5 7 E. Walton, R. F. Nutt, S. R. Jenkins, and F. W. Holly, J . Amer. Chem. Soc.,1964, 86, 2952.5 8 R. J. Suhalolnik, G. Weinbaum, and H. P. Meloche, J . Aww. Chem. SOC., 1964,80, 948.59 K. Overgaard-Hansen, Biochim. Biophys. Acta, 1964, 80, 504.6 o S. Frederiksen and H. Klenow, Biochem. Biophys. Res. Comm., 1964, 17, 165.61 K. Anzai, G. Nakamura, and S . Suzuki, J . Antibiotics (Tokyo), 1957, 10, A , 201;S . Suzuki and S. Marumo, ibid., 1960,13, A , 360; 1961,14, A , 34; Y. Mizuno, M. Ikehara,K. Watanabe, and S. Suzaki, Chem. and Pham. Bull. (Japan), 1963, 11, 1901; Y .Mizuno, M. Ikehara, K. A. Watanabe, S.Suzaki, and T. Itoh, J . Org. Chem., 1963,28, 3329.6 2 H. Nishimura, K. Katagiri, K. Sato, M. Mayama, and N. Shimaoka, J . Anti-biotics (Tokyo), 1956, 9, A , 60; K. Ohkuma, ibid., 1960, 13, A , 361; 1961, 14, A , 343.63 H. Hoeksema, G. Slomp, and E. E. van Tamelen, Tetrahedron Letters, 1964,1787.64 H. Yuntsen, J . Antibiotics (Tokyo), 1958, 11, A , 244.6 5 S. Takeuchi, K. Hiramaya, K. Ueda, H. Sakai, and H. Yonehara, J . Antibiotics66 N. Tanaka, Y . Sakagami, T. Nishimura, H. Yamaki, and H. Umezawa, J .67 H. Iwasaki, J . Pharm. SOC. Japan, 1962, 82, 1358.(Tokyo), 1958, 11, A , 1.Antibiotics (Tokyo), 1961, 14, A , 123ULBRICHT: NUCLEIC ACIDS 451aminonucleosides, in addition to the well-known antibiotic puromycin,have biological activity ; 3’-amino-3’-deoxyadenosine is an antitumouragent,68 and 3’-deoxy-3’-homocitrullylaminoadenosine inhibits proteinsynthesis apparently similarly to puromycin.6pDefinitive evidence for the presence of 2‘-O-methylnucleosides in RNAhas been presented. Enzymic digestion of alkali-stable nucleotide fractionsfrom RNA gives 2’-O-methylguanosine and, probably, 2 ’- O-met hylcytidine. 702‘-O-Methylnucleosides from yeast RNA have been described 71 and shownto be present to the extent of 1% in both s-RNA and ribosomal RNA.72The 2’-O-methyl ethers of all the 5’-mononucleotides have been isolatedby degradation of yeast RNA, and the 2’-O-methyl structure proved.73An isomer of guanosine, called neoguanosine, has been obtained from com-mercial samples of guanylic acid and from acid-treated RNA ;7* spectro-scopic and other evidence has been interpreted in terms of a guanine N1-or N2-riboside ~tructure.‘~, 75Nucleotides and Oligo- and Poly-nuc1eotides.-Nucleoside diphosphatesugars have been reviewed.The synthesis of aminoacyl-nucleotideanhydrides from amino-acid ethyl carbonate anhydrides has been reported,77and Michelson has also published details of his synthesis of nucleotide anhy-drides by anion-exchange.78 The last -mentioned remains the best generalmethod of synthesis for nucleotide anhydrides ; examples given includeco-enzyme A (63 yo yield), adenosine diphosphate glucose (82 %), flavinadenine dinucleotide (70-80 %), guanosine diphosphate (80-85 %), andadenosine triphosphate (77 yo).78 High yields of nucleoside triphosphatescan also be obtained by a modification of the phosphoromorpholidateniethod.79Many papers have appeared on the synthesis of 3’,5‘-linked oligonucleo-tides of defined sequence, including studies of suitable protecting groups 80, 816 9 A.J. Guarino, M. L. Ibershof, and R. Swain, Biochim. Biophys. Acta, 1963,71 R. H. Hall, Biochim. Biophys. Acta, 1963, 68, 278.7 2 R. H. Hall, Biochemistry, 1964, 3, 876.73 M. Honjo, Y. Kanai, Y. Furukawa, Y . Mizuno, and Y . Sanno, Biochina. Biophys.’* W. F. Hemmens, Biochim. Biophys. Acta, 1963, 68, 284; 1964, 91, 332.7 6 R. Shapiro and C . N. Gordon, Biochem. Biophys. Res. Comm., 1964, 17, 160.‘13 E. Cabib, Ann. Rev. Biochem., 1963, 32, 321; L. F. Leloir, Biochem.J., 1964,7 7 A. 31. Michelson and R. Letters, Biochim. Biophys. Acta, 1964, 80, 242.7 8 A. 31. Michelson, Biochim. Biophys. Acta, 1964, 91, 1; 1964, 93, 71.i9 J. G. Moffatt, Canad. J . Chem., 1964, 42, 599.8o F. Cramer, R. Wittmann, K. Daneck, and G. Weimann, Angew. Chem., Internat.Edn., 1963, 2, 43.81 Y. Lapidot and H. G. Khorana, J . Amer. Chem. Soc., 1963, 85, 1363; R. H.Hall and R. Thetford, J . Org. Chem., 1963, 28, 1506; D. H. Rammler, Y . Lapidot,and H. G. Khorana, J . Amer. Chem. SOC., 1963, 85, 1989; F. Cramer, H. P. Biir, H. J.Rhaese, W. Sanger, K. H. Scheit, G. Schneider, and J. Tenningkeit, Tetrahedron Letters,1963, 1039; J. Zemlicka, J. Beranek, and J. Smrt, Coal. Czech. Chem. Comm., 1962,27, 2784; J. Smrt and F. Sorm, ibid., 1963, 28, 61, 887; S.Chladek and J. Smrt, ibid.,p. 1301; J. Smrt and F. Sorm, ibid., p. 2415, 2434; H. Schaller, G. Weimann, B. Lerch,and H. G. Khorana, J . Amer. Chem. Soc., 1963,85,3821; H. Schaller and H. G. Khorana,ibid., p. 3828; G. Weimann, H. Schaller, and H. G. Khorana, ibid., p. 3835; H. Schallerand H. G. Khorana, ibid., p. 3941; Y. Lapidot and H. G. Khorana, ibid., p. 3852;N. S. Gerber and H. A. Lechevalier, J . Org. Chem., 1962, 27, 1731.S. Morisawa and E. Chargaff, Biochim. Biophys. Acta, 1963, 68, 147.72, 62.Acta, 1964, 87, 698.91, 1452 ORGANIC CHEMISTRYand of the synthesis of homologous polynucleotides. 82 Dicyclohexyldi-carbodi-imide (DCC) has been used as the condensing agent in most of thiswork, although picryl chloride appears to be promising and Khorana’scomparative study of reagents for the synthesis of the internucleotidelinkage revealed that aromatic sulphonyl halides also gave high yields ina shorter reaction time.s3 Amongst the more novel approaches are the useof 02,5’-cyclouridine as a 2’,5’-protected nucleo~ide,~~ and the TI-ribonu-clease-catalysed reaction of a dinucleoside phosphate with a cyclic phos-hate.*^ In general, however, the methods depend on a painstaking applica-tion of the use of selective protecting groups; many steps are required, andthe overall yields are inevitably low.An example is the synthesis of theoligoadenylic acids.86 Adenosine 3’-phosphate was converted into itspyridinium salt and acylated with benzoic anhydride, and the mixed anhy-dride was purified by column chromatography and treated successively withpyridine-acetic anhydride, methanol, and aqueous pyridine, to give N,2‘,5’-tribenzoyladenosine-3’-phosphate, from which the O-benzoyl groups wereremoved by reaction with sodium hydroxide.The product was treatedwith monomethoxytrityl chloride and purified by column chromatographyat 2 O (640 fractions), to give pyridinium N-benzoyl-5’-O-monomethoxy-trityladenosine 3’-phosphate ; this was acetylated, then purified by columnchromatography, and the monomethoxytrityl group was removed, yielding2’-O-acetyl-N-benzoyladenosine 3’-phosphate. Polymerization in the pre-sence of N,2’,5’-triacetyladenosine 3‘-phosphate (chain terminator) withDCC in pyridine, removal of protecting groups, and column chromatographygave the linear tri-, tetra-, and penta-adenylic acids (in addition to otherproducts) in a combined overall yield of 7%.Taylor and Hall have found 87 that the method of making dinucleosidephosphates which yields a mixture of the 3’,5’- and 2’,5’-linked isomersis nevertheless the simplest and gives the best overall yield (20-25y0 ofpure 3’,5’-isomer).Oligonucleotides may be separated according to netnegative charge in 7 M-urea on DEAE-cellulose. 89Nucleic Acids.-A striking finding is that a number of cytoplasmicorganelles, in addition to the nucleus, contain DNA: the chloroplasts ofplant cells contain a distinctive DNA 90 and also RNAYg1 and there is evidenceA. L. Nussbaum, G. Scheuerbrandt, and A. M. Duffield, ibid., 1964,86,102; J.Zemlicka,Chem. and Id., 1964, 581; C. 13. Reese and J. E. Sulston, Proc. Chem. SOC., 1964, 214;B. E. GrifXn and C. B. Reese, Tetrahedron Letters, 1964, 2925; S . Chladek and J. Smrt,Coll. Czech. Chem. Comm., 1964, 29, 214; J. Smrt, ibid., p. 2049; R. Lohrmann and)I. G. Khorane, J . Amer. Chem. SOC., 1964, 86, 4188.a2 R. K. Ralph, L. J. Connors, H. Schaller, and H. G. Khorana, J . Amer. Chem.SOC., 1963, 85, 1983; C. Coutsogeorgopoulos and H. G. Khorana, ibid., 1964, 86, 2926.T. M. Jacob and H. G. Khorana, J . Amer. Chem. SOC., 1964, 86, 1630.J. Zemlicka and J. Smrt, Tetrahedron Letters, 1964, 2081.85 I(. H. Scheit and F. Cramer, Tetrahedron Letters, 1964, 2765.86 Y. Lapidot and H. G. Khorana, J . Amer. Chem. SOC., 1963, 85, 3857.P.R. Taylor and R. H. Hall, J. Org. Chem., 1964, 29, 1078.a8A. M. Michelson, J . Chem SOC., 1959, 3655.89 R. V. Tomlinson and G. M. Tener, Biochemistry, 1963, 2, 703.C. R. Stocking and E. M. Gifford, Biochem. Biophys. Res. Comm., 1959, 1, 159;H. Ris and W. Plaut, J . Cell. BioE., 1962, 13, 383; E. H. L. Chun, M. H. Vaughan, Jr.,and A. Rich, J . Mol. Biol., 1963, 7 , 130; R. Sager and M. R. Ishida, Proc. Nat. Acad.Sci. U.S.A., 1963, 50, 725; R. Wollgiehn and K. Mothes, Naturwiss., 1963, 50, 95ULBRICHT: NUCLEIC ACIDS 453for DNA-dependent RNA synthesis in chloroplasts; 92 a DNA, with adifferent base composition to that of the nucleus, is present in the Kappaparticles of Paramecium aurelia; 93 and DNA has also been found in mito-chondria 94 and nucleoli.g5Circumstantial evidence for the cell-free synthesis of infectious tobaccomosaic virus RNA 96 and of infectious units of animal viruses has beenpre~ented.~' A study of DNA-directed synthesis of RNA by RNA poly-merase showed that the RNA produced is a complementary copy of the DNAprimer and that both strands of DNA are copied,9* but there is controversyregarding the latter point.The work of Bresler's school99 supports theidea that both strands of DNA are copied, but studies with phage +X 174single-stranded DNA and its double-stranded replicative form providestrong evidence that, when intact DNA is used, only one strand acts astemplate in RNA biosynthesis; with disrupted DNA, on the other hand,RNA complementary to both strands is obtained.100 A hypothesis ofDNA transcription and m-RNA synthesis has been put forward on thisbasis.lO1It now appears to have been dehitely established that the replicationof RNA viruses involves a replicative double-stranded virus-specific RNA,and RNA-directed RNA synthesis.lo2 A fine piece of autoradiography, inwhich E .coli DNA labelled with 13HJthymidine was used, led to the followingJ. T. 0. Kirk, Biochim. Biophys. Acta, 1963, 76, 417; E. Bactus and J. Brachet, ibid.,p. 490; J. Leff, M. Mandel, H. T. Epstein, and J. A. Schiff, Biochem. Biophys. Res.Comm., 1963, 13, 126; A. Gibor and M. Izawa., Proc. Nut. Acad. Sci. U.S.A., 1963, 50,1164; C. J. Pollard, Arch. Biochem. Biophys., 1964, 105, 114; D. S. Ray and P. C.Hanawalt, J .MoZ. Biol., 1964, 9, 812.91 J. Biggins and R. B. Park, Nature, 1964, 203, 425.92 J. T. 0. Kirk, Biochem. Biophys. Res. Comm., 1964, 14, 393; 1964, 16, 233.93 J. Smith-Sonneborn, L. Green, and J. Marmur, Nature, 1963, 197, 385.9 4 C& Schatz, E. Haslbrunner, and H. Tuppy, Biochem. Biophys. Res. Comm.,1964, 15, 127; D. J. .L. Lush and E. Reich, Proc. Nut. Acad. 815. U.S.A., 1964, 52,931.D. G. Comb, R. Brown, and S. Katz, J . Mol. Biol., 1964, 8, 781; J. McLeish,Nature, 1964, 204, 36.96 G. W. Cochran, A. S. Dhaliwal, G. W. Welkie, J. L. Chidester, M. H. Lee, andB. K. Chandrasekar, Science, 1962, 138, 46; Y . T. Kim and S . G. Wildman, Biochem.Biophys. Res. Comm., 1962, 8, 394; M. Karasek and G. Schramm, ibid., 1962, 9, 63;W. R. Hudson, Y.T. Kim, R. A. Smith, and S. 0. Wildman, Biochim. Biophys. Actu,1963, 76, 257.g 7 A. J. Glasky and J. C. Holper, Biochem. Biophys. Res. Comm., 1963, 12, 87;G. W. Cochran, J. Storz, and A. Mikulska-Macheta, Nature, 1964, 202, 1294.J. Hurwitz, J. J. Furth, M. Anders, and A. Evans, J . Biol. Chem., 1962, 237,3752.gs S. E. Bresler, R. A. Kreneva, V. V. Kushev, and M. I. Mosevitskii, J . Mol. Biol.,1964, 8, 79.loo M. Hayashi, M. N. Hayashi, and S. Spiegelman, Proc. Nut. Acad. Sci. U.S.A.,1963, 50, 664; 1964, 51, 351.lol K. W. Jones and D. E. S. Truman, Nature, 1964, 202, 1264.lo2 P. J. Gomatos and I. Tamm, Roc. Nut. Acud. Sci. U.S.A., 1963, 49, 707; L.Montagnier and F. K. Sanders, Nature, 1963, 199, 664; R. Eason, M. J. Cline, andR. M. S .Smellie, ibid., 1963, 198, 479; C. Weissmann, P. Borst, R. H. Burdon, M. A.Billeter, and S. Ochoa, Proc. Nat. Acad. Sci. U.S.A., 1964, 51, 682; R. B. Kelly andR. L. Sinsheimer, J . Mol. Biol., 1964, 8, 602; H. C. Kaerner and H. Hoffmann-Berling,Nature, 1964, 202, 1012; W. Shipp and R. Haselkorn, Proc. Nat. Acad. Sci. U.S.A.,1964, 52, 401; R. H. Burdon, M. A. Billeter, C. Weissmann, R. C. Warner, S . Ochoa,and C. A. Knight, ibid., p. 768454 ORGANIC CHEMISTRYconclusions: lo3 (1) the chromosome consists of a single piece of two-st’randed DNA, 700-900 p long; (2) it duplicates by forming a fork, and thenew (daughter) limbs of the fork consist of one strand of new, and one ofold material; and (3) the most likely structure of the chromosome is circularbut is usually broken during extraction.It is known that actinomycin binds to DNA and inhibits RNA synthesis,and it now appears that specific complex formation with the deoxyguanosineresidues in the polynucleotide chain is responsible. It is suggested thatactinomycin is bound in the minor groove of DNA, and, since it displacesRNA polymerase from DNA, the minor groove may be the site of RNAsynthesis, and the major groove the site of DNA synthesis.lo4An accurate determinationlo5 of the molecular weight of s-RNA gavea value of 31,000, which is in agreement with an independent estimatethat s-RNA contains about 80 nucleotides.lo6 The inhibition of proteinsynthesis by purornycin is believed to be due to its structural resemblanceto aminoacyl-s-RNA and, when various analogues were tested, it was foundthat S’-isoniers were active and the 2’-isomers inactive.lO‘ This suggeststhat aminoacyl s-RNA is the 3’-isomer (5), but the evidence appears to beconflicting.On the one hand, comparison of the nuclear magnetic reson-ance (n,m.r.) spectrum of aminoacyladenosine, isolated from arninoacyls-RNA, with the spectra of 2’- and 3’-adenylic acid, supports the 3’-structure,as does some chemical evidence; lo8 on the other hand, studies of the ratePolynucleotide chainC \\CH 0 OH1 11R-C-CO(5) N H2of acyl migration between the 2’- and the 3’-position suggest an equilibriummixture.lo9 Since it is possible that the structure of the amino-acid residuehas a strong effect on the position of the equilibrium, it may be possible toloS J.Cairns, J . MoZ. Biol., 1963, 6, 208.lo4 I. H. Goldberg, M. Rabinowitz, and E. Reich, Proc. Nut. Acad. Sci., U.S.A.,1962, 48, 2094; L. D. Hamilton, W. Fuller, and E. Reich, Nature, 1963, 198, 535;E. Reich, Science, 1964, 143, 684.lo5 W. J. Moller, Proc. Nut. Acad. Sci. U.S.A., 1964, 51, 501.lo6 M. Staehelin, M. Schweiger, and H. G. Zachau, Biochern. J., 1964, 84, 1OGP.lo’ N. Nathaus and P. Neidle, Nature, 1963, 197, 1076.loB J. Sonnenbichler, H. Feldmann, and H. G. Zachau, 2. physioE. Chem., 1963,334, 283; H. Feldmann and H. G. Zachau, Biochem. Bioplzp. Res. Comm., 1964, 15, 13.lo9 C. S. McLaughlin and V. M. Ingram, Science, 1964, 145, 942; R. Wolfenden,D. H. Rammler, and F. Lipmann, Biochemistry, 1964, 3, 329ULBRICHT: NUCLEIC ACIDS 455resolve the above results.The initial site of acylation remains to be de-termined; on purely chemical grounds, the 2'-position is the more likely.The inherent difficulty in developing any chemical method for sequencedetermination of polynucleotides is reflected in the paucity of publicationson this important subject. Some useful modifications of the periodateamine method have been reported.l1°The Genetic Code and Protein Synthesis.-This topic was reviewed inthese Reports two years ago 1 and, in greater detail, last year.lll In general,the central idea of a nucleotide code transcribing information from DNAt o m-RNA to protein is accepted without question, despite occasionalcriticism.8, 112 It has been pointed out that unambiguous evidence forthe existence of m-RNA in vivo is lacking; careful studies of rapidly labelledRNA in a wild strain and a constitutive high-catalase mutant of Rhodo-pseudomonas spheroides showed no significant difference in nucleotidecomposition between theThere is, however, some striking evidence in support of the centralidea.Thus, a study of amber mutants in bacteriophage T4D of E. coliclearly indicates that the gene is co-linear with the polypeptide chain ofthe head protein.l14 A number of workers have reported that, when DNAis complexed with histone, RNA synthesis and growth is inhibited.l15The arginine-rich histone fraction which, when complexed with DNA, leadsto least activity in support of RNA synthesis, also stabilizes DNA most tothermal denaturation.ll6 Of particular interest is a study with pea chroma-tin: 117 when a protein-synthesizing system from E.coEi is used, a characteris-tic pea protein (pea-seed reserve globulin) can be obtained; however, if thechromatin used is isolated from pea cells in which this protein is not syn-thesized in vivo, no globulin is detected, unless histone is removed from thechromatin.ll7 This suggests that the complex-formation by specific partsof the DNA in t,he chromosomes with histones may be the molecular basisof cellular differentiation.It appears that two molecules of s-RNA are attached to each ribosomein polyribosomes.ll8 In E. coli, the specific binding of aminoacyl s-RNAto ribosomes requires the presence of the polynucleotide templatle and arather high concentration of ammonium ions, and may be the rate-limitingstep iii amino-acid p~lymerization.~~s In reticulocytes, protein synthesisoccurs in two distinct stages, the first of which-binding of the aminoacyl110 H.C. Neu and L. A. Heppel, J . BioZ. Chem., 1964, 239, 2927.112 R. W. Hendler, Science, 1963, 142, 402.113 E. D. Gray, A. M. Haywood, and E. Chargaff, Biockhn. Biophys. Acta, 1964,87, 397.114 A. G. Sarabhai, A. D. W. Stretton, S. Brenner, and 9. Bolle, Nature, 1964,201, 13.115 R. C. Huang and J. Bonner, Proc. Nat. Acad. Sci. U.S.A., 1962, 48, 1216; V. G.Allfrey, V. C. Littau, and A. E. Mirskey, ibid., 1963, 49, 414; V. I. Vorobyev andV. M. Bresler, Nature, 1963, 198, 545; J.Hindley, Biochem. Biophys. Res. Comm.,1963, 12, 175.116 R. C. Huang, J. Bonner, and K. Murray, J. MoZ. BioZ., 1964, 8, 54.11' J. Bonner, R. C. Huang, and R. V. Gilden, Proc. Nut. Acad. Sci. U.S.A., 1963,56, 893.11* J. Warner and A. Rich, Proc. Nut. A c d . Sci. U.S.A., 1964, 51, 1134.119 G. J. Spyrides, Proc. Nat. Acad. Sci. U.S.A., 1964, 51, 1220.H. R. V. Arnstein, Ann. Reports, 1963, 60, 512456 ORGANIC CHEMISTRYs-RNA to the ribosome-requires GTP and an enzyme; the second stage-peptide bond synthesis-appears to require a different enzyme.120 Proteinsynthesis in anuclear reticulocytes has been reviewed.121The genetic code. For reviews, see Wittmann and Ochoa.122 Theresults of amino-acid incorporation studies involving analogues of polyU,123and the fact that the amino-acid sequence and composition can be alteredby factors other than the nucleotide sequence-for example, temperature,concentration of magnesium ions 124-are difficult to interpret.It appearspossible that the configuration a t the ribosome is being influenced. Butwhich in vitro conditions correspond to the true in vivo environment, andhow arbitrary are the coding triplet assignments?The discovery that a trinucleotide induces binding of a specific [1*CJ-aminoacyl s-RNA to ribosomes is obviously most valuable. The bindingis determined by washing the ribosomes on a millipore filter; only theribosomes with bound s-RNA remain on the filter. By this method, it hasbeen shown that GUU, and not UUG or UGU, is the code-word for valine,125and it should be possible to determine the effective sequence of all thenucleotide triplets by this means.Physical Methods.-Nuclear magnetic resonance.In a number of cases,recent studies have contradicted earlier assignments. The order of theC-H peaks in unsubstituted purine from lower field was supposed to beH2,H,,H,126 or H2,H6,H8,l27 but studies of deuterated purines have shownunequivocally that the correct order is H6,H2,H8.128 Incorrect conclusionshave also been drawn about preferred tautomeric structures in nucleicacid derivatives. The suggestion that cytosine has a zwitterionic struc-ture 129 has been shown by careful studies of ultraviolet and n.m.r. spectrato be ~ntenable.1~0 Similarly, the n.m.r. spectrum of deoxycytidine whichsuggested an imino-structure131 was found to be that of its hydro-chloride ; I329 133 deoxy- l-methylcytidine, which necessarily has an imino-structure, has a spectrum quite different from that of deo~ycytidine.~~~It also now appears1= that unsuitable parameters were used in early120 R. Arlinghaus, J. Shaeffer, and R. Schweet, Proc. Nut. Acad. Sci. U.S.A., 1964,51, 129.121 H. G. Schweiger, Naturwiss., 1964, 51, 521.122 H. G. Wittmann, 2. Vererbungslehre, 1962, 93, 491; Naturwiss., 1963, 50, 76;S. Ochoa., Bull. New Ywk Acad. Med., 1964, 40, 387.12s M. Grunberg-Manago and A. M. Michelson, Biochim. Biophye. Acta, 1964,80,431.134 J . Davies, W. Gilbert, and L. Gorini, Proc. Nut. Acad. Sci. U.S.A., 1964, 51,883; S. M. Friedman and I. B. Weinstein, ;bid., 1964, 52, 988; W. Szer and S. Ochoa,J . Mol. Biol., 1964, 8, 823.126 P. Leder and M. Nirenberg, Proc. Nut. Acad. Sci. U.S.A., 1964, 52, 420.126 C. D. Jardetzky and 0. Jardetzky, J . Amer. Chem. SOC., 1960, 82, 222.127 G. S. Reddy, L. Mandell, and J. H. Goldstein, J . Chem. SOC., 1963, 1414.128 S. Matsuura and T. Goto, Tetrahedron Letters, 1963, 1499; M. P. Schweizer,S. I. Chan, G. K. Helmkamp, and P. 0. P. Ts'o, J . Amer. Chem. SOC., 1964, 86, 696.12s J. P. Kokko, J. H. Goldstein, and L. Mandell, J . Amer. Chem. SOC., 1961,83,2909.180 D. J. Brown and J. M. Lyall, AzcstruZ. J . Chem., 1962, 15, 851; A. R. Katritzkyand A. J. Waring, J . Chem. SOC., 1963, 3046.131 L. Gatlin and J. Davis, Jr., J . Amer. Chem. SOC., 1962, 84, 4464.132 H. T. Miles, J . Amer. Chem. SOC., 1963, 85, 1007.133 T. L. V. Ulbricht, Tetrahedron Letters, 1963, 1027.134 R. J. Abraham, L. D. Hall, L. Hough, and K. A. McLauchlan, J . Chem. Soc.,1962, 3699; R. V. Lemieux, J. D. Stevens, and R. R. Fraser, Canad. J . Chem., 1962,40, 1955ULBRICHT: NTJCLEIC ACIDS 457investigations of the conformation of nucleosides in solution by n.m.r. ,135involving the Karplus equation.136 Karplus himself has drawn attentionto the danger of attempting to estimate dihedral angles from n.m.r. couplingdata without considering other aspects of molecular environment .13‘ How-ever, on the basis of Jardetzky’s analysis of the configuration of a- and/l-ribof~ranosides,1~8 the anomeric configuration of ribonucleosides can bedetermined in some cases by n.m.r. spectroscopy, when both anomers areavailable .139A 31P n.m.r. study of the chemical shifts of five-membered phosphatetriesters, which are significantly different from those of 6-membered estersor acyclic phosphate triesters, indicates that there is less electron-shieldingof the phosphorus nucleus.140 This is consistent with a diminution in thed n q n double-bond character of the cyclic P-0 bonds in the five-memberedring, which had been suggested141 as an explanation of the well-knowngreater reactivity of five-membered phosphate esters, e.g., nucleoside2’,3‘-cyclic ph0~phates.l~~X-Ray crystallography. The structure of the co-crystals of a number ofpurine-pyrimidine nucleoside analogue pairs has been determined. Watson-Crick hydrogen bonding has been found in 9-ethylguanine-3-methylcyto-sine,143 9-ethylguanine-5-bromo-3-methylcytosine,144 and 2’-deoxyguano-sine-5-bromo-2’-deoxycytidine.~~ On the other hand, 9-ethyladenineand 3-methyluracil form a 1 : 1 crystalline complex in which N-7 of adenineparticipates in hydrogen bonding ; 146 and in adenosine-5-bromouridinea third type of hydrogen bonding is found, involving not only N-7 of adenine(instead of N-1) but also uracil 0-2 (instead of 0-6).147 There is, however,no evidence so far that these other kinds of hydrogen bonding are to befound in wivo.X-Ray diffraction of double-stranded RNA’s from certain viruses hasshown that their structure is similar, but not identical, with that of the Aform of native DNA.14S The small-angle X-ray scattering technique hasbeen used to study the structure in solution of DNA (as a function of tem-perature) and of polyA (as a function of pH). There is evidence for astructure intermediate between the Watson-Crick double helix and a randomcoil; this intermediate structure appears to be a rod in which the base135 C. D. Jardetzky, J. Amer. Chem. SOC., 1960, 82, 229; 1961, 83, 2919; R. V.Lemieux, Canad. J. Chem., 1961, 39, 116.136M. Karplus, J. Chena. Phys., 1959, 30, 11.13’ M. Karplus, J . Amer. Chem. SOC., 1963, 85, 2870.138 C. D. Jardetzky, J. Amer. Chem. SOC., 1962, 84, 62.139 L. Goldman and J. W. Marsico, J. Med. Chem., 1963, 6, 413.140 G. M. Blackburn, J. S. Cohen, and Lord Todd, Tetrahedron Letters, 1964, 2873.141 E. T. Kaiser, M. Panar, and F. H. Westheimer, J. Amer. Chem. Soc., 1963, 85,142D. M. Brown and A. R. Todd, J. Chem. SOC., 1952, 52.143 E. J. O’Brien, J. Mol. Biol., 1963, 7, 107.14* H. M. Sobell, K. Tomita, and A. Rich, Proc. Nat. Acad. Sci. U.S.A., 1963, 49,145 A. E. V. Hasheymeyer and H. M. Sobell, Nature, 1964, 202, 969.146 F. S. Matthews and A. Rich, J. Mol. Biol., 1964, 8, 89.14’ A. E. V. Hashemeyer and H. M. Sobell, Proc. Nat. Acad. Sci. U.S.A., 1963,14* R. Langridge and P. J. Gomatos, Science, 1964,141,694; K. Tomita and A. Rich,602.885.50, 872.Nature, 1964, 201, 1160458 ORGANIC CHEMISTRYplanes are still stacked perpendicular to the helix axis, but the specifichydrogen bonds linking the base pairs are broken.149Optical rotatory dispersion and circular dichroism. Early results in thisfield appear to have been rather inaccurate, either because solutions of highabsorbance were used (which can give rotatory artifacts simulating Cottoneffects l 5 O ) or because of the limitations of the available instruments in theultraviolet region. A study of the optical rotatory dispersion (0.r.d.) ofDNA and RNA on one of the more accurate and sensitive instruments nowavailable l 5 l shows reasonable agreement with previous results 152, 153 inthe region down to 350 mp, but marked differences at lower wavelengths.In DNA, for example, there is a trough at 257 mpP1 whereas previouslya peak had been found at this ~ave1ength.l~~ It is interesting that DNAand RNA give an 0.r.d. peak at 200 mp or below,151 a region in which bothmono- and poly-nucleotides possess another absorption maximum, asrecent studies in the far-ultraviolet region have sh0wn.l5~ The markedchanges in the 0.r.d. observed with changes in pH and temperature can becorrelated with helix-coil transitions but, despite much discussion of n-n-*and n-n* transitions and theories of hypochromism, it must be admittedthat the 0.r.d. results are poorly understood. One reason for this is thatvery little work on monomers has been carried out. Only recently havestudies of the four deoxyribonucleotides 155 and of a variety of nucleosides 156shown that, in the p-series, purine derivatives exhibit a negative Cottoneffect, and pyrimidine derivatives a positive Cotton effect. Since thecorresponding a-anoiners give Cotton effects of the opposite sign, 0.r.d.provides a simple method of determining the anomeric configuration ona very small sample of material.156 These results also provide an explana-tion for the observed exceptions to Hudson’s rules of isorotatioii; pyr-imidine N3-~-nucleosides obey these rules in reverse.41Circular-dichroism studies of polynucleotides indicate that the strengthof a positive band is associated with helical structures, but the correlationis not simple and, as with o.r.d., the results cannot yet be properly explained.157149 V. Luzzati, A. Mathis, F. Masson, and J. Witz, J. Mol. Biol., 1964, 10, 28.1 5 0 P. Urnes and P. Doty, Adv. Protein Claerra., 1961, 16, 401.151 T. Sameyima and J. T. Yang, Biochemistry, 1964, 3, 613.152 J. R. Fresco, Tetrahedron, 1961, 13, 185.1 5 3 P. 0. P. Ts’o, G. K. Helmkamp, and C. Sander, Biochim. Biophys. Acta, 1962,154 D. Voet, W. €3. Gratzer, R. A. Cox, and P. Doty, Biopolymers, 1963, 1, 193;M. Falk, J. Amer. Chem. SOC., 1964, 86, 1226.165 J. T. Yang and T. Samejima, J. Arner. Chem. SOC., 1963, 85, 4039.156 T. L. V. Ulbricht, J. P. Jennings, P. M. Scopes, and W. Klyne, Tetrahedron1 5 7 J. Brahms, J. Amer. Chem. SOC., 1963, 85, 3298; J. Brahms and W. F. H. M.55, 584.Letters, 1964, 695.Mommaerts, J . Mol. Biol., 1964, 10, 73

ISSN:0365-6217    

DOI:10.1039/AR9646100193

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

BIOLOGICAL CHEMISTRY1. INTRODUCTIONBy D. F. Elliott(CIBA Laboratories Limited, Research Division, Horsham, Sussex)PRO B L E M s of drug metabolism have not been discussed in Annual Reportssince 1958 Atabout that time much new ground was being broken and in the interveningyears our whole outlook has undergone drastic change.2 These discoveries,especially those in the fields of drug tolerance and drug sensitivity, havehad an important bearing upon clinical practice, and at very least it can besaid that any lingering doubts as to the relevance of metabolic studies todrug therapy have been swept away. In spite of the vast array of structuresthat organic chemists have devised it seems that the living cell has thecapacity, almost without exception, to metabolise any substance with whichit is presented.The phenomenonof drug tolerance is now much better understood and appears to be connectedwith changes in the microsomal part of the cell-an organelle of great bio-chemical interest at the present time. Drug sensitivity to at least two typesof drug has been shown to be directly related to the genetic make-up ofsensitive individuals and it is possible that more examples will be found.The problem of drug sensitivity is analogous to that of derangements ofnormal metabolic pathways in man, which have long been known to be duet o inherited variations of genetic constitution-a field which has attractedconsiderable attention in recent years. These studies have also emphasisedthe very high toxicity of many normal cellular metabolites, which is revealedwhen they accumulate by reason of the inability of the cell to metabolisethem further.Advances since 1963 in the field of heteropolymeric molecules warrant areport again this year, more especially devoted to the carbohydrate-poly-peptide polvvmers from the point of view of their biosynthesis and the natureof the carbohydrate-polypeptide bond.Steady progress is now being madein this very difficult field.For the polypeptides themselves the most remarkable discovery has beenthat the biological activity of the gastrins resides in the C-terminal tetra-peptide sequence. Although it has long been known that part of a poly-peptide sequence may not be essential for activity, this appears to be thesmallest active " stump " yet discovered.when the important field of hydroxylation was surveyed.This intriguing problem awaits a solution.Ann.Reports, 1958, 55, 376." Enzymes and Drug Action ", ed. J. L. Mongar and A. V. S. de Reuck, J. andA. Churchill Ltd., London, 1962.J. C. Anderson, M. A. Barton, R. A. Gregory, P. M. Hardy, G. W. Kenner, J. K.MacLeod, J. Preston, R. C. Sheppard, and J. S. Morley, Nature, 1964, 204, 933; H. J.Tracy and R. A. Gregory, ibid., p. 9352. DRUG METABOLISMBy C . I. Furst(CIBA Laboratories Limited, Research Diwision, Horsham, Sussex)ONLY a few selected topics have been chosen for review because of the scopeof the subject. More comprehensive treatments are to be found in a numberof recent m0nographs.loxidising Enzmes.-In the liver microsomes of reptiles, birds, a.ndmammals there are enzyme systems which appear selectively to hydroxylateforeign organic compounds.2 These drug-metabolising enzymes requirereduced nicotinamide-adenine dinucleotide phosphate (NADPH) and oxygen,but because of difficulties in solubilisation and the presence in the micro-somes of other enzyme systems, with similar co-factor requirements it hasproved extremely difficult to obtain further precise information as to theirnature.Mason3 has termed enzymes of this type “mixed-functionoxidases,” since the introduction of one atom of oxygen into the substrateis coupled with the simultaneous oxidation of NADPH to NADP with theformation of one molecule of water. The stoicheiometry of this reactionhas until recently been difficult to demonstrate because of the “ backgroundoxidation ” of NADPH.4 Improved techniques have now made it possibleaccurately to determine low rates of oxygen uptake and NADPH-oxidation,and the stoicheiometric relation between the two has been shown for themixed- function oxidase involved in the hydroxylation of 17 - hydroxy-progesterone by a bovine adrenal microsome preparation.5 More recently,Blake et aL6 have shown that the drugs SKF525A, Lilly 18947, chlorpro-mazine, and meperidine increased the rate of NADPH-oxidation by -500/6above background in a rat-liver microsome preparation.There is now some evidence that the NADPH-oxidase may be NADPH-cytochrome c reductase which, together with the carbon monoxide-bindingpigment, has been implicated in the demethylation of amin~pyrine.~NADPH-cytochrome c reductase has been solubilised and purified frompig-liver microsomes and seems to be identical with the enzyme firstpurified from whole-liver acetone powder by Horecker in 1950.9 OrreniusJ.R. Gillette, “ Progress in Drug Research ”, Vol. VI, ed. E. Jucker, BirkhiiuserPress, Basle and Stuttgart, 1963, p. 13; R. T. Williams, “ Detoxication Mechanisms ’I,2nd edn., Chapman and Hall Ltd., London, 1959; W. H. Fishman, “ Chemistry ofDrug Metabolism ”, C. C. Thomas, Springfield, Illinois, U.S.A., 1961; E. J. Ariens andA. M. Simonis, ‘‘ Molecular Pharmacology ”, ed. E. J. Ariens, Academic Press, NewYork and London, 1964, p. 53.B. B. Brodie and R.P. Maickel, Proc. First Internat. Pharmacological Meeting,Vol. VI, Pergamon Press, London, 1962, p. 299.8H. S. Mason, Adv. Enzymol., 1957, 19, 79.J. R. Gillette, B. B. Brodie, and B. N. La Du, J . Pharmacol., 1957, 119, 532.R. W. Estabrook, D. Y. Cooper, and 0. Rosenthal, Biochem. Z., 1963, 338, 741.sD. E. Blake, W. F. Bousquet, and T. X. Miya, Fed. Proc., 1964, 23, 538. ’ S. Orrenius and L. Ernster, Biochem. J., 1964,92,37P; S. Orrenius and L. Emster,* C. H. Williams, Jr., and H. Kamin, J . Biol. Chem., 1962, 237, 587.@ B. L. Horecker, J . Biol. Chem., 1950, 183, 593.Biochem. Biophys. Res. Comm., 1964, 16, 60FURST: DRUG METABOLISM 461and his co-workers 7 found that on inducing microsomal drug-metabolisingactivity in rats by pre-treatment with phenobarbitone the demethylationof aminopyrine closely followed the increased amounts of NADPH-cyto-chrome c reductase and of the CO-binding pigment.The levels of threeother microsomal enzymes (NADH-cytochrome c reductase, cytochromeb5, and glucose 6-phosphatase) were either unchanged or slightly decreased.A similar method was used to show a parallel between the CO-binding pig-ment and the rate of oxidation of hexobarbitone.lo A CO-binding pigmentwas first detected in mammalian-liver microsomes by Klingenberg l1 andGarfinkel.12 Estabrook5 has compared it with the pigment from bovineadrenal microsomes involved in the 21 -hydroxylation of 17-hydroxypro-gesterone and has postulated that it is the oxygen-activating enzyme ofthe liver microsomal hydroxylases.The pigment has now been successfullysolubilised and purified from rabbit-liver microsomes.13 The soluble pig-ment had the characteristic spectrophotometric properties of a hzemoproteinand may be regarded as a cytochrome of the b-type. It contained no flavinand the iron content was greater than that of the protohsem. Significantly,the bound form of the pigment was reduced by both NADH (reducednicotinamide-adenine dinucleotide) and NADPH, but the soluble, purifiedform was not so reduced, suggesting that reduction of the bound form maybe carried out by specific reductases lost during steapsin digestion. Thesereductases have not been identified.The CO-binding pigment probably represents the microsomal '' Fex "previously detected in liver microsomes by electron spin resonance.l* Agood correlation has been found between signal height and the content ofCO-binding pigment in rat-liver microsomes under various experimental~0nditions.l~ No correlation was observed with cytochrome b5.The presence of possibly two more CO-binding pigments with strongabsorption peaks a t 450 mp has been reported in rat-adrenal mitochondria.16These differ from the microsomal pigment in their requirement for malateor succinate as reducing agents rather than for reduced pyridine nucleotides.It was suggested that one of these enzymes might be associated with the1 lg-hydroxylating system of mitochondria.Both the microsomal CO-binding pigment and NADPH-cytochrome creductase have been incorporated into a tentative scheme (Fig.1) to accountfor the inhibition of the NADPH-linked lipid peroxidation in liver micro-somes by drugs undergoing demethy1ation.l' According to this postulatethe inhibition occurred a t the level of NADPH-cytochrome c reductase(for the reasons mentioned above it would be necessary to interpose anlo V. R. Reichert and H. Remmer, Naunyn-Schmiedeberg's Arch. exp. Path.Pharmak., 1964, 247, 374.l1 M. Klingenberg, Arch. Biochem. Biophys., 1958, 75, 376.l2 D. Garfinkel, Arch. Biochem. Biophys., 1958, 77, 493.lS T. Omura, and R. Sato, J . BioE. Chem., 1964, 239, 2370, 2379.l4 Y. Hashimoto, T. Yamano, and H. S. Mason, J. BioE. Chem., 1962, 237, PC3843.l5 F. Wada, T. Higashi, Y. Ichikawa, K. Tada, and Y. Sakamoto, Biochim.Biophys.l0 B. W. Harding, S. H. Wong, and D. H. Nelson, Biochim. Biophys. Ada, 1964,l7 S. Orrenius, G. DaIlner, and L. Ernster, Biochem. Biophys. Res. Conam., 1964,Acta, 1964, 88, 654.92, 415.14, 329462 BIOLOCICAL CHEMISTRYelectron-transport system between NADPH-cytochrome c reductase and theCO-binding pigment). Carbon monoxide inhibited tlhe aminopyrine-stimulated increase in oxygen uptake by rat-liver microsomes but wasRCH, L RH + CH,OfCO-binding pigment f 7\fNADPH + NADPH-cyt*C red* /!!PADP-Fe LLipid 0, + CH,(CHO), LipidFIG. 1.without effect on lipid peroxidation,l* suggesting that the terminal oxidasesare not identical. Lipid peroxidation may thus account for some of the“background” oxygen uptake by microsomes in the absence of drugsubstrates.Although in the above scheme the terminal-oxidase is depicted as t,heCO-binding pigment, the mechanism whereby trhe activated oxygen atomis transferred to the substrate molecule remains unknown.Since thediscovery l9 of a non-enzymic system consisting of Fez+, EDTA, ascorbicacid, and oxygen that hydroxylated aromatic compounds, numerous studieshave been performed with such systems because of t,heir similarities to livermicrosome preparations. In the model system the active species has theproperties of a free radical20 which does not appear to be identical with(or solely) the hydroxyl free radical, H00.2~ The ferrous ion can be replacedby other metals 2o or by cytochrome b5, 21a the main criterion for activitybeing that the ‘‘ terminal oxidase ” should have a redox potential between+0.2 and -0.3 v .~ OThe existence of the perhydroxyl radical, HO,., in aqueous solution hasbeen reported.21b The o:m:p ratio for the hydroxylation of acetanilide bythis radical varied greatly from that of HO.; moreover, the production ofthe labile perhydroxyl radical was greatly affected by botch pH and tem-perature. In the presence of a suitable substrate and a strong electron-donor the perhydroxyl radical might be expected to liberate nascent oxygen :H O 2 - + e + H + + : 6 : + H , O -Nillson and his colleagues l 8 have made use of the fact that enzyme-producedfree radicals activate the chemiluminescent oxidation of lurninol (5-amino-R. Nillson, S. Orrenius, and L.Ernester, Biochem. Biophys. Res. Comm., 1964,17, 303.l9 S. Udenfriend, C. T. Clark, J. Axelrod, and B. B. Brodie, J. Biol. Chem., 1951,208, 737; B. B. Brodie, J. Axelrod, P. A. Shore, and S. Udenfriend, &id., p. 741.2o V. H. Staudinger and V. Ullrich, 2. Naturforsch., 1964, 19b, 409.21 (a) H. J. Staudinger and V. Ullrich, Biochem. Z . , 1964, 339, 491; ( b ) V. H.Staudinger and V. Ullrich, 2. Naturforsch., 1964, 19b, 877; (c) 0. A. Hamilton, R. J.Workman, and L. Woo, J. Amer. Chem. SOC., 1964, 86, 3390; ( d ) R. 0. C. Norman andG. K. Radda, Proc. Chem. Soc., 1962, 138; ( e ) E. Boyland, M. Kimura, and P. Sims,Biochem. J., 1964, 92, 631BURST: DRUG METABOLISM 4632,3-dihydrophthalalzine-l ,4-dione)Z2 to study its oxidation by rat-liver micro-somes.While chemiluminescent oxidation did occur and NADPH was anessential co-factor, the reaction was not inhibited by carbon monoxide butcould be blocked by very small amounts of aminopyrine. This reaction thusresembles lipid peroxidation rather than drug hydroxylation.An alternative proposal for the model system, the microsomal drugenzymes, and phenylalanine hydroxylase is an oxygen-insertion from anenzyme-substrate c0rnplex.~3 The main feature of this mechanism is thata metal ion must form a complex with molecular oxygen and some systemcapable of oxidation by two electrons, such as an enediol (e.g., ascorbic acid)or the tetrahydropteridine co-factor for phenylalanine hydr~xylase.~~ Inthis scheme the Fe2+, oxygen, and enediol are in equilibrium with a complex(1) which represents the actual oxidising agent : {IoH f FeZf -2H { l o > F e & {$,.Fe 0, /-o = 00This resembles the oxidising complex proposed by Mason,3 Enzyme-Fe2+0,.A variation on this mechanism is the formation of a complex (2) whichby a shift of electrons and a proton might transfer an oxygen atom to asubstrate (S).This reaction would be subject to acid (HA) and base (B)catalysis.(1)OHWhile the oxidation of drugs may be represented as a general hydroxyl-ation many factors suggest that several different enzymes are involved.Further evidence has been produced for the existence of distinct enzymesfor ortho- and para-hydroxylation of aniline 25 and biphenyl 2G a.nd for 0-and N-demethylation of codeine.27A new enzyme system catalysing S-demethylation of a variety of sulphurcompounds by rat-liver microsomes has also been described? Microsomesfrom the spleen and kidney possessed not more than -10% of the activityof the liver.This system was similar to the N - and O-demethylases in itsrequirement for NADPH, oxygen, Mgaf, and nicotinamide for maximum22 J. R. Totter, E. C. de Dugros, and C. Riveiro, J . Biol. Chem., 1960, 235, 1839.2s G. A. Hamilton, J . Amer. Chem. Xoc., 1964, 86, 3391.24 S. Kaufman, J . Biol. Chem., 1964, 239, 332.26 V. H. Kampffmeyer and M. Kiese, Biochem. Z . , 1964, 339, 454; S. Bauer andM. Kiese, Naunyn-Schmiedeberg’s Arch. exp. Path. Pharmak., 1964, “7, 144; V. H.Kampffmeyer and M. Kiese, ibid., p. 374.26 P. J. Creaven, D.V. Parke, and R. T. Williams, Biochem. J . , 1964, 91, 12P.27 C. Elison and H. W. Elliott, J . Pharmacol., 1964, 144, 265.P. Mazel, J. F. Henderson, and J. Axelrod, J. Pharmol., 1964, 143, 1464 BIOLOGICAL CHEMISTRYactivity but differed in its resistance to stimulation and inhibition by agentssuch as phenobarbitone and SKF525A.29 Among the compounds demethyl-ated was the anti-metabolite S-methylthiopurine (3) which has previouslybeen reported to be metabolised in vivo by man 30 and byMeS H rats.31 A number of other methylated purines and otherIN'6 purine derivatives were also reported to be metabolised2 \ (>?. by the microsomal N - , S- and O-demethylases.32 Com-9 (3) pounds methylated on thiol, amino-, or methoxyl groupswere all demethylated, with one exception, but methylgroups attached directly to the ring at positions 1, 3, 7, and 9 resistedremoval.It is possible that some of the metabolites may be involved in the anti-carcinogenic actions of the parent compounds.Hyiiroxymethylation has been shown to occur in guinea-pig-liver micro-somes 33 and in acid-fast ba~teria.~4 Thus the conversion of aniline intop-hydroxyaniline may proceed to some extent through the intermediacy ofp-hydroxymethylaniline.The hydroxymethylation step occurred in theabsence of NADPH, but the subsequent conversion into p-hydroxyanilinewas NADPH-dependent . Hydroxymethylation of deoxycytidylate haspreviously been reported as one of a number of new enzymic activitiesacquired by E . coli in response to infection with T-even bacteriophage,35 andby animal cells after virus infection.36A setback in attempts to isolate drug enzymes has been the finding37that the activity of the soluble microsomal enzyme reported to hydroxylateacetanilide is due to a soluble e~terase.~* This esterase catalysed the hydro-lysis of acetanilide to aniline which reacted with an acid degradation productEsterase HfPhaNHAc Ph*NH2 + OR' t- NADPHOHC CH-NHRPh.N=HC CH*NHR(4) of NADPH to form a Schiffs base (5) similar in spectrophotometricproperties to p - and o-acetamidophenol.It is not known whether a similar2 9 J. F. Henderson and P. Mazel, Biochem. Pharmucol., 1964, 13, 1471.30 G. B. Elion, S. W. Callahan, and G. H. Hitchings, Proc. Amer. Assoc. CancerRes., 1962, 3, 316:-31 E.J. Sarcione and L. A. Stutzman, Cancer Res., 1960, 20, 387.32 J. F. Henderson and P. Mazel, Biochem. Pharmacol., 1964, 13, 207.N. H. Sloane, Biochim. Biophys. Acta, 1964, 81, 408.34 N. H. Sloane and K. G. Untch, Biochemistry, 1964, 3, 1160.35 J. G. Flaks and S . S. Cohen, Biochim. Biophys. Acta, 1957, 25, 667; C. K.Mathews, F. Brown, and S. S. Cohen, J . BioZ. Chem., 1964, 239, 2957.38 S. Kit, L. J. Piekarski, and D. R. Dubbs, J . MoZ. BioZ., 1963, 6, 22.s8 K. Krisch, Biochem. Z., 1963, 337, 631, 546.K. Krisch, H. J. Staudinger, and V. Ullrich, Life Sciences, 1964, 3, 97FURST: DRUG METABOLISM 405mechanism is responsible for the activity of the aniline-hydroxylating enzymereported by Imai and sat^.^^N-Dealkylation.-Controversy over the role of N-oxide formation inN-dealkylation continues. Ziegler and Pettit 40 have produced furtherevidence in favour of the formation of NN-dimethylaniline oxide as anintermediate in the formation of N-methylaniline from NN-dimethylanilineby showing that N-oxide formation occurred more rapidly than the overalldemethylation in pig- and rat-liver microsome preparations.With agedmicrosomes there was an accumulation of the N-oxide and a correspondingdecrease in formaldehyde formation. The N-oxide-formingactivity required NADPH and oxygen and could be dissociatedfrom the demethylating activity by treating the microsomesHowever, the general nature of this reaction in oxidativeN-dealkylation, as claimed by the authors, is doubtful. The (6)isolation of the glucuronides of (+)- and (-)-N-hydroxy-methylglutethimide (6) as metabolites of (+)- and (- )-N-methylgluteth-mide 41 offers direct confirmation of the alternative pathway:>Me --+ [ >*CH2-OH] + >H + CH20As pointed N-oxidation of the imide is chemically unsound. McMahonand Sullivan 42 observed that, although hydroxylation of the alkyl groupcould occur with O-alkyl compounds, oxide formation would be dependentboth on the basicity of the oxygen acceptor and on steric hindrance.Sincethe amine (7) is extensively N-demeth~lated?~ steric hindrance appears notto be a major factor. A further argument against the general nature of anN-oxide mechanism is provided by the oxidative demethylation of 1-fi?with cholate. * ? CHZ-OHHCFC*CMe,*NMeBut p h v o * C o E tPh*CH2/ \CHMe*CH,*NMe,( 7 ) (8)propoxyphene (8) and its N-oxide by rat-liver microsomes.42 Unlike manyN-oxides, 1 -propoxyphene N-oxide is appreciably lipid-soluble but still wasdealkylated much more slowly than the tertiary amine.The isolation of an FAD-dependent enzyme (FAD = flavine-adeninedinucleotide) catalysing N-oxidation of NN-dimethylaniline 44 and differingfrom NADPH-cytochrome c reductase in its absolute requirement for FADmight help to settle some of the points in this controversy.It will be ofinterest to see whether the same enzyme is involved in the N - and theS-oxidation of other drugs.39 Y. Imai and R. Sato, Biochern. Biophys. Acta, 1960, 42, 164.40 D. M. Ziegler and F.H. Pettit, Biochem. Biophys. Res. Comm., 1964, 15, 188.41 H. Keberle, W. Riess, K. Schmid, and K. Hoffmann, Arch. int. Pharmacodyn.,4 2 R. E. McMahon and H. R. Sullivan, Life Sciences, 1964, 3, 1167.43 R. E. McMahon and N. R. Easton, J . PharmacoE., 1962, 135, 128.44F. H. Pettit, W. Orme-Johnson, and D. M. Ziegler, Biochem. Bzophys. Res.,1963, 142, 125.Comrn., 1964, 16, 444466 BIOLOGICAL CHEMISTRYInhibition and Stimulation of Metabolism.-The mechanisms wherebythe drug SKF525A (9) inhibits drug metabolism remain obscure and complexPr**CPli2*CO*0.[CH,],.NEt, Ph 6 \ CI(9) O-CH2.CH2.NEt2(10)although some progress has been made recently. Competitive inhibitiondoes not seem to be confined to plasma procaine esterase. The inhibitionof demethylation of butynamine (7) by SKF525A, Lilly 18947 (lo), and itsprimary amine analogue (DPEA) has been shown to be competitive.45 Ithas been reported that both SKF525A and Lilly 18947 are dealkylated byliver microsome preparations 46 and that drugs undergoing microsomaloxidation are mutually competitive inhibitor^.^' Gillette and Sasame 48have obtained evidence for an active metabolite of SKF525A which didnot seem to be SKF-acid since the ester was not hydrolysed t o any greatextent by washed liver rnicro~omes.~~ If this metabolite proves to be theprimary or secondary amine obtained by dealkylation then, like DPEA, itmay also act as a competitive inhibitor.SKF525A also altered the microscopic appearance of the smooth- andrough-surfaced endoplasmic reticulum within one hour after intraperitonealinjection (20-80 mg./kg.) in and, although the concentration in theliver fell sharply between 1 and 12 hr.after administration, enzyme inhibitionduring this period remained constant. The inhibitory action may, therefore,be due t o the altered endoplasmic reticulum or the presence of a stronglybound metab~lite.~*Another intriguing effect of SKF525A is its potentiation of some quatern-ary ammonium neuromuscular blocking agents. This effect was f i s treported some time ago5* and the theory was advanced that SKF525Adisplaced the neuromuscular blocking agent from sites of l0ss.5~ There issome evidence in a recent publication 62 to support this; however, SKF525Aalso seems to have a direct action a t the neuromuscular junction.53 As anester SKF525A may competitively block plasma cholinesterase, but if thiswere the case one might expect it to potentiate the competitive agents suchas curare and to antagonise the depolarising ones such as decamethonium.While such an effect was seen in the cat, SKF525A potentiated both competi-t'ive and depolarising agents in the rabbit.5345 R.E. McMahon, J. Phamacol., 1962, 138, 382.o6 M. W. Anders and G. J. Mannering, Fed. Proc., 1964, 23, 537.47 A. Rubin, T. R. Tephly, and G. J. Mannering, Biochem. Phursnacol., 1964, 13,48 J. R. Gillette and H. A. Sasame, Fed. Proc., 1964, 23, 537.*s L. A. Rogers and J. R. Fouts, Fed. Proc., 1964, 23, 537.6o G. J. Navis, J. J. Toner, and L. Cook, Fed. Proc., 1953, 12, 354.61 D.Bovet, F. Bovot-Nitti, A. Bettschart, and W. Scognamiglo, Helw. physiol.62 F. R. Domer and W. Pinto-Scognamiglio, J. Pharm. Xci., 1964, 53, 225.5 3 D. D. Bella, F. Rognoni, and U. Teotino, Brit. J. Phurmacol., 1962, 18, 563.1007.pharmucol. Acta, 1956, 14, 430FURST: DRUG METABOLISM. 467Compounds that prevent the biosynthesis of cholesterol have been foundto be general inhibitors of drug metab0lism.5~ trans-l,4-Di-(2-chlorobenzyl-aminomethy1)cyclohexane dihydrochloride (AY-9944) ( 1 l), a member of anovel class of inhibitors of cholesterol biosynthesis, prolonged the pento-barbitone hypnosis of mice and reduced the toxicity of Schradan (12),suggesting that it, too, blocks drug metab~lisrn.~~ This compound alsoinhibited the 8-hydroxylation of steroids in rat adrenal homogenate~.~~The N-demethylation of codeine, O-ethylmorphine, and laxomethorphanwas inhibited by a series of N-substituted analogues of (-)-3-hydroxy-morphinan, compounds synthesised as potential morphine antagoni~ts.~'The decreased drug metabolism associated with tolerance to morphinemay be due to a non-specific inhibition of morphine produced by its blockingaction on the release of adrenocorticotropic hormone (ACTH).There wasa significant increase in the rate of metabolism of some drugs in " stressed "animals,58 suggesting that the corticosteroids may regulate drug metabolism.Nichol and Rosenl59 found that adrenalectomy of immature rats decreasedthe demethylation of meperidine by 85% and prolonged the hexobarbitonesleeping time.These effects could be reversed by treatment with largedoses of cortisol or deoxycorticosterone, but phenobarbitone was moreeffective. Clouet and Ratner 6O determined the rate of development oftolerance to morphine in rats treated with various agents that increase theactivity of the drug-metabolising enzymes and in this way were able to dis-sociate the two events.on the correlation between hepatic glycogencontent, smooth endoplasmic reticulum, and drug metabolism Dixon andhis colleagues 62 have examined the effects of chronic and acute noradrenalinetreatment on these factors in rat-liver microsomes. Noradrenaline has aselective effect on rat hepatic glycogen and little or no depleting action onskeletal glycogen.63 The results agreed with those obtained by Fouts foradrenaline.64 An acute injection (1 mg./kg.) caused a rapid decrease in5 4 R.Kato, P. Vassanelli, and E. Chiesara, Biochem. Pharmacol., 1963, 12, 349.55 A. V. Marton and C. I. Chappel, Experientia, 1964, 20, 517.56 M. L. Givner, M. Kraml, D. Dvornik, and R. Gavory, Nature, 1964, 203, 317.57 A. Rubin, H. I. Chernov, J. W. Miller, and G. J. Mannering, J. Pharmucol.,68 W. F. Bousquet, B. D. Rupe, and T. S. Miya, Biochem. Pharmacol., 1964,13, 123,5 9 C. A. Nichol and F. Rosen, Fed. Proc., 1964, 23, 386,6o D. H. Clouet and M. Ratner, J. Pharmacol., 1964, 144, 362.61 R. L. Dixon, L. H. Hart, and J. R. Fouts, J. Pharmacol., 1961, 133, 7; J. R.Fouts, R. L. Dixon, and R. W. Shultice, Biochem.Phamacol., 1961, 7, 265.62 R. L. Dixon, L. A. Rogers, and J. R. Fouts, Biochem. Pharmacol., 1964, 13, 623.63 J. Vrij, B. Cho, C. De Groot, and J. Weber, Acta physiol. pharmacol. need., 1956,6 4 J. R. Fouts, Fed. Proc., 1962, 21, 1107.Continuing their studies1964, 144, 346.4, 547468 BIOLOGICAL CHEMISTRYthe concentration of liver glycogen but was without significant effect on theside-chain oxidation of hexobarbitone, the demethylation of aminopyrine, orthe hydroxylation of aniline. Only after repeated injections was there apronounced decline of metabolism in uitro. On cessation of treatment theglycogen levels returned to normal much more rapidly than did drug-metabolising activity. Prior administration of an adrenergic blocking agentprevented the fa11 in glycogen content without affecting the decline in drugmetabolism ; however, two of the blocking agents, phenoxybenzaminehydrochloride ( 13) and dihydroergotamine methanesulphonate, possessedan inhibitory action on drug metabolism per se.Ph.0 CH, CHMe II(13)N*CH,.CH,ClCH,*PhStudies on the biphasic action of inhibitors and inducers, first reportedby Serrone and F ~ j i m o t o , ~ ~ have been extended by Kato and his co-workers.66A number of inhibitors such as SKF525A, Lilly 18947, and DPEA eliciteda stirnulatory effect 48 hours after injection and, conversely, many inducerssuch as glutethimide, chloretone, and nikethamide had an inhibitory actionif given 4 hour before the assay.The relationship is not simply one of thetime factor, since the strong inhibitors were not good inducers and vice versa.Also of interest was that combining an inhibitor with an inducer potentiatedthe stimulation of the latter, presumably because its metabolism andelimination were impeded.The number of compounds whose metabolism may be accelerated byothers continues to grow.Thus, phenobarbitone has been reported tostimulate the metabolism of phenylbutazone, 67 lidocaine, 68 griseofulvin,strychnine,70 p-nitroani~ole,7~ and sulphadimethoxine 72 in rats, rabbits, ormice. Remmer and Siegert have greatly increased the acetylation ofaminoantipyrine in dogs by pre-treating them for several days with pheno-barbitone, thus confirming previous findings that the failure of dogs toacetylate suitable substrates is due to the presence of an inhibitor and notto a deficiency of the responsible enzyme system.74The effects of inducers of drug-metabolising enzymes are not confined t othese enzymes alone but are also seen in a number of other systems.Somesoluble NADP-requiring enzymes are affected. The stimulation of UDP-asD. M. Serrone and J. M. Fujimoto, J . Pharmawl., 1961, 133, 12.R. Kato, E. Chiesara, and P. Vassanelli, Biochem. Pharmacol., 1964, 13, 69.67 K. D. Courteney and H. M. Tepperman, Fed. Proc., 1964, 23, 538.6 8 J. Heinonen, Acta Phrmucol. (Denmark), 1964, 21, 155.6B D. Busfield, K. J. Child, and E. G. Tomich, Brit. J . Plk-mnmoE., 1964, 22, 137.70 H. Tsukamoto, K. Oguri, T. Watabe, and H. Yoshimura, J . Biochem. Japan,71 K.J. Netter and G. Seidel, J . Phrmacol., 1964, 146, 61.7 2 H. Remmer, Naunyn-Schmiedeberg's Arch. exp. Path. Phrmak., 1964, 247, 461.7 a H. Remmer and M. Siegert, Naunyn-Schmiedeberg's Arch. exp. Path. Pharmak.,7 4 K. C. Leibman and A. M. Anaclerio, Proc. First Internat. Pharmacological1964, 55, 394.1964, 247, 522.Meeting, Vol. VI, Pergamon Press, London, 1962, p. 91FURST: DRUG METABOLISM 469glucose-NAD-oxidoreductase has previously been reported, 75 and morerecently pre-treatment with phenobarbitone, arninopyrine, diphenhydramine,or barbital has been found in vitro to increase the activity of D-glucose6-phosphate-NADP-oxidoreductase and 6-phospho-~-gluconate-NADP-oxidoreduct ase. 78 The hydrocarbons 3,4- benzop yrene and 3 - methylcholan-threne were ineffective. DDT which has recently been shown to be aninducer 77 affected the distributive pattern of soluble liver enzymes in therat ' 8 and has also been reported to cause a pronounced fall in liver D-glucose 6-phosphate-NADP-oxidoreductase.79Pre-treatment withphenobarbitone or chlorcyclizine stimulated the microsomal hydroxylationof testosterone (14) and androst-4-ene-3,17-dione (15) in rats.80 Phenyl-butazone has similar effects in both rats and dogs.81 In rats pre-treatmentThe hydroxylation of some steroids is also affected.?H 0(14) (15)with phenylbutazone stimulated the microsomal hydroxylation of testo-sterone in vitro and androst-4-ene-3,17-dione to the respective SF-, 7a-, and16a-hydroxy-compounds.In dogs there was a 2-4-fold increase in the6P- and 16a-hydroxylation of both compounds.82 Phenobarbitone has alsobeen shown to accelerate the metabolism of androsterone and of 17-cestradiolin rats.S3Prior administration of either phenobarbitone or phenylbutazone hadlittle effect on the overall metabolism of cortisone (16) and cortisol (17) byrat-liver microsomes but stimulated the minor metabolic pathway to polar(possibly hydroxy-) compounds by 50-140 %.*l 3-Methylcholanthrene hadlittle effect on this minor pathway but greatly reduced the overall metabolismCO*CH2*OH CO*CH2*OH@ --OH o f l - - - O H H/ '",i"'r" 0o /(16) ('7) (18)7 5 A.H. Conney, G. A, Bray, C. Evans, and J. J. Burns, Ann. New York Acad. Sei.,76 E. Bresnick and Hu-Yu Yang, Biochem.Phamacol., 1964, 13, 497.7 7 L. G. Hart and J. R. Fouts, Proc. SOC. Exp. Biol. Med., 1963, 114, 388.78 D. Wong and I. J. Tinsley, Biochem. Pharmacol., 1964, 13, 534.7 9 I. J. Tinsley, Nature, 1964, 202, 113.A. H. Conney and A. Klutch, J . Biol. Chem., 1963, 238, 1611.81A. H. Conney and K. Schneidman, J . Pharmacol., 1964, 146, 225.8 2 L. D. Garren, A. H. Conney, and G. M. Tomkins, J . Clin. Invest., 1961, 40, 1041.83 R. Kuntzman, M. Jacobson, K. Schneidman, and A. H. Conney, Fed. Proc.,1961, 92, 115; 0. Touster and R. W. Hefter, ibid., p. 318.1964, 23, 537470 BIOLOGICAL CHEMISTRYof cortisone and cortisol. Diphenylhydantoin (18) and its main metabolite,5-(p-hydroxyphenyl)-5-phenylhydantoin, caused a pronounced increase inthe side-chain reduction of cortisol in male-rat-liver incubates and increasedthe reduction of ring A in a similar preparation from female rats, but hydroxyl-ation at position 6 in both sexes was depressed.wIt seems probable that enzyme induction is due to enzyme synthesisde mvo mediated through the production of m-RNA (ribonucleic acid).Gelboin and Blackburn 85 have shown that the induction of benzopyrenehydroxylase in a number of tissues by 3-methylcholanthrene can be inhibitedby puromycin or actinomycin D.The latter antibiotic also. inhibited thephenobarbitone-induced increases in aminopyrine-demethylating activityand in the formation of NADPH-cytochrome c reductase and of CO-bindingpigment.' Recently, cortisol has been shown to stimulate the 32P-turnoverin the nuclear and microsomal RNA of rat-liver cells,86 the nuclear fractioncontaining m-RNA 87 showing the greatest response. The possible role ofcorticosteroids in drug metabolism has already been referred t0.58~59Pyridine Nuc1eotides.-The level of pyridine nucleotides would also beexpected to affect the metabolism of drugs and other substrates, and thismay be a factor in some conditions of decreased drug metabolism.Theconcentrations of oxidised and reduced di- and tri-phosphopyridine nucleo-tides of rat liver a t nine different ages have been measured from the fifthday before birth.88 By 14 days of age a 3-&fold increase in nucleotideconcentration per gram of liver was observed. Metabolising activity indeveloping rats increases with age, reaching a maximum by 30 days of age,after which it gradually decreases.8g Variations in the ratio of oxidised toreduced forms of the pyridine nucleotides may also be of importance.Withstarvation and alloxan-diabetes the NAD : NADH ratio in rat liver decreased,while the NADP:NADPH ratio increased.g0 This increased ratio could beone of the reasons for the depressed drug metabolism found in alloxan-diabetic male rats.g1 Carbon tetrachloride poisoning (0.125 m1./100 g. bodywt.) had a rapid effect on NADP and NADPH levels in the liver of rats, sothat even 1 hour after administration there was a significant increase in theNADP:NADPH ratio.92 In contrast, a single dose of ethanol caused littlechange in the NADP and NADPH content of rat liver but decreased theNAD :NADH ratio by about half within 30 minutes, the ratio only returningto normal after 13 or more h0urs.9~Mercapturic Acid Formation.-A third enzyme has been reported g4 thatthat differs in its substrate requirement from glutathione-S-aryl transferase(glutathiokinase) and the glutathione-S-alkyl transferase recently dis-84 L.J. Sholiton, E. E. Werk, Jr., and J. MacGee, Metabolism, 1964, 13, 1382.* 5 H. V. Gelboin and N. R. Blackburn, Cancer Res., 1964, 24, 356.a6 C. E. Selreris and N. Lang, Life Sciences, 1964, 3, 169.8 7 N. Lang and C. E. Sekeris, Life Sciences, 1964, 3, 161.8 s R. Kato, P. Vassanelli, G. Frontino, and E. Chiesara, Biochem. Pharmacol.,H. B. Burch and P. Von Dippe, J. Biol. Chem., 1964, 239, 1898.A. W.Lindall, Jr., and A. Lazarow, Metabolism, 1964, 13, 259.1964, 13, 1037.SIR. L. Dixon, L. G. Hart, and J. R. Fouts, J . Pharmacol., 1961, 133, 7 .ga T. F. Slater, U. D. Strauli, and B. C. Sawyer, Biochem. J., 1964, 93, 267.s3 T. F. Sleter, B. C. Sawyer, and U. D. Strauli, Biochem. J., 1964, 93, 267.S4 E. Boyland and K. Williams, Biochem. J., 1964, 91, 7PFURST DRUG METABOLISM 47 1c0vered.~5 This new enzyme, prepared from the supernatant liquor fromsoluble rat-liver could be partially purified from glutathione-X-aryl transferaseby absorption on calcium phosphate gel and was identified by its activitytowards 2,3-epoxypropylphenyl ether. Grover and Sims 96 have examinedthe distribution of glutathione-S-aryl transferase in vertebrates and also itsapparent identity with the enzyme involved in the biliary excretion ofconjugated sulphobromophthalein.Cohen and his co-workers 97 havestudied glutathione conjugation in locusts and other insects because of itssignificance in the metabolism of insecticides such as gammexane. Theglutathiokinase of insects differed from that of the rat and rabbit by it'sready inhibition by phthaleins.Further direct evidence has been produced9* for the participation ofglutathione in the formation of alkylrnercapturic acids. After the sub-cutaneous injection of X-alkylglutathiones in rats the mercapturic acid cor-responding to the alkyl group was detected in the urine. The S-oxides ofthe mercapturic acids were also identified. In addition, S-methylglutathione(19) yielded X-methyl-L-cysteine (20) and other compounds which, togetherwith methylniercapturic acid, have been found in the urine of rats afterthe administration of S-methyl-~-cysteine.Qg The formation of ethyl-mercapturic acid sulphoxide in rats from X-ethyl-L-cysteine, S-ethyl-L-cysteine S-oxide, and ethylmercapturic acid has also been reported.lO0Me S *CH ,.CH*C 0 *NH*CH,*C 0 ,H MeS*CH,.CH (NH,)*CO ,HINH*CO*CH,*CH,*CH( NH,) C0,H(19)A novel pathway involving glutathione has been ascribed to the meta-bolism of the in vitro carbonic anhydrase inhibitor, benzothiazole-Z-sulphon-amide (21).lo1 X-2-Benzothiazolylmercapturic acid, benzothiazole-2-thiol,and X-2-benzothiazolylthioglucuronic acid haveand dog.These metabolites were also produced 1 > S 0 2 - ~ ~ 2been detected in the urine of the rabbit, rat,by soluble or supernatant, but not by particu-late, liver fractions.It was suggested that2-benzothiazolylglutathione, formed by a direct replacement of the sul-phonamide group, served as a labile intermediate in their formation. Theisolation of the benzothiazolylt,hioglucuronic acid in the urine of dogsreceiving benzothiazole-2-sulphonamide was reported some years ago,lo2 andat that time it was believed that the sulphonamide group was reduceddirectly to the thiol which was then conjugated with glucuronic acid. Thiswas also a novel reaction for a sulphonamide.0; (2 1)95 M. K. Johnson, Biochem. J., 1963, 87, 9P.geP. L. Grover and P. Sims, Biochem. J., 1964, 90, 603.9 7 A.J. Cohen, J. N. Smith, and H. Turbert, Biochem. J., 1964, 90, 457.gs C. J. Foxwell and L. Young, Biochem. J., 1964, 92, 50P.9 9 E. A. Barnsley, Biochern. J., 1964, 90, 9P.loo E. A. Barnsley, A. E. R. Thomson, and L. Young, Biochem. J., 1964, 90, 588.Io1 D. F. Colucci and D. A. Buyske, Fed. Proc., 1964, 23, 282.Io2 J. W. Clapp, J . Biol. Chem., 1956, 223, 207472 BIOLOGICAL CHXMISTRYMany carcinogenic aromatic hydrocarbons are excreted partially aswercaptyric acids, and 8-arylcysteines have been detected in tissues whichbind these hydrocarbons.lo3 It has now been shown that these arylcysteinesmay be utilised in pathways of protein biosynthesis. Bucovaz and Wood lo4have described an enzyme system from rat-liver which catalysed the activa-tion and transfer of two substituted cysteines, 8-p-chlorophenyl- and S-(1,2,3,4-tetrahydr0-2-hydroxy-l -naphthyl)-~-cysteine, to ribosomes.As theauthors pointed out, this may represent one way whereby these hydrocarbonsbecome protein-bound, although some tissues such as skin, which bindhydrocarbons, do not appear to form mercapturic acids.Cancer and the Metabolism of Aromatic Amines.-Since the originalfinding in 1960 lo5 that 2-acetamidofluorene (22) was metabolised in rats to24 N-hydroxyacetamido)fluorene (23), the hydroxylamines of several other6 5 4 39(22) (2 3)carcinogens have proved to be more potent than their parent compounds,106and this metabolic conversion has been demonstrated with several otheraromatic amines and amides.lo7 It is, therefore, important to extend thesestudies to more species and more compounds.The metabolism of 2-acetamidofluorene has now been examined inman,lo8 in the hamster,l~ and in the cat.ll0 In all three species, both ring-and N-hydroxylation occurred, although in the cat, which is deficient inglucuronyltransferase,lll the hydroxylated compounds were mainly con-jugated through sulphuric acid rather than glucuronic acid.Significantly,however, 10-15% of the urinary metabolites were present as glucuronides,which is evidence that the cat is not completely lacking in glucuronyl-transferase. This has been substantiated by the finding of glucuronide-likemetabolites in the urine of cats receiving the radiopaque substances, iopanoicacid [3-amino-cc-ethyl-~-(2,4,6-tri-iodophenyI)propionic acid], tryopanoicacid (the 3- butyramido-analogue), and buramiodyl [ 3- butyramido-cc-ethyl-18- (2,4,6-tri-iodophenyl)propionic acid].lo3 J.T. Smith and J. L. Wood, J . Biol. Chem., 1959, 234, 3192.lo4E. T. Bucovaz and J. L. Wood, J . Biol. Chem., 1964, 239, 1151.lo5 J. M. Cramer, J. A. Miller, and E. C. Miller, J . Biol. Chem., 1960, 235, 885.lo6 E. C. Miller, J. A. Miller, and H. A. Hartmann, Cancer Res., 1961, 21, 815;J. A. Miller, C. S. Wyatt, E. C. Miller, and H. A. Hartmann, ibid., p. 1465; J. A. Miller,M. Enomoto, and E. C. Miller, ibid., 1962, 22, 1381; E. Boyland, C. E. Dukes, and I?. L.Grover, Brzt. J . Cancer, 1963, 17, 79.lo' C. C. Irving, Cancer Res., 1962, 22, 867; W. Troll and N. Nelson, Fed.Proc.,1961, 20, 41; W. Troll, S. Belman, and E. Rinde, Proc. Amer. Assoc. Cancer Res.,1963, 4, 68; ref. 106.J. H. Weisburger, P. H. Grantham, E. Vanhorn, N. H. Steigbigel, D. P. Rall,and E. K. Weisburger, Cancer Res. 1964, 24, 475.l o o J. H. Weisburger, P. H. Grantham, and E. K. Weisburger, Toxicol. appl.Pharmacol., 1964, 6, 427.110 J. H. Weisburger, P. H. Grantham, and E. K. Weisburger, Biochem. Pharmacol.,1964, 13, 469.111 G. J. Dutton and C. 0. Greig, Biochem. J., 1957, 66, 52P.112 E. W. McChesney, Biochem. Pharmacol., 1964, 13, 1366FURST: DRUG METABOLISM 473There is also a sex difference in the metabolism of 2-acetamidofluoreneby rats,113 since male rats excreted more urinary sulphate conjugates andless of the glucuronic acid conjugates than did females.The latter producedmore 2-(N-hydroxyacetamido)fluorene but less of the 5- and 7-hydroxylatedcompounds.Adult rats with various forms of liver damage, and young growing rats,have been reported to excrete a greater percentage of a test dose of 2-acet-amidofluorene as the N-hydroxylated metabolite than did normal adultcontrols.ll4 Changes in the urinary output of ring-hydroxylated metaboliteswere very small.Irving has reported the N-hydroxylation of 2-acetamidofluorene by livermicrosomes from the rabbit, hamster, dog, cat, chicken, rat, and mouse,but not from the guinea-pig or human.ll5 2-Acetamidofluorene is notcarcinogenic to the guinea-pig and this has been attributed to the absenceof N-hydroxylated metabolites ;log however, the reason why no 2-( N -hydroxyacetamido)fluorene could be detected in human-liver microsomes isnot clear.The same author has also shown that 2-(N-hydroxyacetamido)-fluorene was itself rapidly metabolised by a rabbit-liver 10,000 x g super-natant fraction. Some of the metabolites identified were 2-acetamido-fluorene, 2-arninofluorene and its N-glucuronide, and the O-glucuronide of2- (N-hydroxyacetamido)fluorene. Booth and Boyland have detectedZ-amino- 7 - hydroxy - , 2-amino- 1 - hydroxy - , 2- hydroxyamino- , and 2-amino-fluorene on metabolism of 2- (N-hydroxyacetamido)fluorene by rat- or rabbit-liver microsomes, but on the addition of potassium fluoride ( 0 . 1 ~ ) to preventdeacetylation no metabolites could be detected.The formation of S-amino-1 -hydroxyfluorene is of interest since 2-acetamido-1 -hydroxyfluorene hasnot been detected as a urinary metabolite of 2-acetamidofluorene or of2-(N-hydroxyacetamido)fluorene in the rabbit. It was probably producedin the microsomal preparation by the rearrangement of Z-hydroxyamino-fluorene.The metabolism of trans-4-acetamidostilbene (24), a member of thePh.CH=CH.C,H,*NHAc-p(24)truw-4-aminostilbene and truns-4-aminoazobenzene groups of carcinogens,has been followed in the rat.ll7 Both trans-4-acetamidostilbene and trans-4-aminostilbene formed trans-N-hydroxyacetamidostilbene which was shownto be more carcinogenic than either of its precursors in a number of tests.truns-N-Hydroxyacetamidostilbene was itself metabolised largely to trans-3 - hydrox yace t amidos t ilbene which appeared to have little carcinogenicaction.This was taken by the authors as further evidence that the hydroxyl-amines rather than their corresponding o-aminophenols are more potentllS E. K. Weisburger, P. H. Grantham, and J. H. Weisburger, Biochemistry, 1964,3, 808.l14A. Margreth, P. D. Lotlikar, E. C. Miller, and J. A. Miller, Cuncer Res., 1964,24, 920.115 C. C. Irving, J. Biol. Chern., 1964, 239, 1589.116 J. Booth and E. Boyland, Biochem. J., 1964, 91, 362.11' R. A. Andersen, M. Enomoto, E. C. Miller, and J. A. Miller, Cuncer Res., 1964,24, 128474 BIOLOGICAL CHEMISTRYproximate carcinogens. This rearrangement of N-hydroxylated acetamido-aryl compounds to the corresponding o-acetamidophenols may be a generalreaction catalysed by a, soluble rabbit-liver 105,000 x g supernatantfraction.l1 N-H ydroxyacetanilide, 2 - ( N - hydroxyacetamido)napht halene,4-(N-hydroxyacetamido)biphenyl, and 2-(N-hydroxyacetamido)fluorene (23)all rearranged to the ring-hydroxy-compounds. The activity of thispreparation appeared to be due to an enzyme with a requirement for NAD,NADH, or NADPH. The rearrangement of the N - hydroxyarylaminesthemselves could not be followed since they were rapidly reduced to theparent arylamines.Some metabolites of tryptophan have been implicated in cancer af thebladder,ll* and the metabolism of one of these, anthranilic acid, has nowbeen examined in rats and rabbits for the occurrence of N-hydroxylation;119but no hydroxyaminobenzoic acid could be detected in the urine of animalsreceiving either tryptophan or anthranilic acid.Absolute Co&uration.-The sterospecificity of the microsomal epzymeswas shown by Axelrod120 who found that the laevorotatory isomers of anumber of narcotic drugs were N-demethylated 2-3 times more readilythan their dextro-enantiomorphs.On these grounds it was proposed thatthe microsomal N-demethylases might resemble the receptor for narcoticanalgesics. Differences in the metabolism of optically active " non-specific "drugs are also known.l2l The metabolism of glutethimide (25) and itsderivatives, N-methylglutethimide (26) and the tetralone derivative (27),(27)(25) R = H(26) R = Mehas been studied by using racemates in which the enantiomorphs weredifferentially labelled with 3H and l4C.l22 The pharmacologically moreactive (+ )-glutethimide, (+)-N-methylglutethimide, and the (-)-tetralonewere metabolised more slowly than their enantiomorphs by a rabbit liverhomogenate.These fmdings were paralleled by the higher tissue concentra-tions of (+)-glutethimide and (+)-N-methylglutethimide in the rat in whichthese isomers were also the more active. [The results for the (-+)-tetralonewere inconclusive, possibly because of the insensitivity of the test procedure.]Kinetic studies in rats on the N-demethylation of ( -j-)-N-methylglutethimidesuggested that hydroxylation of the methyl group occurred more rapidlyl 1 8 M . J. Allen, E. Boyland, C. Dukes, E. S. Homing, and G.J. Watson, Brit.119 E. Boyland and A. R. Fahmy, Biochem. J., 1964, 91, 73.120 J. Axelrod, J . PhumacoE., 1956, 117, 322.lZ1 T. C. Butler and W. J. Waddell, J. Pharmacot., 1954, 110, 120; H. Keberle,K. Hoffmann, and K. Bernhard, Experientia, 1962, 18, 105; ref. 41.122 K. Schmid, W. Riess, and H. Keberle, Internat. Conference on the Uses ofIsotopically Labelled Drugs in Experimental Pharmacology, June 6-10, 1964, Chicago.J. Cancer, 1957, 11, 212FURST: DRUG METABOLISM 475in the (-)-isomer and that the resulting hydroxymethyl metabolite wasconjugated with glucuronic acid at a faster rate. On the available evidenceit was believed that the three more active enantiomorphs have the sameabsolute configuration.The (+)- and the (-)-isomers of the antituberculosis drug (28) areexcreted at different rates in the dog.lZ3 The main metabolic pathway forboth isomers is shown in (28) -+ (29).The first step to the aldehyde couldbe performed by soluble or microsomal fractions of rat-liver or by horse-liver alcohol dehydrogenase, but the soluble enzymes were more active thanHO *CH,*CHE t *NH*CH,*CH,.NH*CHE t -CH,*OH (28) 4-1OHC.CH,-CHEt-NH*CH2*CH2*KH*CHEt*CH2*OH(29) HO,C.CH,*CHEt*NH*CH,*CH,.NHCHE t.C02Hthe NADPH-dependent microsomal enzymes. It was not readily apparentwhether the differences in distribution and excretion were due entirely todifferent metabolic rates since both isomers were oxidised at similar ratesby liver alcohol dehydrogenase. The inactive (- )-isomer may also be morestrongly bound by some tissues.Genetic EBects.-Genetically determined differences in the hydrolysis ofsuccinylcholine 124 and in the acetylation of isoniazid lZ5 are well known.It now seems that the rates of acetylation of sulphadiazine 126 and sulpha-dimidine l 2 7 are also polymorphic.Differences in the sulphadiazine acetylaseconcentrations in rabbit-liver have been correlated with the acetylationrate in and both isoniazid and sulphadiazine were metabolised atthe same rate in a given animal, suggesting that the acetylation of both wascontrolled by the same alleles. It has also been stated128 that the meta-bolism of diphenylhydantoin may be genetically controlled. This is ofinterest in view of some recent doubts 129 about the fundamental role of thedrug-metabolising enzymes in liver microsomes, since diphenylhydantoinunlike the above compounds is mainly hydroxylated in man.130 It seemsunlikely that genetic factors should be involved in the metabolism of foreignorganic compounds.It has been suggested129 that the N- and the 0-demet'hylase might be involved in the demethylation of N-methylpurinesand methylated ribose which is found in mammalian RNA. Other workershave also demonstrated a strong resemblance between the drug-hydroxylat-ing enzymes and the enzymes hydroxylating testosterone and estradiol(" steroid hydroxylases ").83123 E. A. Peets and D. A. Buyske, Biochem. Pharmacol., 1864, 13, 1403.lZ4 W. Kalow and N. Staron, Can&. J . Biochem. Physiol., 1957, 35, 1305.125 D.A. P. Evans, K. A. Manley, and V. A. McKusick, Brit. Med. J . , 1960, 2,485; J. H. Peters, K. S. Miller, and P. Brown, Fed. Proc., 1964,23,280; H. W. Goedde,E. Schoepf, and D. Fleischmann, Biochem. Pharmacol., 1964, 13, 1671.las J. W. Frymoyer and R. F. Jacox, J . Lab. Clin. Med., 1963, 62, 891, 905.D. A. P. Evans, Quart. J . Med., 1963, 32, 366.128 I. H. Porter, Tox&.d. Appl. Pharmacol., 1964, 6, 499.129 L. Shuster, Ann. Rev. Biochem., 1964, 33, 571.13* E. W. Maynert, J . Pharmacol., 1960. 130, 275.3. BIOCHEMICAL DISORDERS IN INHERITEDMETABOLIC DISEASESBy J. C. Crawhall(Medical Professorial Unit, St. Bartholomew’s Hospital, London, E.C.l)N u M E R o TJ s advances in our knowledge of intermediary metabolism havebeen made as a result of studying inherited metabolic disorders.Thesedisorders represent genetic variants which are inherited by the patients.Many have been shown to be inherited via a single autosomal recessive gene,and current theory of biochemical genetics would predict that if a genemutation occurred in a structural gene then the inherited defect could belocated in a single enzyme molecule. Mutation of a regulatory gene couldoccur in which case no single enzyme defect would be observed. In manyof these diseases a single enzyme defect has been demonstrated. Inoroticaciduria (see below) two separate enzymes appear to be defective. Byanalogy with microbial genetics, if several enzymes are coded on one operon,then mutation of a single gene can interfere with the synthesis of otherenzymes controlled by the genes of that 0peron.l I f such a mechanism isrelevant to mammalian systems, then multiple enzyme defects could arisefrom a single mutation.In some of the diseases studied the biochemicalabnormality observed may be only an indirect consequence of the primarydefect, and the biochemical and genetic picture will appear confused. Inthis Report only those defects which are detrimental to the patients will beconsidered. The Report is restricted principally to disorders affectingintermediary metabolism ; disorders of porphyrin, bilirubin, thyroid, andsteroid metabolism have been omitted.Disorders of Sugltr Metabolism.-Galactoszmia. Galactoszemia is ahereditary disorder characterized in infants by their failure to thrive and bytheir vomiting after ingestion of food containing galactose.2u The galactoseintolerance is caused by a deficiency of galactose l-phosphate uridyl trans-ferase.Zb The deficiency can be detected in the liver and in the erythrocytes.3Less severe deficiency can be detected in the erythrocytes of parents ofthe affected children.4 Galactose l-phosphate uridyl transferase activityhas been shown to be 50% higher in the leucocytes of patients with Down’ssyndrome (mongolism) than in the normal population, and these authorssuggested that as fhese patients showed C21 trisomy, the genetic locus forgalactose 1 -phosphate uridyl transferase might be on the C21 chromosome.No increase of galactose 1-phosphate uridyl transferase was found in the1 B.N. Ames and P. E. Hartman, Cold Spr. Harb. Syrnp. quant. Biol., 1963, 28,349.(a) G. M. Komrower, V. Schwarz, A. Holzel, and L. A. Golberg, Arch. D i g .Chilo?., 1956,31,254; ( b ) H. M. Kalckar, E. P. Anderson, and K. J. Isselbacher, Biochirn.Bwphys. Acta, 1956, 20, 262.3 E. P. Anderson, H. M. Kalckar, K. Kurahashi, and K. J. Isselbacher, J. Lab.Clin. Med., 1957, 50, 469.H. N. Kirkman and E. Bynum, Ann. hum. Genet., 1959, 23, 117; A. Robinson,J . Exp. Med., 1963, 118, 359CRAWHALL : BIOCHEMICAL DISORDERS 477erythrocytes of the Down's patients.5 Further investigation on theseleucocytes showed that other enzyme activities were also raised, so it appearsthat this is not a specific effect.6 The erythrocytes of some galactoszemicpatients had a low capacity to metabolize galactose and this capacity wasitself familial.' There was no evidence that this small amount of galactosewas being metabolized by a different pathway, as had been previouslysuggested.* Cells of skin and bone marrow grown in tissue culture showed adifferent rate of growth in media containing either glucose or galactose.Itwas possible to distinguish cells from normal, homozygous, and heterozygouspatients by their rate of oxidation of [1-14C]galactose.9 It has been shownthat galactose was the most rapid of the sugars to induce lens cataract in therat. This was related to its rapid rate of reduction to dulcitol in the lensand to the fact that dulcitol itself was not removed by the non-specificpolyol dehydrogenase. As the sugar alcohols diffuse only slowly, waterenters the lens fibres by osmosis and leads to their rupture with cataractformation.1° Galactitol (dulcitol) was isolated from the urine of two patientswith galactoszemia by gas-chromatography as the O-trimethylsilyl ethers.llThis finding indicates that there may be a reductive pathway for galactosemetabolism.It had previously been thought that the demonstration of absence ofgalactose 1 -phosphate uridyl transferase from the erythrocytes indicated atotal absence of galactose metabolism in the patient, but it has recentlybeen shown by [14C]galactose infusion tests that there is a small sub-group ofgalactossemic patients who have a limited capacity for metabolizing galactose.There was a complete deficiency of galactose 1 -phosphate uridyl transferasein the erythrocytes, but liver biopsy tissue from these patients was able toconvert [14C]galactose into carbon dioxide.12 The conclusion is drawn thatthere is no evidence that galactossemics overcome their metabolic defectas they grow older, but an in uivo test of galactose metabolism might indicatethat some patients have a limited facility for galactose metabolism.This is an entirely benign hereditary condition,13in which the phosphorylation of fructose to fructose 1 -phosphate, broughtabout by fructokinase, is thought to be defective.14 These patients are,however, able to absorb fructose from the gut and this suggests the presenceof an intestinal fructokinase.Hereditary fructose intolerance.This is characterized by failure to thrive,Essential fructosuria.D. Y. Hsia, T. Inouye, P. Wong, and A. South, New Engl. J. Med., 1964, 270,W. J. Mellman, F. A. Oski, T. A. Tedesco, A. Maciera-Coelho, and H. Harris,1085.Lancet, 1964, ii, 674. ' WonGin, Ng, W. R. Bergren, and G. N. Donnell, Nature, 1964, 203, 845.a A. N. Weinberg, Metabolism, 1961, 10, 728.R. S. Krooth and A. N. Weinberg, J. Exp. Med., 1961, 113, 1155.lo J. M. Konoshita, S. Futterman, K. Satoh, and L. 0. Merola, Biochim. Biophys.Acta, 1963, 74, 340.l1 W. W. Wells, T. A. Pittman, and T. J. Egan, J . Biol. Chem., 1964, 239, 3192.l2 S. Segal, A. Blair, and Y. J. Topper, Science, 1962, 136, 150; S. Segal, A. Blair,and H. Roth, Amer. J . Med., 1965, 38, 62.l3 M.Lasker, Hum. Biol., 1941, 13, 51.l4 E. R. Froesch, A. Prader, A. Labhart, H. W. Stuber, and H. P. Wolf, Schweiz.rned. Wschr., 1957, 87, 1168478 BIOLOGICAL CHEMISTRYvomiting, hepatomegaly, hypoglycaemia, albuminuria, and aminoaciduria,commencing in infancy. There was thought to be a deficiency of hepaticfructose 1-phosphate-splitting ald01ase.l~ Direct enzyme analysis of hepatictissue has now confirmed this.16 Extensive studies in vivo have been carriedout on five patients.17 Ingestion of fructose leads to an increase of serum-magnesium and may be related to the consumption of the ATP-magnesiumcomplex with liberation of ADP and free magnesium ions. Increase of bloodfructose is associated with hypoglyczemia and low circulating-insulin values.This demonstrates that fructose per se does not stimulate insulin release andthat the hypoglycaemic episodes of hereditary fructose intolerance are notdue to excessive insulin release.18One patient having fructosuria on a fructose-free diet has been reported.lgThe patient also had sickle-cell thalassaemia (HbS + high foetal haemo-globin). A patient has been reported as having a combined intolerance tofructose and galactose; fructose, galactose, and glucose were found in thepatient's urine.20Hereditary disaccharide intolerance.Hereditary intolerance in infancy tolactose 21 and sucrose 22 has been described. Intolerance to isomaltose hasalso been reported.23 The specificity of intestinal disaccharidases has beenstudied.24 Continued exposure to these disaccharides can be fatal in infancy,but compensatory mechanisms appear to develop after the first year.22 Newmethods of assaying intestinal disaccharidases have been reported.25 In-testinal disaccharidase activity was measured in biopsy specimens ofduodenal mucosa in an infant with sucrose intolerance.Decreased activityof isomaltase, sucrase, and maltase were found.26 Similar intestinal di-saccharidase deficiencies have now been reported in adults.27This subject has recently been reviewed byH. G. Hers,28 and his classification will be used in this review. Recent workhas principally centred on finding diagnostic enzymic procedures for thecharacterization of the type of glycogenosis without having recourse to liverbiopsy.l6 E.R. Froesch, A. Prader, H. P. Wolf, and A. Labhart, Helv. P z d i a t . Acta,1959, 14, 99.16 E. R. Froesch, H. P. Wolf, and H. Baitsch, Amer. J. Merl., 1963, 34, 151;R. Dubois, H. Loeb, H, A. Ooms, P. Gjllet, J. Bartman, and A. Champernois, Helv.Padiat, Acta, 1961, 16, 90; H. G. Hers and G. Joassin, Enzymol. Biol. Clin., 1961, 1, 4;B. Levin, V. G. Oberholzer, G. J. A. Snodgrass, L. Stirnmler, and M. J. Wilmers,Arch. Dis. Child., 1963, 38, 220.1' M. Cornblath, I. M. Rosenthal, S. H. Reisner, S. H. Wybregt, and R. K. Crane,New Engl. J . Med., 1963, 269, 1271.18 E. Samols and T. L. Dormandy, Lancet, 1963, i, 479.19 A. K. Khachadurian, Pediatrics, 1963, 32, 455.20 T. L. Dormandy and R. J . Porter, Lancet, 1961, i, 1189.21 A. Holzel, V.Schwarz, and K. W. Sutcliffe, Lancet, 1959, i, 1126; S. Darling,2 2 A. Prader, 8. Auricchio, and G. Miirset, Schweiz. med. Wschr., 1961, 91, 465.23 C. M. Anderson, M. Messer, R. R. W. Townley, and M. Freeman, Pediatrics,24 A. Dahlquist, J . Clin. Invest., 1962, 41, 463.z 5 A. Dahlquist, Analyt. Biochem., 1964, 7, 18.26 K. Launiala, J. Perheentupa, J. Visakorpi, and N. Hallmann, Pediatriw, 1964,27 G. R. Plotkin and K. J. Isselbacher, New Engl. J . Med., 1964, 271, 1033.28 H. G. Hers, Adv. Metabolic Disorders, 1964, 1, 1.Glycogen storage diseases.0. Mortensen, and G. Sondergaard, Acta Padiat. (Uppsala), 1960, 49, 281.1963, 31, 1003; T. M. Barratt, Proc. Roy. SOC. Med., 1964, 57, 838.34, 615CRAWHALL : BIOCHEMICAL DISORDERS 479Diseases principally afecting the liver and in which muscle function is notagected. ( A ) Type I-glycogenosis of Cori, in which liver glucose-6-phos-phatase is absent.It was thought that the original disease described by vanCreveld 29 and by von Gierke 30 was of this type, but no enzyme assays wereavailable a t that time. Two of these original patients who still survivehave been reinvestigated by modern enzymic rneth0ds.~1 Glucose-6-phosphatase activity was present but there was a deficiency of debranchingenzyme. Hence these cases belong to the Type 111 glycogenosis (see below).Attempts to estimate deficiencies of glucose-6-phosphatase activity incirculating leucocytes were not successful as glucose-6-phosphatase is notpresent in normal le~cocytes.~~ Glucose-6-phosphatase activity has beenstudied in biopsy material from human jejunal mucosa and was found to beabsent for patients with Type I glycogen~sis.~~ Elevated levels of pyruvatehave been found in the plasma of these patients.34 Elevated plasma a-oxo-glutarate levels have also been rep0rted.~5 There is a report of an infantwith glycogen storage hepatomegaly who appeared clinically to be of Type I,but in whom glucose-6-phosphatase activity was only slightly reduced.Noother enzyme deficiency was detected.36(B) Type III-glycogenosis of Cori, '' limit dextrinosis " or Forbes disease.This group is subdivided into IIIA, in which muscle glycogen is found elevated,and IIIB, in which muscle glycogen is only slightly elevated. Both typesare characterized by an absence of liver amylo- 1,6-glucosidase.There havebeen three reports of low or absent amylo-1,6-glucosidase activity in thecirculating leucocytes of these patient~,3'-~9 and reduced levels were foundin hetero~ygotes.~' There is one report of an increased concentration ofglycogen in the erythrocytes of these patients, but the glycogen was foundto have abnormal side chains.40 This was not confirmed later,3* though theglycogen content of leucocytes was elevated.3g Normal levels of aniylo-l,6-glucosidase were found in erythrocyte^.^^ The original patients describedby van Creveld 29 have been reinvestigated:31 there was no deficiency ofglucose-6-phosphatase activity but there was a deficiency of amylo- 1,6-glucosidase. These patients had a high glycogen content in the erythrocyteswith low debranching enzyme activity. Debranching enzyme activity wasabsent from the leucocytes, and the patients showed normal ability to convertgalactose into glucose.(C) Type IV-glycogenosis, or Anderson's disease.*2 This disease is29 S.van Creveld, Ned. T. Geneesk., 1928, 72, 5282.30 E. von Gierke, Beitr. path. Anat., 1939, 82, 47.31 S. van Creveld and F. Huijing, Metabolism, 1964, 13, 191.a2 W. C. Hulsmann and T. L. Oei, unpublished report (referred to in F. Huijing,Clin. Chim. Acta, 1964, 9, 260).33 B. A. Ockerman, Clin. CiLim. Acta, 1964, 9, 151.3 4 T. L. Oei, Clin. Chim. Acta, 1963, 7, 193; H. E. Holling, Ann. Intern. Med.,36 J. N. Briggs and J. C. Haworth, Arner. J. Med., 1964, 38, 443.37 K.Steinitz, H. Bodur, and T. Arman, Clin. Chim. Acta, 1963, 8, 807.38 H. E. Williams, E. Kendig, and J. B. Field, J. Clin. Invest., 1963, 42, 656.3Q F. Huijing, Clin. Chim. Acta, 1964, 9, 269.4* J. B. Sidbury, M. Comblath, J. Fisher, and E. House, Pediatrics, 1961, 27, 103.41 K. Steinitz, Harefuah, 1962, 62, 275.4 2 D. H. Anderson, Lab. Invest., 1956, 5, 11.1963, 58, 654.E. ZelniEek, A. Mrskog, and F. Krystik, Clin. Chim. Acta, 1964, 9, 587480 BIOLOGICAL CHEMISTRYcharacterized by a deposition of amylopectin in the liver and is thought tobe caused by a deficiency of amylo-I ,4 -+1,6-transgly~osidase,4~ but nofurther case has been available for investigation.(0) Type VI-glycogenosis. In these patients glucose-6-phosphatase andamylo-l,6-glucosidase are present but liver phosphorylase may be diminished.Phosphorylase levels in circulating leucocytes are low in these cases.44(A) Type II-glycogenosis, orPomp6’s disease.Hepatomegaly is present and cardiomegaly with myopathymay occur. This disease is characterized by an absence of liver lysozomala-glucosidase (amylo- 1,4-glu~osidase).~~ Low levels of a-glucosidase havealso been found in circulating leucocytes.46(B) Type V-glycogenosis, or McArdle’s disease. This disease ischaracterized by muscular pain on exercise, accompanied by a lowering ofserum lactate level. Muscle phosphorylase is absent but hepatic phosphoryl-ase is present. The subject has recently been reviewed by McArdle.47 Theenzyme abnormality has been confirmed in another patient 48 and a variantof the disease has been rep~rted.~SDisorders of Amino-acid Met~bolism.--rlrgininosuccinicacidi~. Anunknown amino-acid abnormality was found in two mentally retarded ~ibs.~OThis was characterized as argininosuccinic and the findings wereconfirmed in further e~amples.5~ Argininosuccinic acid occurs in variouslactam forms and their properties have been characteri~ed.5~ Arginino-succinase is present in the erythrocytes and leucocytes of normal subjectsbut absent from these patients with the disease.The cells of the parentsof these patients had reduced enzyme activity.54A mentally retarded child, aged 1i years, was found tohave elevated levels of citrullin in the plasma, cerebrospinal fluid, and urine.Excretion of several other amino-acids was also elevated in the urine.55Citrullinuria is not reduced by antibiotic^.^^ Some abnormality of the ureacycle is indicated by the very high post-absorptive blood-ammonia levelfound in this ~atient.~7Diseases Aflecting Muscular Function.Citrullinuria.Is G.T. Cori, Harvey Lectures, Academic Press Inc., New York, 1952-1953,44 W. C. Hulmann, T. L. Oei, and S. van Creveld, Lancet, 1961, ii, 581; H. E.45 H. G. Hers, Biochem. J., 1963, 86, 11.* 6 F. Huijing, S. van Creveld, and G. Losekoot, J. Pediat., 1963, 63, 984.4 7 B. McArdle, Amer. J. Med., 1963, 35, 661.48 L. P. Rowland, S . Fahn, and D. L. Schotlend, Arch. Nezlrol. (Chic.), 1963, 9, 325.W. K. Engel, E. L. Eyerman, and H. E. Williams, New Engl. J .Med., 1963,50 J. D. Allen, D. C. Cusworth, C. E. Dent, and V. K. Wilson, Lancet, 1958, i, 182.51 D. G. Westall, Biochem. J., 1960, 77, 135.5 2 B. Levin, H. M. M. Mackay, and V. G. Oberholzer, Arch. Dk. Child., 1961,ss M. D. Armstrong, K. M. Yates, end M. G. Stemermann, Pediatrics, 1964, 33,54 S. Thomlinson and R. G. Westall, Clin. Sci., 1964, 26, 261.65 W. C. McMurray, F. Mohyuddin, R. J. Rossiter, J. C. Rathbun, G. H. Valentine,56 W. C. MeMurray end F. Mohyuddin, Lancet, 1962, ii, 352.67 W. C. McMurray, J. C. Rathbun, F. Mohyuddin, and S. J. Koegler, Pediatrics,p. 145.Williams and J. B. Field, J. Clin. Invest., 1961, 40, 1841.268, 135.36, 622.280.8. J. Koegler, and D. E. Zarfas, Lancet, 1962, i, 138.1963, 32, 347CRAWHALL : BIOCHEMICAL DISORDERS 481Cystinosis.This condition appears to be a variant of the De Toni-Fanconi syndrome which is characterized by multiple abnormalities of renaltubular function. In the cystinosis variant, cystine crystals are depositedin the reticuloendothelial system 58 and in the conjunctiva and cornea. Theplasma concentration of cystine is slightly raised,59 and it is not clear whycystine is deposited in the tissues. Secondary disorders of glycolysis ariseas the result of the cystine deposition,6* and these can be reversed by useof BAL or penicillamine.61 An adult variant of this disease has beendescribed. 62Cystathioninuria was found in a mentally defectiveadult with some skeletal abnormalities.63 (A further case has recently beenrep0rted.)~4 This patient was excreting one gram of cystathionine a day witha plasma level of 0.45 mg.per 100 ml. Somewhat more cystathionineappeared to be excreted by the kidney than was filtered from the plasma onthe basis of clearance data. The excretion of cystathionine could be reducedby administration of vitamin B,. The patient's sister and the sister'schildren excreted abnormal quantities of cystathionine but were physicallyand mentally normal. Cystathioninuria has also been reported as occurringin patients with ganglioneuroma, ganglioneuroblastoma, and malignantneur~blastoma.~~ Cystathionine has been shown to increase in the brainsof rats maintained on a vitamin B,-deficient diet. These combined resultssuggest that the defect may be in the structure of cystathioninase such thatits affinity for vitamin B6 is low.66Two siblings were found with elevation of their plasmaand urinary histidine levels.(Afurther patient was reported who also had speech defects.) This patientexcreted histidine and imidazolylpyruvic, imidazolylacetic, and imidazolyl-lactic acid. As a result of feeding experiments it was suggested that theenzyme histidase was absent.68 A defect of histidase in the epidermis oftwo patients has been demonstrated.69 Failure of growth and mentalretardation in a patient with histidinamia had recently been reported.'*The urine of these patients gives a green colour with ferric chloride, thusCystathioninuria.Histidiwmia.One of the patients had a speech defect.6758 S. E.Gould, D. L. Hinerman, J. G. Batsakis, and P. B. Beamer, Amer. J . Clin.69 M. P. Brigham, W. H. Stein, and S. Moore, J . Clin. Invest., 1960, 39, 1633.6o B. E. Clayton and A. D. Patrick, Lancet, 1961, ii, 909.61 H. Berger, I. Antener, T. Brechb&ler, and G. Stalder, Ann. Padiat., 1964,202, 465; A. Rossier, R. Caldera, and M. Odievre, Bull. SOC. mLd. Hdp. (Paris), 1963,114, 1215.62 D. G. Cogan, T. Kuwabara, J. Kinoschita, L. Sheehan, and L. Merola, J . Amer.Med. Ass., 1957, 164, 394.63 H. Harris, L. S. Penrose, and D. H. H. Thomas, Ann. hum. Genet., 1959,23, 442.64 G. W. Frimpter, A. Haymovitz, and M. Homith, New Engl. J . ,Wed., 1963,6 5 L. R. Gjessing, Lancet, 1963, ii, 1281.66 D. B. Hope, J. Neurochm., 1964, 11, 327.13' H. Ghadimi, M.W. Partington, and A. Hunter, New Engl. J . Med., 1961, 265,68 V. H. Auerbach, A. M. DiGeorge, R. C. Baldridge, C. D. Tourtellotte, and69 B. 37. La Du, R. R. Howell, G. A. Jwoby, J. E. Seegmiller, E. K. Sober, V. G.70 M. E. David amd M. J. Robinson, Arch. Dk. Child., 1963, 38, 80.Path., 1964, 41, 419.268, 333.221.M. P. Brigham, J . Pediat., 1962, 60, 487.Zannoni, J. P. Canby, and L. K. Ziegler, Pediatrics, 1963, 32, 216482 BIOLOGICAL CHEMISTRYcausing confusion with the condition of phenylketonuria. The substanceresponsible has been isolated from the urine and shown to be imidazolyl-pyruvic acid. 71 Imidazolaminoaciduria has been reported in associatioilwith cerebromacular degeneration. Carnosine, anserine, histidine, and 1 -methylhistidine were excreted in the urine.The plasma levels of theseamino-acids were nomal. 72This abnormality was originally found during a surveyof urine samples obtained from 2,000 mentally retarded patients.73 50-100mg. of homocystine were excreted per day and plasma homocystine levelswere also elevated. The renal clearance of homocystine was 3.3 ml. perminute, but the normal value for this amino-acid is not known. Methionineloading did not affect the homocystine e~cretion.7~ The presence of homo-cystine in the urine of a mentally defective child has been reported in-de~endently.~~ Enzyme studies have been carried out on a liver biopsyspecimen and a deficiency of hepatic cystathionine synthetase was demon-strated.76 Reduced levels of hepatic cystathionine synthetase activity havebeen found in liver biopsy tissue of relatives of this patient. 77 Cystathioninehas been shown to be absent from the brain tissue of one of these patients.78Rats fed with an excess of DL-homocystine in the diet show inhibition ofgrowth and extensive cellular damage.79An infant suffering from vomiting, failure to thrive,t hrombocytopaenia, and neutropaenia was found to have hyperglycinaemiaand hyperglycinuria. Vomiting was induced by milk-protein and byleucinc.80 It has now been shown that leucine, isoleucine, valine, threonine,and methionine are unfavourable in the diet and induce ketosis. Thepatient showed great benefit from a low protein intake supplemented by thenon-ketogenic amino-acids.8l It has been shown that these patients havean increased glycine pool size, but the glycine turn-over rate was similar tothat in normal children.Conversion of glycine into serine was delayed.82Further examples of this condition have been rep0rted.8~ The parents ofone patient who were given oral glycine loading tests were shown to have areduced ability to metabolize glycine. **Homocystinuria.HypergZycinzmia.71 R. C. Baldridge and V. H. Auerbach, J . Biol. Chena., 1964, 239, 1557.7 2 S. P. Bessmann and R. Baldwin, Science, 1962, 135, 789.73 N. J. Carson and D. W. Neill, Arch. Dis. ChiM., 1962, 37, 505.7 4 N. A. J. Carson, D. C. Cusworth, C. E. Dent, C. M. B. Field, D. W. Neill, andR. G. G. Westall, Arch. Dis. Child., 1963, 38, 425.75 T. Gerritsen, J. G.Vaughn, and H. A. Waisman, Biochem. Biophys. Res. Comm.,1982, 9, 493; T. Gerritsen and H. A. Waisman, Pediatrics, 1964, 33, 413.76 S. H. Mudd, J. D. Finkelstein, F. Irreverre, and L. Laster, Science, 1964,143, 1443.7 7 J. D. Finkelstein, S. H. Mudd, F. Irreverre, and L. Laster, Science, 1964,146, 785.7B J. V. Klavins, Brit. J. Exp. Path., 1963, 44, 507.8o B. Childs, W. L. Nyhan, M. Borden, L. Bard, and R. E. Cooke, Pediatrics, 1961,27, 522; W. L. Nyhan, M. Borden, and B. Childs, Pediatrics, 1961, 27, 539.81 B. Childs and W. L. Nyhan, Pediatrics, 1964, 33, 403.* 2 W. L. Nyhan and B. Childs, Amer. J. DiS. Child., 1962,104, 509; W. L. Nyhanand B. Childs, J. Clin. Invest., 1964, 43, 2404.asK. Tada, T. Yoshida, T. Morikawa, A. Minakawa, Y. Wada, T.Ando, andK. Shimura, Toh6ku J . Exper. Med., 1963, 80, 218; W. L. Nyhan, J. J. Chisolm, andR. 0. Edwards, J. Pediat. 1963, 62, 540; H. K. A. Visser, H. W. Veenstra, and C.Pik, Arch. Dis. ChiEd., 1964, 39, 397.T. Gerritsen and H. A. Waisman, Science, 1964, 145, 588.8 4 K. Tada and T. Ando, l’ohbkzl J. Exper. Med., 1964, 82, 164CRAWHALL: BIOCHEMICAL DISORDERS 483A physically and mentally retarded child who alsohad weakness, anaemia, and convulsions was found to have an elevatedplasma lysine level and a great increase of urinary lysine excretion. Aasoci-ated with this was an occasional elevation of arginine and ornithine excretion.The plasma lysine level did not seem to be affected by restriction of proteinintake and it was suggested that the defect was of utilization of lysine by thetissues. 8jA family has been reported with a high incidenceof nephritis and deafness who also had hyperprolinaemia with elevatedurinary proline, hydroxyproline, and glycine.86 The syndrome was laterinvestigated in further detail 87 and it was shown that the elevated urinaryhydroxyproline and glycine was secondary to the hyperprolinzemia.88HydroxyprolinEmia and hydroxyprolinuria have been found in aneleven-year-old mentally defective child. 89Hypervalinzmia. Hypervalinaemia has been reported in an infantsuffering from vomiting and failure to thrive. Hypervalinuria was alsopresent. An abnormal amount of valine was found in the urine of theparents. The patient improved on a low valine diet. The disease showssome clinical and biochemical similarities to maple-syrup urine di~ease.~OMaple-syrup urine disease.This is a familial disorder occurring inchildhood, characterized by cerebral dysfunction and unusual odour in theurine.g1 Elevated levels of valine, leucine, and isoleucine were found in theplasma and ~rine.~2 A further abnormal plasma and urinary amino-acidwas shown to be alloisoleucine.93 Early restriction of these amino-acids.from the diet limits the progress of the disease,94 but irreversible cerebral!degeneration may already have occurred.95 It was postulated that anenzyme defect of clecarboxylation of long-chain aliphatic keto-acids waspresent. It has recently been demonstrated that the decarboxylation stepis greatly reduced in the peripheral leucocytes of these patients and that asingle enzyme system may be involved.g6 It was not possible to demonstratea decarboxylation abnormality in the leucocytes of the parent^.^' A smallreduction of evolution of carbon dioxide was observed when the blood ofheterozygotes for this disease was incubated with [ 14C]leucine, as comparedwith normal controls.98Hyperlysinzmia.Hyperprolinzmia.85 N.C. Woody, Amer. J . Dis. Child., 1964, 108, 543.86 C. R. Scriver, I. A. Schafer, and M. L. Efron, Nature, 1961, 192, 672.87 I. A. Schafer, C. R. Scriver, and M. L. Efron, New Engl. .J. Med., 1962, 267, 51.88 C. R. Scriver, M. L. Efron, and I. A. Schafer, J . Clin. Invest., 1964, 43, 374.M. L. Efron, E. M. Bixby, L. G. Palattao, and C. V.Pryles, New Engl.Y . Wada, K. Tada, A. Minakawa, T. Yoshida, T. Monhawa, and T. Okomora,.J. Med., 1962, 267, 1193.Tohdlcu J . Exper. Med., 1963, 81, 46.Q1 J. H. Menkes, P. L. Hurst, and J. M. Craig, Pediatrics, 1954, 14, 462.s2 R. G. Westall, J. Dancis, and S. Miller, A.M.A. J . Dis. Child., 1957,94, 571.S3 P. M. Norton, E. Roitman, S. E. Snyderman, and L. E. Holt, Lancet, 1962, i, 26,@ * S. E. Snyderman, P. M. Norton, E. Roitman, and L. E. Holt, Pediatrics, 1964,S 5 R. G. Westall, Arch. Dis. Child., 1963, 38, 485.913 J. Dancis, J. Hutzler, and M. Levitz, Pediatrics, 1963, 32, 234.O 7 H. W. Goedd, E. Richter, C. Stahlmann, and B. Sixel, Klin. Wschr., 1963, 41,.s8 F. Linneweh, 31. Erlich, E. H. Graul, and H. Hundeshagen, Klin. Wschr., 1963,34, 454.953.41, 941484 BIOLOGICAL CHEMISTRYA familial late mtAfestation of this disease has been reported.99Phenylketonuria.This abnormality invariably gives rise to progressivedementia in early infancy and may be accompanied by involuntary move-ments and poor pigmentation of the skin and hair.loO The principal bio-chemical abnormalities were described before the period of this review.101The subject has been recently reviewed.lo2 The disease is transmitted bya single autosomal recessive gene, and the plasma phenylalanine concentra-tion is raised. It has been shown that heterozygotes also have a significantlyincreased fasting level of phen~1alanine.l~~ Phenylalanine oxidase wasshown to be absent from the liver of the homozygotes.lo4 Phenylalanineloading tests in the neonate give abnormal plasma phenylalanine levelsboth in the homozygotes and in probable heterozygotes.lo5 The conditionresponds well to a diet low in phenylalanine if diagnosis is made in theneonatal period.lo6 It has been suggested that the low phenylalanine dietcould be relaxed after three years of age.lo7 Children of phenylketonuricmothers have been shown to be mentally retarded.108A patient with a myasthzenia-like syndrome was foundto have a reducing substance in the urine and the substance was identifiedas p-hydroxyphenylpyruvic acid.log Abnormal urinary tyrosine metaboliteswere found after oral administration of tyrosine and a metabolic block atthe p-hydroxyphenylpyruvic acid oxidase stage was suggested.Fourfamilies have been described as having tyrosinosis without any m yasthzeniasymptoms but with hepatomegaly and progressive renal tubular disorders.ll*A similar metabolic block was proposed.A further case has been reportedin which the plasma, as well as urinary, tyrosine concentration was elevated.111Improvement of renal function was observed during a short trial of a dietlow in tyrosine and phenylalanine.ll2Disorders Principally of Amino-acid !Cransport.-Cystinuria. This is oneof the fist of the inherited biochemical abnormalities described.ll3 Theprincipal clinical presentation is of recurrent cystine calculus formation.The urine contains elevated quantities of cystine, lysine, ornithine, andarginine. This specific amino-aciduria was shown to be caused by a renalTyrosinosis.99 R.Kiil and T. Rokkones, Actu Pzdiat. (Uppsalu), 1964, 53, 356.100 A. Folling, 2. physiol. Chem., 1934, 227, 169.101 W. E. Knox, " The Metabolic Basis of Inherited Disease ", ed. J. B. Stanbury,l o 2 D. S . Kleinman, Pediatrics, 1964, 33, 123.103 W. E. Knox and E. C . Messinger, Arner. J. Hum. Genet., 1958, 10, 53.104 R. J. Block, G. A. Jervis, D. Bolling, and M. Webb, J. Biol. Chem., 1940, 134,105 R. J. Allen, J. C. Heffelfkger, R. E. Masotti, and M. U. Tsau, Pediatrics, 1964,108 F. A. Horner and C. W. Streamer, A.M.A. J. Dk. ChiZd., 1959, 97, 345.107 P. R. Vandeman, Amer. J. Dis. ChiZd., 1963, 106, 492.108 C. C. Mabry, J. C. Denniston, T. L. Nelson, and C . D. Son, New Engl. J . Med.,109 G. Medes, H.Berglund, and A. Lohmann, Proc. SOC. Exp. BioE., N . Y., 1927,1l0 R. Zetterstron, Ann. New Yorlc Acad. Sci., 1963-64, 111, 220.111 S. Fritzell, 0. R. Jagenburg, and L.-B. Schniirer, Acta P z d i a t . (Stockh.), 1964,112 8. Halvorsen and L. R. Gjessing, Brit. Med. J., 1964, 11, 1171.113 A. E. Garrod, Lancet, 1908, ii, 142.J. B. Wyngaarden, and D. S. Fredrickson, McGraw Hill, New York, 1960.567.33, 512.1963, 269, 1404.25, 210; G. Medes, Biochem. J., 1932, 26, 917.53, 18CRAWHALL : BIOCHEMICAL DISORDERS 485absorption defe~t.11~ The concentration of cystine in the plasma of thesepatients is reduced in comparison with that of normal patients. Carefulrenal clearance measurements in these patients have shown that the tubulardefect for cystine absorption is nearly complete, though there has been onereport of a patient in whom the clearance of cystine was greater than theglomerular filtration rate.115 It has also been shown that there is an amino-acid absorption defect in the gut of these patients.l16 Studies in d r o ofgut amino-acid transport have revealed a deficiency of cystine and lysinetransport,ll' and in another report cystine, lysine, ornithine, and arginineabsorption defects were described.ll8 Further investigation of the defectof the renal transport of cystine have given less conclusive results.Studiesin wivo of arteriovenous differences of amino-acid concentration across thekidney of a cystinuric patient showed only a minimal difference of cystineconcentration but a large difference of cysteine concentration. These resultscould be interpreted as showing that the absorption defect was of cysteineand not of cystine.l19 Studies in vitro of kidney cortex from a cystinuricpatient have confirmed the transport defect for lysine, ornithine, and arginine,but cystine appeared to be transported at a rate similar to that observedwith normal renal tissue.No competition for the transport of cystine wasobserved by adding lysine, ornithine, or arginine to the incubation medium.120Abnormal quantities of another amino-acid, cysteine homocysteine mixeddisulphide, are excreted in this disease,l21 and the metabolism of this di-sulphide has been studied.l22 The disulphide may be a normal metabolitewhich is rapidly lost into the urine as a result of the renal absorption defect.A specific chemical treatment for cystinuria has been described.la3 Onadministration of D-penicillamine to these patients, the urinary cystineexcretion is reduced and an alternative disulphide, cysteine penicillaminemixed disulphide, is excreted.This is 50 times more soluble than cystineat pH 7 and 37" and would not lead to calculus formation. It has now beenshown that the cysteine penicillamine mixed disulphide is present in theplasma of these patients during treatment and the plasma cystine level iscorrespondingly reduced. The renal absorption defect is not altered, butless cystine passes through the kidney, so that the urinary cystine levelfalls.124 A family has been described in which six members had hereditarypancreatitis.Various members of the family, with and without pancreatitis,ll*C. E. Dent and G. A. Rose, Quart. J. Med., 1951, 20, 205.115 G. W. Frimpter, M. Horwith, E. Furth, R. E. Fellows, and D. D. Thompson,116 M. D. Milne, A. M. Asatoor, K. D. G. Edwards, and L. W. Loughridge, Gut,ll7S. Their, M. Fox, S. Segal, and L. Rosenberg, Science, 1964, 143, 482.C. F. McCarthy, J. L. Borland, H. J. Lynch, E. E. Owen, and M. P. Tyor,119 G. W. Frimpter, J . Clin. Invest., 1963, 42, 1956.120 M. Fox, S . Their, L. Rosenberg, W. Kiser, and S. Segal, New Engl. J. Med.,lal G. W. Frimpter, J . Biol. Chem., 1961, 236, PC 51.122 G. W. Frimpter, J . Clin. Invest., 1963, 42, 1956.I a 3 J. C. Crawhall, E. F. Scowen, and R. W. E. Watts, Brit.Med. J., 1963, I, 588;124 J. C. Crawhall and C. J. Thompson, Science, 1965, 147, 1459.J . Clin. Invest., 1962, 41, 281.1961, ii, 323.J . Clin. Invest., 1964, 43, 1518.1964, 270, 556.1964, I, 1411486 BIOLOGICAL CHEMISTRYhad excessive urinary excretion of cystine and lysine.l25 Various aspectsof cystinuria in Sweden have been reviewed.126 A case of acquired cystinuria,secondary to glomerulonephritis, has been reported.127This is a hereditary disorder characterized by apellagra-like rash with intermittent cerebellar ataxia, excessive excretion ofurinary indole metabolites, and a specific amino-aciduria.128 The diseaseis considered to be primarily a disease of amino-acid transport in whichfryptophan is poorly absorbed from the The excessive amounts ofurinary indole metabolites arise as the result of gut bacterial activity onthe poorly absorbed dietary tryptophan. During nicotinic acid therapytryptophan was absorbed equally as well by the patient as by the controlindi~idua1s.l~~ It has now been shown that indole inhibits tryptophan pyr-rolase and kynurenine formamidase activity in rats, and it has been suggestedthat the abnormality of nicotinamide synthesis in Hartnup disease couldbe secondary to the abnormal levels of circulating indoles which have beenabsorbed from the gut.131 On the other hand, it has also been suggestedthat the poor absorption of tryptophan, coupled with urinary loss of amino-acids, including tryptophan, would be sufficient to account for the nicotin-amide deficiency.132HyperqZycinuria.A family has been described in which a single defectin the excretion of glycine was observed. Three patients in one family withthis anomaly had nephrolithiasis. Analysis of one stone showed it to beprincipally calcium 0xalate.1~3 It is thought that this is an isolated tubulardefect. Two variants of this condition have been reported. The first isa specific hereditary glycinuria associated with glycosuria.lM The secondpatient had rickets, renal hyperglycinuria, glycosuria, and glycyl-prolinuria.lsThe infantile form ofthis disease is commonly known as Tay-Sachs disease and is characterizedby a progressive, diffuse, cerebroretinal degeneration in infants. Biochemicalstudies have shown an increase of ganglioside in the ganglion cells of thecentral nervous system of these patients.13B Recent studies have shown thatthe structure of this ganglioside is that of a ceramide coupled to three hexoseu n i t s plus N-acetylneuraminic acid (NANA).The normal gangliosidefound in the brain is a monosialoganglioside. This is a ceramide coupledwith four hexose units and N-acetylneuraminic acid.137 NANA can be125 J. B. Gross, J. A. Ulrich, and J. D. Jones, Gastroenterology, 1964, 47, 41.126 H. Bostrom and L. Hambraeus, Acta Med. Scand. Suppl., 1964, 411.127 J. Sedlak and V. Galanda, Cas. Lek. Cek., 1963, 102, 1070.128 D. N. Baron, C. E. Dent, H. Harris, E. W. Hart, and J. N. Jepson, Lancet,129 A. M. Asatoor, J. Crash, D. R. London, and M. D. Milne, Lancet, 1963, i, 126.130 P.delaey, C. Hooft, J. Timmermans, and J. Snoeck, Ann. Pzediat., 1964, 202,1 3 1 P. delaey, C. Hooft, J. Timmermans, and J. Snoeck, Ann. Pgdiat., 1964, 202,132 M. D. Milne, Brit. Med. J . , 1964, I, 327.133 A. deVries, S. Rochwa, J. Lazebnik, M. Frank, and M. Djaldetti, Amer. J . Med.,134 H. Kaser, P. Cottier, and I. Antener, J . Pediat., 1962, 61, 386.135 C. R. Scriver, R. B. Goldbloom, and C . C . Roy, Pediatrics, 1964, 34, 357.136 E. Rlenk, 2. physiol. Chern., 1939, 262, 128.137 L. Svennerholm, Biochem. Biophys. Res. C'omm., 1962, 9, 436.Hartnup disease.Lipid Storage Disease.-Amuurotic fumiZy idiocy.1956, ii, 421.145.253, 321.1957, 23, 408CRAWHALL: BIOCHEMICAL DISORDERS 487transferred from cytidine monophosphate-N-[14C]acetylneuraminic acid tothe ceramide trihexose, but not to the tetrahexose.This indicates that theTay-Sachs ganglioside is the true precursor of monosialoganglioside. Themetabolic defect in Tay-Sachs disease could therefore be at the final stageof addition of the fourth hexose molecule.138Ceramide-glucose-galactose-N-acetylgalactosamine + UDP Gal --j.INANACeramide-glucose-galactose -N-acetylgdaetosamine-galact ose1N r n ANiemann Picks diseuse. In this disease, which usually commences inearly childhood, there is widespread deposition of sphingomyelin in thetissues, leading to severe hepatosp1en0megaly.l~~ Thin-layer chromato-graphy has shown that the C,, and C2* sphingomyelins are greatly increasedin the cerebral cortex and medulla, spleen, and kidney of these patients andit is suggested that there is a deficient breakdown of sphing~myelin.~~~In patienh with this disease there is an accumulationof cerebroside in the reticuloendothelial system.The disease may run arapidly destructive course in childhood, or a comparatively benign course,with gross hepatosplenomegaly, in adult life. The cerebroside whichaccumulates is the glucose cerebroside, not the galactose cerebroside whichnaturally occurs in myelin sheath. It has been shown that the enzymesresponsible for the synthesis of glucose and galactose cerebroside are normalin these patients.l41 This leads to the possibility that they may have adefect in the catabolic pathway of glucose cerebroside. Synthetic [14C]-glucose-cerebroside has been prepared and used to study the rate of liberationof [14C]glucose from it in the spleen of these patients.142 It was reduced to20% of the normal value, expressed as mg.of protein-nitrogen. The mem-brane of normal erythrocytes contains “ globoside ” (sphingosine-g’iucose-galactose2-N-acetylgalactosamine). The red cells are being constantlydestroyed in the spleen and the globosides would normally be degraded, butin the case of Gaucher’s disease the catabolism would cease at the sphingosineglucose level, leaving a residue of the characteristic glucose cerebroside.Childrenwith this inherited disease are born with multiple skeletal and soft-tissuedefects which are generally characteristic of the disease. They have mentalretardation and a high predisposition to pulmonary infections, so that fewsurvive beyond adolescence.Biochemically the disease is characterized bytlhe deposition of ganglioside in the central nervous system and by abnormalityof the structural and excreted mucopolysaccharide.143This is characterized by aJ. N. Iianfer, R. S. Blacklow, L. Warren, and R. 0. Brady, Biochem. Biophys.Gaucher’s disease.Lipochondrodystrophy (gargoylism, Pfaundler- Hurler syndrome).Globoid cell leucodystrophy (Krabbe disease).Res. Comm., 1964, 14, 287.139 M. L. Menten and J. P. Welton, Amer. J. Dis. Child., 1946, 72, 720.140 H. Pilz and H. Jatzkewitz, J. Neurochem., 1964, 11, 603.l r l E . G. Trams and R. 0. Brady, J . Clin. Invest., 1960, 39, 1546.l r 2 R. 0.Brady, K. Kanfer, and D. Shapiro, J . BioE. Chem., 1965, 240, 39.143 A. Dorfman and A. E. Lorincz, Proc. Nat. Acad. Sci. U.S.A., 1957, 43, 443488 BIOLOUICAL CHEMISTRYdiffuse cerebral sclerosis commencing in early infancy. In a recent studyit was shown that the lipid and phospholipid of the brain of patients werereduced but there was also an almost total loss of sulphatides.lM Theseauthors contrast this disease with metachromatic leucodystrophy whichcharacteristically shows an increase of cerebral sulphatides.Diseases of Purine and Pyrimidine Metabolism.-Orotic aciduria. Crystal-uria was observed in an infant with vitamin BIZ-refractory megaloblasticanaemia.145 The crystals were identified as orotic acid and it was proposedthat in this infant there was an enzymic block between orotic and uridylicacid.The patient subsequently died, but enzyme studies were carried outon the parents and two siblings of the propositus.146 The investigatorsdeveloped a new assay procedure and showed that the erythrocytes of theserelatives were deficient in orotidylic pyrophosphorylase and orotidylicdecarboxylase. Similar defects have been demonstrated in circulatingleucocytes of these re1ati~es.l~~ These results indicated the nature of theenzyme block and it was suggested that the inheritance was via an autosomalrecessive trait in which the homozygous state was generally not viable.Presumed heterozygotes for orotic aciduria excrete elevated quantities ofurinary orotic acid.148 The enzyme defect has now been traced throughfour generations of this family.l49Hyperuriczmia and gout.The biochemistry of uric acid and its relationto gout has been reviewed.lS0 The exact hereditary mechanism will bedifficult to define as the presenting symptom of gout occurs only irregularlywith hyperuriczmia, such that 25% of the relatives of gouty subjects havehyperuriczmia. The hyperuricemia may arise by three mechanisms :(a) overproduction of uric (b) diminished excretion of uric acid,15Q or(c) by a combination of (a) and (b).l5l One investigation has failed to showany renal defect in patients with An abnormality of glutaminemetabolism has recently been reported to occur in patients with gout.153[15N]Glutamine was fed to normal and gouty subjects; a greater enrichmentof 15N was found at N-9 in the uric acid isolated from the latter subjects.It is known that N-9 is incorporated into the molecule via 5-phosphoribosyl-amine, which derives its nitrogen specifically from glutamine.Supportingevidence for this theory came from the observation that gouty patients had areduced ability to excrete ammonium ion in the urine and this has beenshown to arise principally from g1~tamine.l~~ It has been suggested lS3that the primary metabolic defect in gout could arise at the amino-acid144 B. J. Wallace, S. M. Aronson, and B. W. Volk, J . Neurochem., 1964, 11, 367.145 C. M. Huguley, J. A. Bain, S. L. Rivers, and R. B. Scoggins, Blood, 1959,14,615.1Q6 L. H. Smith, M. Sullivan, and C. M. Huguley, J . Clin. Invest., 1961, 40, 656.14'H.J. Fallon, M. Lotz, and L. H. Smith, Blood, 1962, 20, 700.148 M. Lotz, H. J. Fallon, and L. H. Smith, Nature, 1963, 197, 194.149 H. J. Fallon, L. H. Smith, J. B. Graham, and C. H. Burnett, New Engl. J .lSo J. E. Seegmiller, L. Laster, and R. R. Howell, New Engl. J . Med., 1963, 268, 712.151 J. E. Seegmiller, A. I. Grayzel, L. Laster, and L. Liddle, J . Clin. Invest., 1961,152 C. A. Nugent and F. H. Tyler, J. Clin. Invest., 1959, 38, 1890.1S2aT. F. Yu, L. Berger and A. B. Gutman, Amer. J . Med., 1962, 33, 829.153 A. B. Gutman and T. F. Yu, Amer. J . Med., 1963, 35, 820.154 R. F. Pitts, J. deHaas, and J. Klein, Amer. J. Physiol., 1963, 204, 187.Med., 1964, 270, 878.40, 1304CBAWHALL : BIOCHEMICAL DISORDERS 489level, possibly by a decrease of deamination of glutamine, such that uricacid synthesis was stimulated.The first established case of hereditary xanthinuria wasreported as that of a child aged 4 years who passed a urinary calculus com-posed of pure xanthine.155 Abnormally low levels of uric acid were foundin the serum and urine.Further examination of this patient showed thepresence of hypoxanthine as well as xanthine in the urine,15g and a defectof xanthine oxidase was suggested. Two further patients with this diseasehave recently been investigated. One was a 23-year-old female patientwith xanthinuria and ph~ochrom~cytoma.~~~ A method for measurementof tissue xanthine oxidase has been described.158 By this method onlyminimal enzyme activity could be demonstrated in biopsy tissue from thepatient's liver and jejunal mucosa.Renal clearance of oxypurines, carriedout in normal patients, gave similar results if the circulating xanthine levelwas raised, by infusion, to that found in xanthinuria. The second patientwas a 47-year-old man who presented with hzernochromatosis.159 It wassuggested that there was an association between the inability to transportiron and the marked reduction of xanthine oxidase activity that wasobserved on liver biopsy. Neither of these patients had formed calculi.I n none of the cases reported above had the parents any abnormality ofurinary purines, and the mother of the patient reported by Engelman et aE.had normal xanthine oxidase activity in a jejunal mucosa biopsy specimen.There is an unpublished report of xanthinuria occurring in two siblings,160but at present there is no further direct evidence that the condition isinherited by an autosomal recessive character.This is an inherited disease in which the oxalatecontent of the urine is elevated and leads to formation of calcium oxalatecalculi in the kidney and nephrocalcinosis.Renal failure generally developsin adolescence. Glycine was shown to be a principal precursor of urinaryoxalate in this disease.161 It was thought that a metabolic block could bepresent in the metabolism of glyoxylate such that an abnormal quantity ofoxalate was produced. However, no abnormality of glyoxylate metabolismcould be observed in liver mitochondria from these patients .162 Ascorbicacid is also a precursor of oxalate.Feeding experiments in which [13C]-ascorbate was given to an hyperoxaluric subject and to a normal subjectshowed that the turnover times of ascorbic acid in the two subjects werecomparable. The contribution of ascorbate to urinary oxalate appearedsimilar after correction had been made for the high oxalate excretion of thepatients.163 A more detailed account of the metabolism of ascorbate toXanthinuria.Primary hyperoxahria.ls5 C. E. Dent and G. R. Philpott, Lancet, 1954, i, 182.156 C. J. Dickinson and J. M. Smellie, Brit. Med. J., 1959, 11, 1217.15' R. W. E. Watts, K. Engelman, J. R. Klinenberg, J. E. Seegmiller, and A.Sjoerdsma, Bwchem. J., 1964, 90, 4P; K. Engelman, R. W. E. Watts, J. R. Klinenberg,A.Sjoerdsma, and J. E. Seegmiller, Amer. J . Med., 1964, 37, 839.158 R. W. E. Watts, J. E. M. Watts, and J. E. Seegmiller, J . Biol. Chem., in the press.159 J. H. Ayvazian, New Engl. J . Med., 1964, 270, 18.160 J. Diaz, L. Cifuentos, and C. Mendoza, personal communication; cf. ref. 157.161 J. C. Crawhall, E. F. Scowen, and R. W. E. Watts, Lancet, 1959, ii, 806.16* J. C. Crawhall and R. W. E. Watts, Clin. Sci., 1962, 23, 163.163 G. L. Atkins, B. M. Dean, W. J. Griffin, E. F. Scowen, and R. W. E. Watts,Lancet, 1963, ii, 1096490 BIOLOGICAL CHEMISTRYoxalate in normal man has appeared.lM The metabolism of glyoxylate hasbeen shown to be abnormal after its intravenous injection in these patients.The incorporation of l4C into respiratory carbon dioxide after intravenousinjection of [14C]glyoxylate was less in four patients than in the normalcontr01s.l~~ Excretion of glycollic acid in the urine was found to be increasedand the incorporation of [ 14C]glyoxylate into urinary oxalate and glycollatewas also increased.This subject has been recently reviewed by Hockadayet ~ 1 . 1 ~ 6 who suggest that the findings are compatible with a block in theconversion of glyoxylate into glycine.Tryptophan was shown to be a precursor of oxalate in the vitamin €3,-deficient rat by a pathway which does not cause randomization of C-2 andC-3.167 A sensitive fluorimetric method for estimating plasma oxalate hasbeen devised and it has been shown that oxalate levels were not elevatedin hyperoxaluria.16s Renal clearance of oxalate was markedly elevated inthese patients.This finding would suggest that there was a defect of oxalatetransport as well as oxalate production. Oxalosis can occur withouthyperoxaluria .lA child has been described as having delayedphysical and mental development, stomatitis, hypermnia, and anEmia.The urine contained elevated quantities of xanthurenic acid, hydroxy-kynurenine, kynurenine, and kynurenic acid. It was suggested that therewag a deficiency of kynureninase activity.l’OHydroxykynureninuria.16* G. L. Atkins, B. M. Dean, W. J. Grith, and R. W. E. Watts, J . Biol. Chern.,113~ E. W. Frederick, M. T. Rabkin, R. H. Richie, and L. H. Smith, New Ewl.T. D. R. Hockaday, J. E. Clayton, E. W. Frederick, and L. H. Smith, Medicine,1964, 239, 2975.J .Med., 1963, 269,.821.1964, 43, 315.167 F. F. Faragalla and S. N. Gershoff, PTOC. SOC. Exp. Biol., 1963, 114, 602.168 P. Zarembski and A. Hodgkinson, Invest. Urol., 1963, 1, 87.169 G. Gasser and St. Wuketick, Dtsch. Arch. klin. Mecl., 1964, 209, 257.170 G. M. Komrower, V. Wilson, J. R. Clamp, and R. G. Westall, Arch. Dis. Child.,1964, 39, 2504. STRUCTURE AND BIOSYNTHESIS OFCARBOHYDRATE-POLYPEPTIDE POLYMERSBy P. T. Grant and J. L. Simkin(Deparfiment of Biological Chemistry, University of Aberdeen, Marischal College,A b erde en)T HI s Report will be concerned mainly with two topics, namely: (1) the typesof covalent bonds known to join carbohydrates to polypeptide in naturallyoccurring polymers; and (2) the biosynthesis of such compounds, withparticular reference t'o the formation of the carbohydrate components.They have been selected because they have received particular attentionin the last feu- years. For other and more general treatment, the readeris referred to the following recent reviews: structure, metabolism, andbiology of glycoproteins ;l, isolation, purification, and analysis of glyco-proteins ;3 structure of orosomucoid ;4 chemistry of glycosaminoglycans 5and of glycosaminoglycans and glycoproteins ;6 chemistry and metabolismof glycosaminoglycans of connective tissues ; 7 9 8 the structure and biosynthesisof chitin and related substance^;^ and the structure and metabolism ofbacterial cell walls.lo, l1 The papers presented in a symposium on mucoussecretions have been published.l2Carbohydrate-Polypeptide Bonds.-Sufficient evidence has now accumu-lated to allow the following classification of carbohydrate-polypeptide bondsto be made.Glycosylamine bonds.This type of bond appears to occur in a widevariety of glycoproteins. It is comparatively stable to acid and alkali.13Recent reports have supplemented evidence previously obtained whichindicated the occurrence in hen ovalbumin of an acyl-glycosylamine bondlinking the carbohydrate prosthetic group to polypeptide. In earlierwork l4 (see also previous Report 15), partial acid-hydrolysates of glyco-Protides Biological Fluids ", ed. H. Peeters, Eleventh Colloq.,1 R. G. Spiro, Ney"I,ngland J. Med., 1963, 269, 566, 616.2 H.E. Schultze in8K. Schmid, Chimia (Switz.), 1964, 18, 321.4 R. W. Jeanloz, MEdicine, 1964, 43, 363.* R. W. Jeanloz, Adv. Enxymol., 1963, 25, 433.Elsevier, Amsterdam, 1964, p. 288.R. W. Jeanloz in Comprehensive Biochemistry ", ed. M. Florkin and E. H.Stotz, Vol. V, Elsevier, Amsterdam, 1963, p. 262.H. Mub, Internat. Rev. Connective Tissue Bee., 1964, 2, 101.S. Fitton Jackson in " The Cell ", ed. J. Brachet and A. E. Mirsky, Vol. VI,P. W. Kent in " Comparative Biochemistry ", ed. M. Florkin and H. S . Mason,Academic Press, Inc., New York, 1964, p. 387.Vol. VII, Academic Press, Inc., New York, 1964, p. 93.lo M. R. J. Salton, " The Bacterial Cell Wall ", Elsevier, Amsterdam, 1964.11W. Weidel and H. Pelzer, Adv. Enzymol., 1964, 26, 193.l2 Ann.New York Acad. Sci., 1963, 106, 157+309.l3 A. Neuberger, Abs. Sixth Internat. Congress Biochemistry, New York, 1964, Vol.11, p. 105.l4 G. S. Marks, R. D. Marshall, and A. Neuberger, Bioc7hem. J., 1963, 87, 274;A. P. Fletcher, R. D. Marshall, and A. Neuberger, Biochim. Biophya. Acta, 1963, 74,311; I. Yamashina, K. Ban-I, and M. Makino, ibid., 1963, 78, 382.l5 D. W. Russell and R. J. Sturgeon, Ann. Reports, 1963, 60, 486492 BIOLOGICAL CHEMISTRYpeptides isolated from ovalbumin had yielded a product which gave riseon hydrolysis to aspartic acid, ammonia, and glucosamine in equimolarquantities. This product was shown to have some properties in commonwith 2-acetamido-l-~-~-~'-aspartamido-l,2-dideoxy-~-glucose (1). The link-age would thus involve the amide group of asparagine and the reducing groupof N-acetylglucosamine. Marshall and Neuberger l6 have recently describeda more detailed examination of the product of partial hydrolysis, comparingit with synthetic compound (1) and N-2-p-~-aspartylarnino-%deoxy-~-glucose (2).The product was isolated in crystalline form in about 30%CH2.OH CH2.OHyield, and it was similar by a variety of criteria to compound (1). Severalother groups l7 have also recently reported the isolation from ovalbuminglycopeptides of a product with properties similar to those of compound(I). Marshall and Neuberger l6 reported an improved method of synthesisof compound (1); a different route of synthesis has also been indicated.18Several workers l9 have prepared amino-substituted derivatives of glucos-amine [cf.compound (2)], including some with more than one amino-acidresidue. A glycopeptide isolated from ovalbumin and which contained noamino-acid other than aspartic acid yielded a phenylthiohydantoin (PTH)derivative onreaction with phenyl isothiocyanate followed by cyclization withtrifluoroacetic acid. Furthermore, the derivative yielded PTH-aspartic acidon hydrolysis with hydrochloric acid. These results provide confirmatoryevidence for the involvement of the p- rather than the a-carboxyl group ofaspartic acid in linkage with carbohydrate.20Earlier work suggested that a number of other glycoproteins, such ashuman orosomucoid (al-acid glycoprotein),2l human y-globulin,22 bovinefetuin,l and hen ovom~coid,~~, 24 contained a similar type of glycosylaminebond to that present in ovalbumin (for other references to earlier work, seeprevious Report l5).The evidence for the occurrence of such a bond inthese glycoproteins has not, however, been as comprehensive as that avail-16 R. D. Marshall and A. Neuberger, Biochemistry, 1964, 3, 1596.17V. P. Bogdanov, E. D. Kaverzneva, and A. P. Andreyeva, Biochim. Biophys.Acta, 1964, 83, 69; H. Tsukamoto, A. Yamamoto, and C. Miyashits, Biochem. Biophys.Res. Comm., 1964, 16, 151.1SC. H. Bolton and R. W. Jeanloz, J . Org. Chem., 1963, 28, 3228.19 M. Liefliinder, 2. physiol. Chem., 1962, 329, 1; M. Liefliinder and K. Thomas,ibid., 1963, 331, 154; 0. Wacker and M. Liefliinder, ibid., 1964, 335, 255; F. Micheel,E.-A.Ostmann, and F. Alfes, Tetrahedron, 1962, 18, 1155; F. Micheel, E.-A. Ostmann,and G. Pielmeier, Tetrahedron Letters, 1963, 115; S . M. Amir, J. S. Brimacombe, andM. Stacey, Nature, 1964, 203, 401.20 A. P. Fletcher, R. D. Marshall, and A. Neuberger, Biochem. J . , 1963, 88, 37P.21 S. Kamiyama and K. Schmid, Biochina. Biophys. Acta, 1962, 63, 266; E. H.22 J. A. Rothfus and E. L. Smith, J. Biol. Chem., 1963, 238, 1402.23 R. Montgomery and Y . - C . Wu, J . Biol. Chem., 1963, 238, 3547.24 J. Montreuil, G. Biserte, and A. Chosson, Compt. rend., 1963, 256, 3372.Eylar, Biochrn. Biophys. Res. Comm., 1962, 8, 195GRANT AND SIMKIN: CARBOHYDRATE-POLYPEPTIDE POLYMERS 493able for ovalbumin, and in some instances the presence of additional typesof bonds cannot yet be excluded; indeed, it has been suggested2* thatovomucoid also contains an ether bond linking threonine to carbohydrate.Wherever definite evidence has been obtained, N-acetylhexosamine has beenimplicated as participating in the linkage, and two recent reports have pro-vided further evidence for the involvement of N-acetylhexosamine in carbo-hydrate-polypeptide bonds in orosomucoid 25 and fetuin.26 In both in-stances, the carbohydrate prosthetic groups were progressively degradedby repeated cycles of oxidation with periodate, followed by reduction andpartial hydrolysis.Other recent work suggests that ti, glycosylamine bondmay be present in some other glycoproteins. Thus, aspartic acid or as-paragine appears to play a rnajor role in carbohydrate-polypeptide linkagein calf 1, 27 and sheep thyroglobulin.2* The carbohydrate prosthetic groupof bovine pancreatic ribonuclease B is attached to an aspartic acid orasparagine residue.29 Although the yield of ammonia obtained on acid-hydrolysis of the glycopeptide isolated was not reported, the residue sub-stituted with carbohydrate corresponds to an asparagine residue in theunsubstituted ribonuclease A.Cunningham and Simkin 30 have isolated,from an acidic glycoprotein-containing fraction from guinea-pig serum,glycopeptides which contain aspartic acid as the main amino-acid present,yield ammonia in quantities approximately equimolar to aspartic acid onacid-hydrolysis, and give rise on partial acid-hydrolysis to a product whichbehaves on ion-exchange chromatography in a, similar way to compound(1).Results obtained with a soya bean hzemagglutinin 31 suggest that aglycosylamine bond might occur in plant glycoproteins.As with the glycoproteins to which reference was made earlier in thissection, those investigated in these recent studies 27-30 also appear topossess relatively large carbohydrate prosthetic groups ; this is also true ofthyr~tropin.~z Calf 27 and sheep 28 thyroglobulins both contain two differentkinds of group: a smaller type which contains only N-acetylglucosamineand mannose, and a larger type which contains in addition to these sugars,galactose, sialic acid, and possibly fucose. Several workers 33, 3* havequestioned the view 35 that y-globulins contain only a single carbohydrateprosthetic group. For example, Clamp and Putnam 33 have suggestedfrom a detailed study that there are two prosthetic groups in human y-globulin.Their results suggested that the carbohydrate groups werez5 R. C. Hughes and R. W. Jeanloz, Abs. First Meeting Federation European26 R. G. Spiro, J. BioE. Chem., 1964, 239, 567.27 R. G. Spiro and M. J. Spiro, Fed. Proc., 1963, 22, 538.2 8 C. Cheftel, S. Bouchilloux, and S . Lissitzky, Compt. rend., 1964, 259, 1458.29 T. H. Plummer and C. H. W. Hirs, J . BioE. Chem., 1964, 239, 2530.30 W. L. Cunningham and J. L. Ximkin, Abs. Sixth Internat. Congress Biochem.,New York, 1964, Vol. 11, p. 146; and unpublished results.31 H. Lis, N. Sharon, and E. Katchalski, Biochim. Biophys.Acta, 1964, 83, 376,32 M. E. Carsten and J. G. Pierce, J. BioE. Chem., 1963, 238, 1724.33 J. R. Clamp and F. W. Putnam, J . Biol. Chem., 1964, 239, 3233.34 J. B. Fleischman, R. R.‘Porter, and E. M. Press, Biochem. J., 1963, 88, 220;Protides Biological Fluids ”, ed. H. Peeters, Eleventh35 C. Nolan and E. L. Smith, J. BioE. Chem., 1962, 237, 446, 453.Biochemical Societies, London, 1964, p. 62.Z. Dische and E. C. Franklin inColloq., Elsevier, Amsterdam, 1964, p. 301494 BIOLOGICAL CHEMISTRYhsterogeneous ; the relative contributions of intra- and inter-molecularheterogeneity towards the production of this heterogeneity are not yet clear.A technique has been described 36 which may be of value in studies onthe sequence of residues adjacent to the carbohydratepolypeptide glycosyl-amine bond.It was found that the glycosylamine bond of a glycopeptideisolated from ovalbumin and in which aspartic acid was the sole amino-acidpresent was split on prolonged incubation with almond emulsin. Freemannose and a series of .mannose-N-acetylglucosamine-containing oligo-saccharides could be isolated after incubation. On the other hand, theglycosylnmine bond of a derivative of the glycopeptide in which the a-amino-group of the aspartic acid residue was substituted with the 2,4-dinitrophenylgroup was not split by emulsin, and a series of oligosaccharides attachedto 2,4-dinitrophenylaspartic acid were obtained. The pattern of actionof emulsin appeared to be changed by the substitution.It has been suggested 37 that in pleuromucoid the sequences of amino-acidresidues adjacent to the aspartic acid or asparagine residues substitutedwith carbohydrate are not identical in all cases.Pleuromucoid containsabout six prosthetic groups.38 Interpretation of this kind of study isrendered difficult by the discovery of the microheterogeneity of a varietyof glycoprotein~.~~ Until the precise cause of such heterogeneity is known,it is =cult to exclude variation in the sequences of amino-acid residuesbetween different polypeptide chains.Glycosidic bonds. Glycosaminoglycans (mucopolysaccharides) of con-nective tissue are characterized by a small repeating unit and a high degreeof polymerization.' In the native state these polymers are associated withsmall amounts (about 20%) of protein which is difficult to remove by mildphysical procedures.The supposition that this associated protein is co-valently bound to the carbohydrate constituent has been confirmed.The irreversible dissociation 40-42 of chondroitin 4-sulphate from itsassociated protein at about pH 12 has been shown p3 to be essentially com-plete with a fraction of bovine nasal septa after 120 minutes at 25". Thesensitivity of the bond to dilute alkali suggested an ester linkage, possiblyinvolving the p-hydroxyl group of a serine residue.40 Treatment of theglycosaminoglycan-protein complex with hydrazine yielded results incom-patible with the presence of an ester b0nd.~2, ** Another possibility is aglycosidic bond involving the p-hydroxyl group of a serine or threonineresidue.The p-elimination of an 0- or S-substituent readily occurs whenO-substituted seryl or S-substituted cysteinyl derivatives in synthetic36 Y. C. Lee, Y.-C. Wu, and R. Montgomery, Biochem. J., 1964, 91, 9C.3 7 R. Bourrillon, R. Got, and D. Meyer, Biochim. Biophys. Acta, 1964, 83,178.38 R. Bourrillon, R. Got, and D. Meyer, Biochim. Biophys. Acta, 1963, '94,255.39 K. Schmid, J. P. Binette, S. Kamiyama, V. Pfister, and S. Takahashi, Bio-chemistry, 1962, 1, 959; K. Tolrita and K. Schmid, Nature, 1963, 200, 206; K. Schmidand S. Takahashi, ibid., 1964, 203, 407.4oH. Muir, Biochem. J., 1958, 69, 195.4 1 S. M. Partridge and D. F. Elsden, Biochem. J., 1961, 79, 26.42 B. Anderson, P. Hoffman, and K. Meyer, Biochim. Biophys.Acta, 1963, '74, 309.43P. T. Donganges and M. Schubert, J. Bid. Chem., 1964, 239, 1498,4 4 J. D. Gregory, T. C. Laurent, and L. RodBn, J . Biol. Chem., 1964, 239, 3312GRANT AND SIMKIN : CARBOHYDRATE-POLYPEPTIDE POLYMERS 495peptides 45-47 or in substituted proteins 48, 49 are treated with dilute alkalia t room temperature. The yields of the leaving group (RX-) from the0- or X-substituted seryl or cysteinyl residue (3) and of the dehydroalanineresidue (4) formed in this p-elimination reaction are usually quantitativebut certain serine derivatives can also yield oxaz~lines.~~, 46 The presenceof a glycosidic bond involving the /3-hydroxyl group of hydroxyamino-acidscan thus be inferred from the observations that treatment of the proteincomplexes of chondroitin 4-sulphate or keratosulphate with alkali resultsin extensive destruction of hydro~yamino-acids,~~, 50 which can be partiallyaccounted for, after reduction, by an increase in the amount’s of alanineand a-aminobutyric acid.50 The latter was presumably the reductionproduct of an a-aminocrotonic acid derivative formed in the @-eliminationreaction from an O-substituted threonine residue in the protein.51More direct evidence on the nature of the bond between chondroitin4-sulphate and protein has been obtained from a study of glycopeptidesisolated after digestion of a heterogeneous fraction of bovine nasal septawith testicular hyaluronidase and papain.44, 52 The smallest glycopeptideswere non-reducing and contained uronic acid and galactosamine (in a ratioZ : l ) , D-galactose, and xylose, with serine as the main amino-acid present.After further proteolysis, the ratio of serine to all other amino-acids waschanged to 1 :0*4.Neither galactose nor xylose is a component of thechondroitin 4-sulphate repeating unit and both must be located near thebond to A preliminary report on the isolation of the fragments,xylosylserine and galactosylxylosylserine,54 supports the suggestion 44 thatat least some chondroitin 4-sulphate chains are joined to galactose by a glu-curonidic bond and that the bond to protein is glycosidic and probablyinvolves xylose and the /3-hydroxyl group of serine.The same glycopeptides, xylosylserine and galactosylxylosylserine, havealso been isolated after partial acid-hydrolysis of a commercial sample ofheparin.54 The electrophoretic behaviour of these glycopeptides indicatedthat both the amino- and the carboxyl group of serine were unsubstituted,so that a glycosidic bond between xylose and the @-hydroxyl group of serineis probable.There is some evidence that the same type of glycosidic bond5345 S. Ginsberg and I. W. Wilson, J . Amer. Chem. SOC., 1964, 86, 4716.46 L. Benoiton, R. W. Hanson, and H. W. Rydon, J . Chem. SOC., 1964, 824.4 7 M. Sokolovsky, T. Sadeh, and A. Patchornik, J . Anaer. Chem. SOC., 1964, 86,48 M. Sokolovsky and A. Patchornik, J . Amer. Chent. SOC., 1964, 86, 1859, 1860.40 Z. Bohak, J . Biol. Chem., 1964, 239, 2878.B. Anderson, P. Hoffman, and K. Meyer, J .Biol. Chem., 1964, 239, PC2716.51 B. Witkop, Adv. Protein Chem., 19G1, 16, 221.5 2 L. Roden, J. D. Gregory, and T. C. Laurent, Biochcna. J . , 1964, 91, 2P.53 P. W. Kent and F. K. Stevenson, Biochem. J . , 1963, 89, 114P.5 4 U. Lindahl and L. Rodeh, Biochem. Biophys. Res. Comnz., 1964, 17, 254.1286, 1212496 BIOLOGICAL CHEMISTRYis present in the hyaluronic acid-protein complex of human umbilicalThe bond between carbohydrate and protein in a salivary glycoproteinor mucin from ovine and bovine submaxillary glands also appears to bemainly of the glycosidic type. Ovine submaxillary mucin (OSM) is composedof about 800 a-~-N-acetylneuraminyl(2 -+6)-N-acetylgalactosamine disac-charide units covalently bound at intervals along the length of a polypeptidechain.Studies by Gottschalk and his colleagues on OSM56 and on thesimilar bovine submaxillary mucin (BSM) 57 suggested that most of thecarbohydrate units were linked to the polypeptide by ester bonds involvingthe reducing hydroxyl group of N-acetylgalactosamine and the cu-carboxylgroups of dicarboxylic amino-acids.15 The kinetics of the reaction of OSMwith dilute alkali containing hydroxylamine, under carefully controlledconditions, did not, however, support this s~ggestion.~8 Moreover, afterdigestion of BSM 59 and OSM 60, 61 with proteolytic enzymes, a glycopeptidefraction was isolated which contained galactosamine, dicarboxylic amino-acids, and hydroxyamino-acids in the molar ratio of 1:0*1:1.2.61 It hasbeen suggested that at least 50% of the total hexosamine in these glyco-proteins is linked by glycosidic bonds involving the p-hydroxyl groups ofserine or threonine.60, 6lor with dilute alkalicontaining borohydride, 62 released the carbohydrate components and effectedan extensive destruction of the hydroxyamino-acids in the non-diffusibleprotein.In the presence of alkaline borohydride,62 there was a discrepancybetween the amounts of serine and threonine destroyed and the concomitantincreases in the alanine and a-aminobutyric acid contents of the protein.A partial explanation of this discrepancy may be that both dehydroamino-acids and oxazolines were formed in the ,!?-elimination reaction 45 or that therewas an addition of spatially adjacent E-NH~ groups of lysine residues acrossI INH2 NH2( 5 )the double bond of some dehydroamino-acid residues to form W-(DL-~-amino-Z-carboxyethyl)-L-lysine (5). This unnatural amino-acid has beenshown to be present in acid-hydrolysates of X-dinitrophenyl-ribonuclease 48and O-substituted proteins 49 which had been previously treated with dilute56 P.T. Grant and A. M. Mackie, Biochem. J., 1964, 92, 34P; A. M. Mackie, Ph.D.Thesis, University of Aberdeen, 1964.66 A. Gottschalk, W. H. Murphy, and E. R. B. Graham, Nature, 1962, 194, 1051.5 7 E. R. B. Graham, W. H. Murphy, and A. Gottschalk, Biochim. Biophys. Acta,68 S. Harbon, G. Herman-Boussier, and H. Clauser, Bull. SOC. Chim. biol., 1963,69 Y. Heshimoto and W. Pigman, Ann. New York Acad. Sci., 1963, 106, 233.60 S. Harbon, G.Herman, B. Rossignol, P. Jollhs, and H. Clauser, Biochem. Biophys.61V. P. Bhavanandan, E. Buddecke, R. Carubelli, and A. Gottschalk, Biochem,8 2 K. Tanaka, M. Bertolini, and W. Pigman, Biochem. Biophys. Res. Comm., 1964,Treatment of OSM or BSM with dilute alkali,50, 60,HO~C-CH--CH~--NH-[CH~]~-CH-CO~H1963, 74, 222.45, 1279.Res. Comm., 1964, 17, 57.Biophys. Res. Comm., 1964, 16, 353.16, 404GRANT AND SIMKIN : CARBOHYDRATE- POLYPEPTIDE POLYMERS 497alkali. Nevertheless, the result of treatment of salivary glycoproteins withalkali is consistent with the view that most of the sensitive bonds are glyco-sidic in nature and involve the fi-hydroxyl group of serine or threonine resi-dues. The possibility cannot be excluded that a small proportion of thebonds may be of an ester type as suggested by G0ttschalk.~7, The rapidinitial release of a small amount of carbohydrate from BSM in dilute a.lkaliwas followed by a slower but more complete liberation and would be compat-ible with the presence of two types of alkali-sensitive bonds.62 In anyconsideration of these results it should be noted that BSM prepared byGottschalk’s procedure (BSM-G) differs in its gross chemical compositionfrom that obtained bythe procedure of Pigman and his co-workers (BSM-P).g3Moreover, both preparations were apparently heterogeneous as judged byprecipitin-curve analysis.Immunoelectrophoresis showed that BSM-Gcontained 4-9 components, three of which were glycoproteins. In contrast,BSM-P did not contain extraneous protein but consisted of at least twoglycoproteins.64fi-N-Acetylhexosaminidase preparations have been extensively purifiedfrom beef-li~er,~~ spleen,61 3 66 and DipEococcus pneumonia?. s7 Severalnatural and synthetic glycosides with a terminal N-acetylhexosamine residuehave been shown to act as substrates for the enzyme preparations. Ofgreat potential interest is the observation that the spleen enzyme willcleave glycopeptides derived from OSM, presumably at the glycosidic bondbetween N-acetylgalactosamine and a hydroxyamino-acid. 61There are some indications that a glycosidic bond may be involved inthe linkage between the carbohydrate and polypeptide moieties of taka-amylase A 68 and of some blood-group substan~es.~9The possibility that salivary glycoproteins contain a smallproportion of ester bonds linking the carbohydrate and polypeptide moietieshas already been discussed.Another ester bond occurs in teichoic acids present in the cell-wall orcell-wall region of many bacteria.These water-soluble polymers &re com-posed of either glycerol or ribitol residues joined through phosphodiesterbonds to form a chain; D-alanine and sugar residues are attached to thepolyol units.’* The teichoic acid of LactobaciEZus buchneri, like all otherglycerol teichoic acids, contains alanine linked by an ester bond to C-2of a glycerol resid~e.7~ The location of alanine in ribitol teichoic acid ofXtaphyEococcus aureus was indicated by the stability of the ribitol residuesto periodate before, but not after, removal of the alanine by mild hydrolysis,showing that the ester bond was a t either C-2 or C-3 of a ribitol residue.726 s W.Pigman and Y. Hashimoto, Biochim. Biophys. Acta, 1963, 69, 579.6 4 M. Horowitz, L. Martinez, and V. Murty, Biochim. Biophys. Acta, 1964, 83, 306.6 5 B. Weissmann, S. Hadjiioannou, and J. Tornheim, J . BioE. Chem., 1964, 239, 59.66 E. Buddecke and E. Werries, 2. Naturforsch., 1964, 19b, 798.6 7 R. C. Hughes and R. W. Jeanloz, Biochemistry, 1964, 3, 1543.68A. Tsugita and S. Akabori, J . Biochem. Japan, 1959, 46, 695.69 G. Schiffman, E. A. Kabat, and W. Thompson, Biochemistry, 1964, 3, 113, 587;K. 0. Lloyd and E. A. Kabat, Biochem. Biophys. Res. C’omm., 1964,16,385; A. Pusztaiand W. T. J. Morgan, Biochern.J., 1964, 93, 363.7 0 J. Baddiley, J . Roy. Inst. Chem., 1962, p . 366,71 N. Shaw and J. Baddiley, Bwchem. J., 1964, 93, 317.‘2 J. Baddiley, J. Buchanan, R. Martin, and U. Rajbhandary, Biochem.J., 1962,85,49.Ester bonds498 BIOLOGICAL CHEMISTRYIt has been suggested 73 that alanine is linked by an ester bond involvingthe 6-hydroxyl group of N-acetylglucosamine in the ribitol teichoic acid ofShphylococcus azcreus, Copenhagen.Amide bonds. Cell-walls of Gram-positive and many Gram-negativebacteria are partly composed of a unique group of heteropolymers termedmucopeptides. These structural components are polymers of N-acetyl-glucosamine and N-acetylmuramic acid believed to be joined by B(1-A)-glycosidic links ;74 small peptide units usually containing D- or L-alanine,D-glutamic acid, and either lysine or diaminopimelic acid are attached tothe polymer.75 In some cases lysine has been replaced by its lower homo-logues, either ad-diarninobutyric acid 76 or 0rnithine.~7, 78 The linkagebetween carbohydrate and peptide is usually an amide bond between alanineand the carboxyl group of N-acetylmuramic 79, 80 In contrast toglycosidic bonds in these compounds, the amide bond is not appreciablyhydrolysed by x-acetic acid at 110" in a sealed system.80Mucopeptides from several organisms, when incubated with an extra-cellular enzyme preparation of Streptomyces albus, released peptides contain-ing alanine as the N-terminal residue.81 It is now known that this prepar-ation is a mixture of lytic enzymes and contains an N-acetylmuramideglycanohydrolase (lysozyme) as well as the N-acetylmuramyl-L-alanineamidase. Purified preparations of the amidase only act after the muco-peptide has been hydrolysed by the N-acetylmuramide glycanohydro-lase.82-84 Amidases of apparently similar specificity have been purifiedfrom extracts of Bacillus subtilis 84 and Escherichia ~0Zi.85Biosynthesis.-Several recent reviews 86 have dealt with the formationand metabolism of nucleotide sugars.Glycoproteins. Much of the work carried out so far on the biosynthesisof glycoprot'eins has concerned the formation of plasma proteins. Asknowledge concerning the characteristics of individual plasma proteins hasaccumulated, it has become evident that most contain carbohydrate.l, *7It has been known for some time that in the rat t,he liver is the main or sole73 A.Sanderson, W. Juergem, and J. L. Strorninger, Biochem. BWphys. Res. Comm.,7 4 R. W. Jeanloz, N. Sharon, and H. M. Flowers, Biochem. Biophys. Res. Comm.,7 5 H. Perkins, Bacteriol. Rev., 1963, 27, 18.76 H. Perkins and C. Cummins, Nature, 1964, 201, 1106.7 7 E. Work, Nature, 1964, 201, 1107.78 H. Duc-Nguyen and L. West, J . BioZ. Chem., 1964, 239, 2981.79 H. Heyman, M. Manniello, and S. S. Barkulis, J . BWZ. Chem., 1964, 239, 2981.80 S. Hanessian and T. Haslrell, J . Biol. Chem., 1964, 239, 2758.89 J. M. Ghuysen, M. Legh-Bouille, and L. Dierickx, Biochim. Biophys. Acta, 1962,e3 J . M. Ghuysen, Biochim. Biophys. Acta, 1964, 83, 132.F. Young, D.Tipper, and J. L. Strominger, J. Bid. Chem., 1964, 239, PC3600.8 5 H. Pelzer, 2. Nuturforsch., 1963, 18b, 950; D. Mass, H. Pelzer, and W. Weidel,%id., 1964, lgb, 413.86E. F. Neufeld and W. Z. Hassid, Adv. Carbohydrate Chem., 1963, 18, 309;L. Glaser, Physiol. Rev., 1963, 43, 215; V. Ginsburg, Adv. Enzymol., 1964, 26, 35;L. F. Leloir, Biochem. J., 1964, 91, 1.87 N. Heimburger, K. Heide, H. Haupt, and H. E. Schultze, CZin. Chim. Acta,1964, 10, 293.1961, 5, 472.1963, 13, 20.M. Salton, Biochim. Biophys. Acta, 1961, 52, 329.03, 297GRANT AND SIRIKIN: CARBOHYDRATE- POLYPEPTIDE POLYMERS 499site of synthesis of most plasma proteins with the exception of y-globulins.88Some other tissues do have some capacity for the synthesis of certain plasma,proteins; e.g., the spleen can synthesize some a- and #l-globulins in addition toy-globulins.89 Apart from a few well-characterized proteins such as serumalbumin and fibrinogen, earlier studies were concerned only with the syn-thesis of broad classes of proteins, and very little was known about thebiosynthesis of carbohydrate prosthetic groups. More recently, throughincreasing knowledge of the characteristics of individual plasma proteins,studies have been carried out on the biosynthesis of plasma glycoproteinfractions of varying degrees of homogeneity and extent of physical andchemical characterization, and some preliminary information with respectto synthesis of the carbohydrate groups has been obtained from experimentsinvolving the use of labelled sugar precursors.It is perhaps unfortunate that in some of the studies the precise natureof the glycoprotein or glycoprotein fraction investigated has not beenapparent.The demonstration of homogeneity by a few simple character-ization techniques is now clearly inadequate in the light of knowledge con-cerning the heterogeneity of a variety of serum glycoprotein preparationsthat have been subjected to detailed examination.39, 90 Furthermore, theattribution of homology between serum glycoproteins from different speciesshould await, not only the demonstration of a close similarity in a widevariety of chemical and physical characteristics, but also the possession ofsimilar biological functions. While the latter criterion can be readilyestablished with glycoproteins such as haptoglobins and transferrins, thebiological role of many serum glycoproteins is as yet unknown.While earlier work demonstrated the liver to be the main site of synthesisof the polypeptide moieties of most plasma glycoproteins, the question ofwhether the liver was also the site of synthesis of the carbohydrate prostheticgroups has been settled only in recent years, although the origin of thegroups had been the subject of discussion for some time particularly withreference to clinical problems.Spirogl obtained evidence with [14C]glucose as precursor that in theintact rat the liver was the major site of addition of glucosamine to serumproteins.Winzler 92 and Shetlar 93 and their co-workers later concludedthis to be true from studies with [14C]glucosamine in the intact rat and rabbit.Winzler's group favoured, however, an interpretation of the kinetics ofincorporation of glucosamine different from that put forward by Spir0.91Glucosamine is used very efficiently for the synthesis of serum glycoproteinsand, while there is some conversion of it into sialic acid, there is little con-version into neutral hexoses or amino-acids.92, O3 Hepatectomy in the dogwas found 94 to abolish incorporation of [14C]glucosamine into '' al-acidL. Miller and W.F. Bale, J . Exp. Med., 1954, 99, 125; L. L. Miller, C. G.Bly, and W. F. Bale, ibid., p. 133.O 0 J. L. Simkin, E. R. Skinner, and H. S. Seshadri, Biochem. J., 1964, 90, 316.O1 R. G. Spiro, J. Biol. Chem., 1959, 234, 742.82 G.B. Robinson, J. Molnar, and R. J. Winzler, J . Biol. Chem., 1964, 239, 1134.g3 M. R. Shetlar, J. C. Capps, and D. L. Hem, Biochirn. Biophys. Acta, 1964,83, 93.9 * E. Athineos, J. C. Kukral, and R. J. Winzler, Arch. Biochem. Biophys., 1964,E. Espir,oja, Internat. J . AppE. Radiation Isotopes, 1961, 12, 122.108, 338500 BIOLOGICAL CHEMISTRYglycoprotein.” Several studies have demonstrated that the isolated per-fused rat liver can bring about the incorporation of various labelled sugarsinto serum glycoproteins. Thus, Sarcione 95 showed that [14C]glucose servedas a precursor of the galactose, mannose, and glucosamine residues of per-chloric acid-soluble and -insoluble serum glycoproteins, the former showinga much higher rate of incorporation than the latter.He also obtainedsimilar results when studying the synthesis of an a-globulin fraction;96 heshowed by use of [14C]leucine that the perfused liver also synthesized thepolypeptide of the material studied. Richmond 97 also demonstrated theincorporation of [14C]glycine and various [14C]labelled sugars into an a-globulinfraction under similar conditions. Krauss and Sarcione 98 later showedwith [14C]galactose and [14C]leucine as precursors that the perfused ratliver can synthesize haptoglobin. Experiments both in vivo and by per-fusion with [3H]valine have shown that the liver is the main or sole site ofhaptoglobin synthesis in the rabbit.99Several reports have provided some information concerning the subcellularlocation of glycoprotein synthesis in liver.From the intracellular distri-bution of trichloroacetic acid-insoluble radioactive material in liver afteradministration of [14C]glucosamine to the intact rat, Winzler’s group 92concluded that the microsome fraction played a major part in the incorpor-ation of glucosamine into serum glycoproteins. In a more detailed studyof the role of the microsome fraction, Sarcione loo demonstrated, with per-fused rat liver and [14C]galactose as precursor, that protein-bound galactoseand mannose appeared in the deoxycholate-soluble fraction of the micro-some material rather than in the ribosomes. Similar results on exposureto [14C]glucosamine were briefly reported.lol He suggested that the mem-brane structures of the endoplasmic reticulum, from which the deoxycholate-soluble fraction is believed to be derived,lo2 are responsible for the additionof the carbohydrate prosthetic groups of glycoproteins whilst the ribosomessynthesize their polypeptide moieties.These investigations have notinvolved the study of individual glycoproteins. Simkin and Jamieson lo3obtained evidence from experiments with [14C]leucine or [14C]valine in vivoand in a cell-free system that the microsome fraction of guinea-pig liver isresponsible for the synthesis of a number of acidic serum a-globulins. Withrespect to other tissues, a brief report lo4 has described experiments in vivowith [14C]glycerol as precursor which showed that the microsome fractionof hog gastric mucosa is involved in the synthesis of blood-group substance.On the other hand, in work which involved the use of calf thyroid slices or95 E.J. Sarcione, Biochemistry, 1962, 1, 1132.96 E. J. Sarcione, Arch. Biochem. Biophys., 1963, 100, 516.9 7 J. E. Richmond, Biochemistry, 1963, 2, 676.98 S. Krauss and E. J. Sarcione, Bioehim. Biophys. Acta, 1964, 90, 301.99 H. Mouray, J. Moretti, and M.-F. Jayle, Compt. rend., 1964, 258, 5095; 1964,259, 2721.100 E. J. Sarcione, J. Bid. Chem., 1964, 239, 1686.101 E. J. Sarcione and J. E. Sokal, Fed. Proc., 1964, 23, 273.102 P. Siekevitz, Ann. Rev. Physiol., 1963, 25, 15; Y. Mod6 and J. Chauveau in“The Liver”, ed. C. Rouiller, Vol. I, Academic Press, Inc., New York, 1963, p.379.103 J. L. Simkin and J. C. Jamieson, Biochem.J., 1964, 93, 8P.104 S. Kornfeld, R. Kornfeld, and V. Ginsburg, Fed. Proc., 1964, 23, 274GRANT AND SIMKIN : CARBOHYDRATE-POLYPEPTIDE POLYMERS 501isolated subcellular fractions therefrom,l05 a number of different particlefractions were found to incorporate label from [14C]glucose and [l4C]1eucineinto thyroglobulin. The particle fractions involved may not, however, bedirectly comparable with those of liver because the ribonucleic acid to proteinratio of each was similar.From an autoradiographic study of the subcellular location of radio-activity in a variety of mucin-producing cells and chondrocytes, Petersonand Leblond lo6 have suggested that the Golgi system is responsible for thesynthesis of the carbohydrate prosthetic groups of glycoproteins (see alsobelow), In common with others (see above), they envisage that the poly-peptide moieties are synthesized by ribosomes.The Golgi system is amembranous structure which is believed to have connexions with theendoplasmic reticulum and to play some role in the secretion of proteins andpossibly other substances from the cell.10‘ On disruption of the cell, it willdisintegrate into fragments which can appear in the microsome fraction.lO2It is possible, therefore, that only a small proportion of the membrane frag-ments found in the microsome fraction are connected with the biosynthesisof the carbohydrate groups. It has, in fact, been found that a “smoothmembrane ” subfraction of liver microsome material shows a greater in-corporation of [14C]glucosamine into glycoprotein than a ‘‘ rough membrane ’’subfraction.lO* It is of interest that the Golgi system has been implicatedas the site of sulphation of glycosaminoglycans 109,110 (see below).The results discussed above suggest that the synthesis of the polypeptidecomponents of glycoproteins, and the formation of most or all of theircarbohydrate prosthetic groups, are dissociated processes which take placeat different sites within the cell.While further information is required toconfirm this suggestion and to provide a detailed picture of the processesinvolved, it is of interest that it can provide a reasonable interpretation fora number of other findings. For example, Parker and his co-workerslllhave suggested that forms of transferrins exist in human foetal serum whichare deficient with respect to their carbohydrate prosthetic groups.Little is yet known about how carbohydrate prosthetic groups areadded to polypeptide or how the prosthetic groups are built up.An im-portant question is whether sugar residues are added singly or as oligo-saccharides or in both forms. There seem to be some elements of commondesign in the structure of many of the prosthetic groups.ll As discussedabove, where evidence is available, an N-acetylhexosamine residue hasbeen implicated in linkage with polypeptide. Some groups consist simplyof N-acetylhexosamine and mannose residues, as with, e.g., ovalbumin,lo5 R. G. Spiro and M. J. Spiro, Fed. Proc., 1964, 23, 316.lo6 M. R. Peterson and C.P. Leblond, J. Cell BioZ., 1964, 21, 143; Exp. CeZl Res.,1964, 34, 420.lo’ R. F. Zeigel and A. J. Dalton, J . CeEZ BioZ., 1962, 15, 45; C. Rouiller and A.-M.JQzequel in “ The Liver ”, ed. C. Rouiller, Vol. I, Academic Press, Inc., New York,1963, p. 195.lo* R. J. Winzler, personal communication.lo9 N. Lane, L. Caro, L. R. Otero-Vilardeb6, and G. C. Godman, J . CeZZ Biol., 1964,G. C. Godman and N. Lane, J. CeZZ Biol., 1964, 21, 353.W. C. Parker, J. W. C. Hagstrom, and A. G. Bearn, J. Exp. Ned., 1963,118, 975.21, 339502 BIOLOGICAL CHEMISTRYribonuclease B, and some of those of thyroglobulin. Others appear toconsist of an inner '' core " of N-acetylhexosamine and mannose residuesattached a t one point to polypeptide, and joined to this core are severalbranches each consisting of the trisaccharide sequence : sialyl-galactosyl-N-acetylhexosaminyl- (in some instances, the terminal sialyl residue isreplaced by fucosyl).It may be that these trisaccharide units are attacheden bloc, as uridiiie diphosphate (UDP) derivatives of them have been dis-covered in goat colostrum 112 and human milk.l13 On the other hand, Rose-man and his co-workers 114 have found enzymes in goat colostrum andsheep submaxillary gland that can catalyse the addition of terminal sialicacid residues to neuraminidase-treated human orosomucoid and ovine sub-maxillary mucin, respectively. The donor is cytidine monophosphate(CMP) sialic acid. A tlhird sialyl transferase from rat mammary glandcatalysed the transfer of a sialyl residue to a variety of galactosides oflow molecular weight, but was inactive with polymers.The colostrumenzyme showed some activity with small galmctosides, but the submaxillaryenzyme did not. The physiological significance of the sialyl tranaferases withrespect to glycoprotein synt'hesis is not yet clear. Those active with galacto-sides of low molecular weight may play an important part in the synthesisof compounds such as the UDP-trisaccharides which were mentioned aboveand which might be used as building blocks in glycoprotein synthesis.While it is possible that those enzymes whose specificity is directed mainlytowards polymers are involved in de novo synthesis, it may be that theaddition and removal of the terminal sialic acid residues of some glyco-proteins without further change in the molecules might constitute a mechan-ism which controls the biological function of the glycoproteins. Oroso-mucoid with a subnormal content of sialic acid has been reported recentlyto be present in the serum of humans with certain chronic diseases.l15Several groups 11% 117 have studied the conversion of glucosamine intocompounds of low molecular weight in rat liver.It has been shown thatUDP-N-acetylhexosamine is a major product of glucosamine metabolismand that the main route leading to it passes through N-acetylglucosamineand N-acetylglucosamine 6-phosphate. The administration of puromycinas an inhibitor of protein synthesis did not alter appreciably the maximumlevel of radioactivity in UDP-N-acetylhexosamine reached after adminis-tration of [W]glucosamine to the intact rat, but it did markedly reduce thesubsequent fall in radioactivity observed in its absence.ll7, 11* These resultssuggest t'hat UDP-N-acetylhexosamine plays some part in the biosynthesisof glycoproteins.Molnar and his co-workers 117 found that puromycin112 G. W. Jourdian, F. Shimizu, and S. Roseman, Fed. Proc., 1961, 20, 161.113 A. Kobata, Biochem. Biophys. Res. Comm., 1962, 7, 346.114 S. Roseman, Abs. Sixth Internat. Congress Biochemistry, New York, 1964,115 K. Schmid, J. F. Burke, M. Debray-Sachs, and K. Tolrita, Nature, 1964, 204, 75.116 J. F. McGarrahan and F. Maley, J. Biol. Chem., 1962, 237, 2458; R. DelGiaccoand F. Maley, ibid., 1964, 239, PC2400; P.J. O'Brien and E. F. Neufeld, Biochim.Biophys. Acta, 1964, 83, 352.11' J. Molnar, G. B. Robinson, and R. J. Winder, J. Biol. Chem., 1964, 239, 3157.118 S. Kornfeld, R. Kornfeld, E. F. Neufeld, and P. J. O'Brien, Proc. Nat. Acad.Sci. U.S.A., 1964, 52, 371.Vol. VI, p. 467GRANT AND SIMKIN: CARBOHYDRATE- POLYPEPTIDE POLYMERS 503strongly inhibited the incorporation of both [ 14C]leucine and [WJglucosamineinto liver and plasma proteins in the intact rat. They pointed out thatthe precise mode of action of puromycin in these circumstances was notknown. On the other hand, Richmond 97 did not find a very marked effectof puromycin on the incorporation of labelled sugars into glycoproteins onaddition to perfused rat liver, but his results are somewhat difficult tointerpret in the absence of reported controls.Feed-back mechanisms havebeen reported to operate in rat liver in pathways leading to the formation ofUDP-N-acetylhexosamine and CMP-N-acetylneuraminic acid.llsNo definite information has been reported concerning the mechanism ofbiosynthesis of carbohydrate-polypeptide bonds or with regard to theproblem of “ coding ” for the points of substitution with carbohydrate.The way in which coding is effected will probably depend upon whether sugarresidues are added to an already completed polypeptide chain or whetheramino-acids bearing one or more sugar residues are incorporated into t’hepolypeptide chain during its formation. It is not yet clear whether theNH grouping of the glycosylamine type of bond (see above) comes from theamide group of asparagine or elsewhere, i.e., whether the residue substitutedis asparagine or aspartic acid.Results obtained z9 with bovine pancreaticribonucleases A and B may, however, be of some significance as regards theproblems mentioned above. These two proteins have a common biologicalorigin. On present evidence, they appear to have very similar or identicalamino-acid sequences but differ in that B has a carbohydrate prostheticgroup. The residue in A which corresponds to that substituted in B isasparagine. Furthermore, if their amino-acid sequences are identical, thesegment of the peptide chain around the substituted residue is likely to besituated at or near the “surface” of the molecule.If the synthesis ofpolysaccharide is dissociated from that of polypeptide, this kind of conform-ation might facilitate the addition of carbohydrate to the residue substituted.The fact that glycopeptides isolated after proteolysis of a wide variety ofglycoproteins often have a rather similar complement of amino-acids (seepapers referred to in earlier section) may indicate that there is some favouredsequence of residues around those substituted with carbohydrate.Changes in the type of glycosaminoglycan syn-thesized by tissue cells cultured in vitro have been demonstrated to occurin established cell lines grown as monolayers 119 and in short-term cultureexperiments.l2*9 lZ1 One observation which may be related to these changesis that explanted chick embryo somites contain sulphate-activating enzymesonly when cultured in the presence of extracts of embryonic notochord orspinal cord.These enzymes catalyse the formation of 3’-phosphoadenosine5’-phosphosulphate (PAPS) from inorganic sulphate and adenosine triphos-phate (ATP), and their induction by tissue extracts is an interestingpossibility.lZ1Glycosaminoglycan sulphotransferases catalyse the transfer of sulphatefrom PAPS to acceptor polymers with some degree of substrate specificity.CZycosarninogZycuns.11* E. Davidson, J . Gen. Physiol., 1963, 46, 983.1 2 0 M. Glick and F. Stockdale, Biochim. Biophys. Acta, 1964, 83, 61.M. Glick, J. Lash, and 5. Madden, Biochim. Biophys. Acta, 1964, 83, 84504 BIOLOGICAL CHEMISTRYEarlier work on this subject has been revie~ed.~ Some of these enzymes arepresent in serum122 and there is some evidence that beef cornea containsboth a keratan sulphate and a chondroitin 4-sulphate sulphotransferase.123Nucleotide-bound sugars are intermediates in the biosynthesis of glycos-aminoglycans. A cell-free particulate preparation of rat embryonic tissueis capable of the synthesis of hyaluronic acid, as judged by the incorporationof istotope from UDP-N-[3H]acety~glucosamine into the polymer in thepresence of UDP-glucuronic acid and ATP.Treatment of the particulatematerial with papain released about 40% of this '' hyaluronate synthetase "in a soluble form (not sedimented a t 105,000 g).124 Polymer formation hasalso been demonstrated with a particulate preparation obtained from heparin-forming mast cell tumours which incorporated UDP-[14C]glucuronic acidand UDP-N-[3H]acetylglucosamine into a non-sulphated polysaccharidewhich may be a precursor of heparin.125 A glycosaminoglycan with a lowdegree of sulphation, and with many of the properties of a desulphatedchondroitin sulphate, has been shown to be formed by a particulate pre-paration obtained from chick epiphyses in the presence of labelled UDP-glucuronic acid and UDP-N-acetylgalactosamine.12" The Dorfman grouphave found that washing the cell-free particles further reduced the incor-poration of labelled sulphate into the polymer.Supernatant liquid from theoriginal preparation contained the enzymes necessary for the formation ofPAPS and the subsequent transfer of sulphate to the polymer.These studiesindicate that the penultimate step in the biosynthesis of sulphated glycos-aminoglycans is the formation of the polymer which subsequently under-goes sulphation. In contrast, UDP-hexosamine derivatives containingsulphate have been isolated127 and it has been claimed that only a smallproportion of the heparin synthesized by mast cell tumours can be formedby sulphate transfer to a polymer precursor.128It has been shown that subcellular particles from mast cells, fibroblasts,and epithelial cells contain most of the enzymes concerned with the bio-synthesis of glycosaminoglycans. Some indication of the nature of thesubcellular site has been given by radioautography. Rat tissues werefixed 5 minutes after the administration of glucose labelled with tritium atposition 1 or 6.The sections of fixed tissue showed an identical radio-autographic reaction which was concentrated in the Golgi system of mucin-secreting cells and of chondrocytes.lo6 High-resolution radioautographyhas been used to demonstrate that the goblet cells of rat colon lo9 and chondro-cytes 110 utilize administered labelled sulphate and concentrate it initiallyinto the paranuclear part of the Golgi system of the cell. Neither mito-chondria nor endoplasmic reticulum showed any significant radioautographicreaction. The possibility that both glycoproteins (see above) and glycos-122 J. Adams, Biochim. Biophys. Acta, 1964, 83, 127.123 B. Wortman, Biochim. Biophys.Acta, 1964, 83, 288.124 S. Schiller, Biochem. Biophys. Res. Comm., 1964, 15, 250.1 z 5 J. Silbert, J . Biol. Chem., 1963, 238, 3542.126 R. L. Pcrlman, A. Tesler, and A. Dorfman, J . Biol. Chem., 1964, 239, 3623;12' J. L. Strominger, Biochim. Biophys. Acta, 1959, 31, 283; J. Piclrard, A. Gardais,12* I;. Spolter, L. Rice, and W. Marx, Biochim. Biophys. Acta, 1963, 74, 188.J. Silbert, ibid., p. 1310.and L. Dubernard, Nature, 1964, 202, 1213GRANT AND SIMKIN: CARBOHYDRATE-POLYPEPTIDE POLYMERS 505aminoglycans may be synthesized in the Golgi system of the cell is of greatinterest and remains to be confirmed by more direct means.Mwopeptides of bacterial cell wlk. The major uridine-containingglycopeptide which accumulates intracellularly when the growth of Staphy-lococci is inhibited by penicillin has been characterized previously, andit's identity has now been confirmed by the total chemical synthesis ofthe glycopeptide, Na-[ 1 - (2-acetamido-3-0-~ -glucosyl) -D-propionyl-L-alanyl-~-y-glutamyl]-~-lysyl-~-alanyl-~-alanine.~~~ This UDP-N-acetylmuramyl-peptide could also be synthesized by isolated enzymes from Stap7zyZococciby the sequential addition of the appropriate single amino-acids to UDP-N-acetylmuramic acid, followed by the dipeptide ~ - a l a n y l - ~ - a l a n i n e . ~ ~ ~ 131This dipeptide was formed from D-alanine and ATP by a relatively specificD-alanyl-D-alanine synthetase and is added enzymically as a unit to UDP-N-acetylmuramyl-~-alanyl-~-y-glutamyl-~-l~sine.~~~ The kinetics of in-hibition of the synthetase by u-cycloserine would indicate that both bindingsites were blocked by the antibiotic.133The UDP-N-acetylmuramyl-peptide did not penetrate the intact cellbut its identity as a precursor of cell-wall mucopeptide was indicated by itsutilization in a cell-free system.Particulate enzyme preparations of 8.uureus catalysed the formation of a radioact,ive non-dialysable polymer fromUDP-N-acetylgalactosamine, A4TP, and UDP-N-acetylmuramyl-peptidelabelled with either [14C]lysine or [3H]glutamate.131y 134 Since isotope fromboth amino-acids in the added peptide was incorporated into the polymer,whereas free [3H]lysine was not, it seems probable that the peptide wasincorporated as a unit.134 The identification of some of the fragmentsobtained after digestion of the polymer with lysozyme indicated that insome respects the polymer was similar to mucopeptide formed by the intactGlycine, another component of the mucopeptide of 8.aureus, was alsoincorporated into the polymer when potassium chloride, a ribosome fraction,and a non-dialysable fraction of cell-sap were included in the polymer-formingsystem. Ribonuclease inhibited glycine incorporation but had no effect onthe utilization of the UDP-N-acetylmuramyl-~eptide.l~~ It has been sug-gested that the glycine of mucopeptides is present as a chain of five or sixglycine residues which serves as a cross-linking bridge between adjacentpeptide units attached to the carbohydrate chain.135 The poor incorporationof glycine when UDP-N-acetylmuramyl-~-alanine was used instead of theentire UDP-N-acetylmuramyl-peptide in the polymer-forming system wouldbe consistent with this view.134ce11.131129 A.E. Lanzilotti, E. Benz, and L. Goldman, J. Amer. Chem. SOC., 1964, 86, 1880.130 E. Ito and J. L. Strominger, J. Biol. Chern., 1962, 237, 2689, 2696; E. Ito andJ. L. Strominger, ibid., 1964, 239, 210; P. Meadow, J. Anderson, and J. L. Strominger,Bwchem. Biophys. Res. Comm., 1964, 14, 382.P. Meadow, J. Anderson, and J. L. Strominger, Biochern. Biophys. Res. Comm.,1964, 14, 382.132 F. Neuhaus and W. Struve, Abs. Sixth Internat. Congress Biochemistry, NewYork. 1964, Vol. VI, p. 520.133 F. Neuhaus and J. Lynch, Biochemistry, 1964, 3, 471.134 A. N. Chatterjee and J.T. Park, Proc. Nut. Acud. Sci. U.S.A., 1964, 51, 9.136 M. Mandlestam and J. L. Strominger, Biochem. Biophys. Res. Cornrn., 1961,5,446506 BIOLOGICAL CHEMISTRYTeichoic acids. The net synthesis of polyglycerophosphate from cyt-idine diphosphate (CDP) glycerol is catalysed by a particulate enzymepresent in the protoplast membrane of Bacillus licheniformis and Bacillussubtilis. The enzyme required high concentrations of Ca2+ and Mg2f andthe product, which cannot be separated from teichoic acid, is thought to bea linear chain of glycerophosphate residues with phosphodiester bondslinking C-1 and C-3 of successive glycerophosphate residues.136 A similarrequirement for Ca2f and Mg2+ has also been found for a cell-wall enzymeprepared from Lactobacillus plantariurn which catalysed the formation ofa polyribitol phosphate from CDP-ribit01.l~' Further work on the bio-synthesis of teichoic acids has been concerned with the formation of glu-cosylpolyglycerophosphate from UDP-glucose and polyglycerophosphateby a membrane preparation of B.subtilis. Treatment of the product ofbiosynthesis with hydrofluoric acid a t 0 O hydrolysed phosphodiester bondswithout afEecting glucosidic linkages. Glucosylglycerol was isolated andhydrolysed by an a-glucosidase but did not yield formaldehyde on oxidationwith periodate. It was concluded that glucose was linked to C-2 of glycerolby an a-glucosidic bond.13*136M. Burger and L. Glaser, J. Biol. Chem., 1984, 239, 3168.137 L. Glaser, J . Biol. Chern., 1964, 239, 3178.158 L.Glaser and M. Burger, J . Biol. C'hein., 1964, 239, 31875. PROTEINS AND PEPTIDESBy D. G. Smyth(National Institute for Medical Research, Mill Hill, London, N . W . 7)THE field of protein and peptide chemistry has again shown extensive progressand increasingly invades contiguous areas of the biological sciences. Thisyear three proteins-chymotrypsinogen,l azurin,2 and ferredoxin 3 h a v ejoined the seven 4-insulin, ribonuclease hzemoglobin, myoglobin, cytochromec, TMV protein, and lysozyme-of which the complete amino-acid sequencesare firmly established. The new peptide hormones, gastrin 5-7 andphysahmin,* have been isolated, their amino-acid sequences determined,and syntheses achieved. In addition, the primary structures of a numberof bacterial enzymes such as takadiastase ribonuclease and Pseudomomscytochrome 10 have been elucidated; although similar in function to proteinslisted above and bearing the same name, their sequences have little incommon with the related proteins.Preliminary sequences of trypsinogen,llpapain, l2 and pancreatic trypsin inhibitor 13 have been proposed, and studiesare in progress on carb~xypeptidase,~~ subtili~in,~~ and RNA (ribonucleicl(a) B. S . Hartley, Nature, 1964,201, 1284; B. S. Hartley, " Structure and Activityof Enzymes ", Academic Press, Inc., New York, 1964, p. 47; ( b ) B. Keil and F. germ,* M. Tanaka, T. Nakashima, A. M. Benson, H. F. Mower, and K. T. Yasunobu,Eoc. cit., p. 37.R. P. Ambler and L. H. Brown, J . Mol. Biol., 1964, 9, 825.Ann.Reports, 1963, 60, 468.ti R. A. Gregory and,H. J. Tracey, J . Brit. SOC. Castroendocrinology, 1964, 5, 103.H. Gregory, P. M. Hardy, D. S . Jones, G. W. Kenner, and R. C . Sheppard,Nature, 1964, 204, 931.J. C. Anderson, M. A. Barton, H. Gregory, P. M. Hardy, G. W. Kenner, J. K.MacLeod, J. Preston, R. C. Sheppard, and J. S. Morley, Nature, 1964, 204, 933.V. Erspamer, A. Anastasi, G. Bertaccini, and J. M. Cei, Experientia, 1964, 20,489, 676; L. Bernardi, G. Bosisio, 0. Gaffredo, and R. de Castiglione, ibid., p. 490.SF. Egami, K. Takahashi, and T. Uchida, Abs. 6th Internat. Congress Bio-chemistry, 1964, Vol. IT, p. 247; K. Takahashi, Proc. 16th Ann. Meeting Chem. SOC.Japan, 1963, p. 96.lo R. P. Ambler, Biochem. J., 1963, 89, 349.l1 ( a ) V.Tomasek, 0. Mikes, V. Holeysovsky, and F. Som, CoEZ. Czech. Chem.Comm., 1964, 12, 3122; (b) 0. Mikes, V. Holeysovsky, V. Tomasek, and F. Born, Abs.6th Internat. Congress Biochemistry, 1964, Vol. 11, p. 131; (c) K. A. Walsh and H.Neurath, Proc. Nut. Acad. Sci. U.S.A., 1964,52, 884; ( d ) K. A. Walsh, D. L. Kauffman,K. S. V. S. Kumar, and H. Neurath, ibid., 1964,51, 301; ( e ) T. Hofmann, Biochemistry,1964, 3, 356.la A. Light, R. Frater, J. R. Kimmel, and E. L. Smith, Proc. Nat. A d . Sci.U.S.A., 1964, 52, 1276; A. Light and E. L. Smith, Abs. 6th Internat. Congress Bio-chemistry, 1964, Vol. 11, p. 116; J. R. Kimmel, H. J. Rogers, and E. L. Smith, J . Biol.Chem., 1966, 240, 266.l3 J. Chauvet, G. Nouvel, and R. Acher, Biochim. Biophys.Acta, 1964, 92, 200;B. Kassell, M. Radicevic, M. J. Ansfield, and M. Laskowski, Biochem. Biophys. Res.Comm., 1965, 18, 255.l4 K. S. V. S. Kumar, K. A. Walsh, J. P. Bargetzi, and H. Neurath, Biochembtry,1963,2, 1475; J. P. Bargetzi, E. 0. P. Thompson, K. S. V. 8. Kumar, K. A. Walsh, andH. Neurath, J . Biol. Chem., 1964, 239, 3767.l5 C. B. Kasper and E. L. Smith, Abs. 6th Internat. Congress Biochemistry, 1964,Biochern. Biophys. Res. Comm., 1964, 16, 422.Vol. 11, p. 89.508 BIOLOGICAL CHEMISTRYacid) phage protein.le The knowledge of the amino-acid sequences of thesepeptides and proteins provides a firm foundation for studies on the relationbetween their biological activities and their molecular structures.In studies on the modification of pure proteins, there has been increasingemphasis on the use of chemical reagents under conditions defined by carefulstudies with model compounds, and on the identification of sites of reactionafter isolation and purification of homogeneous derivatives.Indin.-The amino-acid sequence of insulin as elucidated by Sanger/SI NI&NH2 SI 1 I /NH,.Phe.Val.Asp.Glu.His.Leu.Cys.Gly.Ser.His.Leu.Val.Glu.Ala.Leu.Tyr.Leu.Val.Cys.Gly.Glu.HO. Ala.Lys.Pro.Thr .Tyr.Phe.Phe.Gly.i&gFIG.1. Arnino-acid sequence of sheep insulin.(A, P. Ryle, F. Sanger, L. F. Smith, and R. Kitai, Biochem. J., 1955, 60, 541.)and his colleagues has served as a model for synthesis of the chains. Con-current with the synthetic work of Katsoyannis and his colleagues werethe parallel studies of Meienhofer, Schnabel, and Zahn, and of Wang andhis colleagues; all must be applauded.The achievements of the threegroups will here be considered in turn.The first publication of the total synthesis of insulin17 appeared inDecember 1963 from Aachen ; the biological activities obtained by hybridiza-tion of the synthesized chains are recorded in Table 1.l* It should be notedthat recombination of the reduced chains of natural insulin restores only1-2% of the activity.TABLE 1.Preparation mouse oxidn. by rat uptake by ratA + B convulsionb adipose tissuec diaphragmb((2 concns.) ( ( 4 concas.)Biological activities of insulin preparations 1% aConcns. for Glucose Glucose0*5-1.0% 0.6-0.7% -Synth. Nat. o-9-1*0yo 1.5-1.6 % 2.0 %Eat. Synth.0.6-0.7 0.6--0.7% -Synth. Synth.a All three preparations gave complete neutralization of antiserum (E. P. Pfeiffer, Frankfurt).determined by E. P. Pfeiffer, Frankfurt.Determined by C. Oloxhuber (Baey, Elberfeld).Determined by H. Clauser, Paris.16 M. A. Naughton, personal communication; G. W. Notmi, W. Konigsberg, L. C.Craig, and N. D. Zinder, Abs. 6th Internat. Congress Biochemistry, 1964, Vol. 11, p. 140.1' J. Meienhofer, E. Schnabel, H. Bremer, 0. Brinkhoff, R. Zabel, W. Sroka,H. Klostermeyer, D. Brandenburg, T. Okuda, and H. Z&n, 2. Nuturforsch., 1963,18b, 1120.la 0. Brinkhd, Thesis, Technische Hochschule, Aachen, 1964; J. Meienhofer,personal communicationSMYTH: PROTEINS AND PEPTIDES 509Some details of the A-chain synthesis l9 and full details of the B-chainsynthesis 20 have now been published.An A-chain derivative isolated fromnatural insulin, and with the intra-chain disulphide bridge intact (A-chain6,l l-disulphide 7,20-bi~thiosulphate),~~ was found to give small but definiteinsulin activity (06%) ; a partially oxidized preparation of synthetic A-chainalso showed activity,22 confirming the view that bioactivity is an intrinsicproperty of the A-chain and was not due to contamination by B-chainTherefore, when biological activity is used as a means of assessing the purityof the synthetic peptides, the activity of the recombined A- and B-chainashould be substantially greater than that of the A-chain alone.From Pittsburgh, the first partial synthesis of insulin from syntheticA-chain and natural B-chain was published in September 1963;23 therecovery of insulin activity was @5-1-270.An attempted total synthesiswas described at the Brook Lodge Conference on Proteins and Polypeptidesin October 1963 a6 a preliminary communication;% approximately 0.01 yoactivity was announced. Some details of the syntheses were publishedlater but no data on biological activity were included. The total synthesiswas described in full in March 1964,26 and hybridization experiments byG. H. Dixon and S. Wilson were reported at the 5th Congress of the Inter-national Diabetes Federation, Toronto, July 1964. The activities obtainedwere :Synthetic A, $- synthetic B,: 0.07%Synthetic A, + synthetic B,: 0.02%Compared with natural A + natural B: 0.65%A third group has reported a complete synthesis of the B-chain and itsreconstitution with natural A-chain t o generate insulin activity ;27 Synthesisof fragments of the A-chain was also reported.28The activities obtained by the three groups are given in Table 2.TABLE 2.Activities (in units per mg.) of regenerated insulinGroupPreparation , \A + B Aachen Pittsburgh ChinaSynth. Spth. 0*15-0*27 0.005-0.02 -Synth. Nat. 0.4-0.54 0 . 1 3 4 . 3 2 -Nat. Spth. 0 . 1 8 4 - 1 9 0.09 1.1lB H. Bremer, Thesis, Technische Hochschule, Aachen, 1964.2o H. Zahn, J. Meienhofer, and H. Klostermeyer, 2. Naturforsch., 1964, 19b, 110;J. Meienhofer, ibid., p. 114; E. Schnabel, ibid., p. 120; E. Schnabel, Annalen, 1984.674, 218 ; H.Klostermeyer, Thesis, Technische Hochschule, Aachen, 1964.21 J. Meienhofer and 0. Brinkhoff, Nature, 1963, 199, 1095.sa P. V o f i , A. M. Chambant, D. Ebone-Bonis, H. Clauser, 0. Brinkhoff, H. Bremer,J. Meienhofer, and H. Zahn, Nature, 1964, 203, 408.2r P. G. Katsogannis, A. Tometsko, and K. Fukuda, J . Amer. Chern. Soc., 1963.85, 2863.2o P. G. Katsoyasmis, Chem. Eng. New8, 1963, 4l, 45.26 P. G. Kataoyannis, Vox Sanpkis, 1964, 9, 227.z 6 P. GI. Katsoymis, K. Fukuda, A. Tometsko, K. Suzuki, and M, Tilak, J . Amer.Chem. Soc., 1964, 86, 930.27 C. I. Nui, Y. T. Rung, W. T. Huang, L. T. Ke, C. C. men, Y. C. Du, R. Q.Jiang, C. L. Tsou, S. C. Hu, S. Q. Chu, and K. Z. Wang, Sci. Sinica, 1964, 13, 1343.28 T. Wang, C. C. Hsu, J.Y. Lu, K. Huang, and C . C. Huang, Acta Chim. Sinica.1963, 29, 114; 1964, 30, 206510 BIOLOGICAL CHEMISTRYThe appearance of activity after hybridization of synthetic chains,compared with natural chains, is an inadequate measure of the success ofthe syntheses in reproducing the structure derived by Sanger and his school.29At present, the recovery of the native protein from the reduced chains ofnaturul insulin is very low, and therefore total synthesis of the whole insulinmolecule must await new methods for specific chemical or enzymic couplingof the disulphide bridges to generate the intrinsic activity of the naturalhormone. The reduction of all the disulphide bonds of natural insulin hasbeen performed electrolytically under very mild conditions, but the A- andB-chains were released as random coils and showed little tendency to re-combine correctly on oxidation.30 The integrity of the disulphide bonds ofinsulin appears to be a prerequisite to the restoration of the native con-formation of the active molecule.Modification of the terminal amino-groups of insulin by two differentchemical reagents resulted in remarkably different effects on hormonalactivity.Reaction with homocysteine thiolactone caused almost totalinactivation, whereas reaction with methionine N-carboxyanhydride allowed50 % retention of activity.31 Similarly, in studies with ribonuclease guani-dination of amino-groups by O-methylisourea 32 has little effect on activitywhereas carbamoylation of amino-groups33 in the same enzyme has beenreported to cause inactivation.While in none of these cases ~7as a homo-geneous derivative isolated and thoroughly characterized, the observationsserve to emphasize that chemical modification of functional groups in anenzyme or hormone provides direct information only on the properties ofthe derivative, and caution must be exercised in deducing the role playedby the functional groups in the initial protein.Some information concerning the conformation of the insulin moleculehas been obtained from studies with inhibitors. A basic protein isolatedfrom pancreas was found to inhibit the action of insulin,34 and this effectwas attributed to a direct binding between the inhibitor protein and theinsulin molecule, resulting in a conformational change in the hormone whichreduced its affinity for the physiological receptor.On the other hand,inhibition of insulin action by an antiserum to insulin 35 probably occurs bycompetition between the antiserum and the physiological receptors, forbinding of free hormone. The antisera, however, contain a number ofchemically distinct proteins, which interact with insulin and can be separatedby electrophoresis.3~ It may also be noted that weak antagonistic activity 3'and weak insulin activity 38 have been claimed as a property of the isolatedB-chain.Considerable interest has arisen in the development of immunoassays29 A. P. Ryle, F. Sanger, L. F. Smith, and R. Kitai, Biochem. J., 1955, 60, 5-41.30 G. Markus, J . Biol. CJbem., 1964, 239, 4163.a1 T.K. Virupashka and H. Tamer, Biochemistry, 1964, 3, 1507.88 W. A. KIee and F. M. Richards, J . BioL Chem., 1957, 229, 489.a3 G. R. Stark, W. H. Stein, and S. Moore, J . Biol. Chm., 1960, 235, 3177.34 J. W. Czerkawski and J. P. Bingle, Biochem. J . , 1963, 87, 33P.8 6 C. B. Mann and G. H. Smith, Biochem. J . , 1963, 88, 13P.s6 M. L. Heideman, Biochemistry, 1964, 3, 1108.s7 J. W. Ensinck, R. J. Mahler, and J. Vallance-Owen, Biochem. J., 1965, 94, 150.38 R. G. Langdon, J . Biol. Chsm., 1960, 235, PC 15SMYTH: PROTEINS AND PEPTIDES 51 1for the quantitative measurement of insulin.39 Antisera are prepared tothe hormone, and the insulin in solutions to be assayed is allowed to competewith a known amount of 1FI-labelled insulin for binding to antiserum in vitro.In precipitation methods,40 anti-y-globulin is added to the mixture to favourprecipitation of soluble antigen-antibody complex.41 For the high specificlabelling of insulin with 1311, the use of iodine monochloride may be preferredbut it should be noted that the introduction of more than one iodine atomper molecule of insulin results in changes in molecular conformation andreduction in biological activity.42Ribonuclease.-The present concept of the active site of bovine pancreaticribonuclease-A involves two histidine residues a t positions 12 and 119 43 inthe established amino-acid sequence,44 acting in concert with an &-amino-group at position 41.45 Chemical modification at any of these positionsis prevented by the presence of substrate or phosphate.From a considera-tion of the atomic dimensions of iodoacetate and of ions that inhibit theiodoacetate reaction, the three groups postulated as part of the active centreof the enzyme are considered to be situated spatially at distances no greaterthan 5 A from each other.43 Intricate experimental evidence for a sreciairelationship between the two histidine residues has been provided by alkyi-ation of the dimer of ribon~clease.~~ In contrast with the same reaction onthe monomer, a new disubstituted species was produced (Fig. 2; numbers I1and III).I I1 I11 IVFIG. 2.represents site of carboxymethylation.The possibility that the inactive l-CMHisl19-RNAase or 3-CMHis12-RNAase might still retain the structural features required, for binding of sub-strate has been excluded by examination of difference spectra which show thatcarboxymethylation destroys both the nucleotide binding and the anion-binding site at the active centre.4' With either carboxymethylated deriva-tive, the alkylation transforms a cationic imidazole group into one bearing89 R.S. Yalow and S. A. Berson, " Methods of Biochemical Analysis ", ed. D. Click,40 C. N. Hales and P. J. Randle, Biochena. J., 1963, 87, 137; C. R. Morgan and*I J. H. Skom and D. W. Talmadge, J . CZin. Invest., 1958, 57, 783.J. L. Izzo, W. F. Bale, M. J. Izzo, and A. Runcone, J. BioZ. Ch., 1964, 239,4s A. M. Crestfield, W. H. Stein, and S. Moore, J. BioE. Chem., 1963, 288, 2421.D. G. Smyth, W. H. Stein, and S .Moore, J. BioZ. Chem., 1963, 238, 227.o5 C. H. W. Hirs, Brookhaven Symposia in Biology, 1962, Vol. XV, p. 154.46 A. M. Crestfield and R. Fruchter, Fed. Proc., 1964, 25.4's. T. Yang and J. P. Hummel, J. Biol. Chem., 1964, 239, 3776-Interscience, London, 1964, Vol. XII, p. 69.A. Lazarow, Diabetes, 1963, 12, 115.3749612 BIOLOGICAL CHEMISTRYa carboxylate anion. Electrostatic interaction can then take place with thecomplementary positively charged imidazolium residue in a similar mannerto the binding of phosphate across the separate cationic sites in the nativeenzyme. Thus, at pH 5 the two carboxymethyl derivatives are denaturedmore slowly than ribonuclease and have higher transition temperatures.With the demonstration by Koshland and his colleagues 48 that substratebin% by phosphoglucomutase causes changes in the conformation of theenzyme which alter the reactivity of some amino-acid residues, the classicalprotective effect of substrates against modification of certain residues cannotbe taken as proof that these form a part of the active site.For this reason,the products of reaction of ribonuclease with iodoacetate have been emminedto decide whether their lack of enzymic activity might be caused by distortionof tertiary structure. Evidence to the contrary was obtained by measure-ments of thermal transition tern~erature,~' by titration of normal and buriedtyrosine residues>', 49 and by immunological comparisons.sO That the twoinactive carboxymethyl derivatives of ribonuclease appear to retain thetertiary structure of the native enzyme is strong support for a unique andessential function for the two histidine residues at the active site.The subtilisin pieces or ribonuclease, S-peptide (1-20) and S-protein(21-124), which aggregate to restore the activity of the native enzyme, haveprovided valuable information on particular covalent portions of the moleculerequired for structure stabilization at the active centre.51 In recent experi-rnents,62 digestion of the S-protein with carboxypeptidase resulted specificallyin the removal of the C-terminal valine residue and was without effect onthe recovery of enzymic activity appearing on addition of S-peptide.Furtherdigestion led to the release of serine; the reconstituted RNAase-S, lackingvaline-124 and serine-123, still retained 50% of the activity of RNAase-A.Thus, this serine is not directly involved in the catalytic mechanism; thedecrease in activity probably results from changes in the conformation ofthe enzyme secondary to the covalent modification. Finally, S-proteinlacking the C-terminal tetrapeptide was completely inactive in the presenceeven of 100-fold molar excess of S-peptide.The extensively degradedS-protein (21-120), however, was still capable of associating with S-peptide,but the afhity was weak. This interaction between peptide and proteinis similar to that observed in the interaction between nitrous acid-treatedS-peptide and normal S-protein;63 the fragments associate without producingactivity, and inhibition is present against other fragments capable of causingactivation.The binding of inactive S-peptide to inactive S-protein toproduce an active complex has been compared with the binding of a peptidehormone to a protein receptor.61, 54 The above examples with derivativesof S-peptide and of S-protein serve as a model for the inhibition of the actionD. E. Koshland, J. A. Yankeelov, and J. A. Thoma, Ped. Proc., 1962, 21, 1031.4D G. R. Stark, W. H. Stein and S. Moore, J . Biol. Chem., 1961, 236, 436.61 F. M. Richards, " Structure and Activity of Enzymes ", Academic Press, London,68 J. T. Potts, D. M. Young, C. B. Anfinsen, and A. Sandoval, J. Bid. Chern.,68 P. J. Vitbyathil and F. M. Richards, J . BWZ. Chern., 1960, %, 1029.s r K .Hofmann, Proc. Chm. SOC., 1963, 363.K. Brown, Ann. New York Acad. Sci., 1963, 103, 754.1964, p. 6.1964, 239, 3781SMYTH: PROTEINS AND PEPTIDES 513of a peptide hormone by an analogue of the hormone, each competing forbinding to the same receptor.55Some evidence has been obtained that monosubstituted methioninederivatives of ribonuclease may be partially active whereas disubstitutedderivatives are probably inactive.66 Modification of a single methionineresidue in the S-peptide had previously been shown to decrease the bindingafbity of S-protein but did not markedly affect the activity of the complex.67The chemical probing of the three-dimensional structure of a proteinwould be considerably advanced if successful cross-linking by a bifunctionalreagent could be achieved with retention of activity.Exposure of ribo-nuclease to alkaline conditions resulted in some hydrolysis of cystine residuesfollowed by p-elimination to form residues of dehydroalanine.s8 Additionof a lysine E-amino-group then took place at the double bond, but the cross-linked derivative was inactive.58, 59 Successful cross-linking with retentionof activity has been attained on carboxypeptidase in the crystalline stateby using glutardialdehyde to couple amino-groups.60 In this experiment,the separation of reactive groups could be calculated; the distance must becompatible with biological activity of the molecule carboxypeptidase mole-cule, either free in solution or within the crystal lattice.Ribonuclease-B, an enzyme present as a minor component of bovinepancreatic secretion, has been isolated in the pure state.A surprising featureis the presence of a glycopeptide in which the carbohydrate-protein linkageoccurs on the /3-carboxyl group of an aspartic acid residue.61 In detailedexperiments on the carbohydrate-peptide link in egg albumin, a similarlink between the /?-carboxyl group of an aspartic acid residue and a residueof N-acetyl-D-glucosamine has been described and characterized. 62Chymotrypsinogen A.-The complete primary structure of chymo-trypsinogen, a protein of molecular weight 25,000, has been elucidated inCambridge by Hartley la (Pig. 3). In a parallel investigation, Keil andhorm and their colleagues in Prague have deduced an almost completesequence in substantial agreement.lb The special difficulties associatedwith this protein arise principally from its size, the single chain containing250 amino-acid residues; from the occurrence of autolytic digestion duringthe preparation of fragments by specific methods of cleavage; and frommajor problems with solubility.In Hartley’s work, the difficulties were overcome by the division ofchymotrypsinogen into A-, B-, and C-chains.Activation of the zymogento a-chymotrypsin, followed by oxidation, provided the oxidized A-chain(1-13); activation of the zymogen, followed by reduction and carboxy-methylation of (di-O-isopropylphosphory1)-a-chymotrypsin led to a cleanseparation of the B- and the C-chain, isolated by column chromatography.The B-chain (16-146) was digested with trypsin and gave five solubles~ D.G. Smyth, Nature, in the press.s6 G. R. Stark and W. H. Stein, J . Bid. Chem., 1964, 239, 3755.s7 P. J. Vithayathil and F. M. Richards, J . Biol. Chem., 1960, 236, 2343.s8 Z. Bohak, J . Biol. Chem., 1964, 239, 2878.6g A. Patchornik and M. Sokolovski, J . Amer. Chem. SOC., 1964, 88, 1860.6o F. A. Quiocho and F. M. Richards, Proc. Nat. A d . Sci. U.S.A., 1964, 52, 833.6aR. D. Marshall and A. Neuberger, Biochemhtry, 1964, 3, 1598.T. H. Plummer and C. H. W. Hirs, J . Biol. Chem., 1964, 329, 2530514 B I 0 LO GI C AL CHI MIS TRYCys.Gly. Val.Pro. Ala.110 . Gln. Pro. Val.Leu.Ser . Gly. L e u . 4 e r . Arg.-Ile . Val.Gly. -1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 14 15 16 17 18Asp.Glu.Glu. Ala.Val.Pro. Gly. Ser . Try.Pro.Try.Gln.Va1.Ser. Leu.Gln. Asp.Lys.Thr.Gly. -19 20 21 22 23 24 26 26 27 28 29 30 31 32 33 34 35 36 37 38Phe. His. Phe.Cys. Gly. GIs. Ser Leu.Ile . Asn.Glu. Asn.Try.Va.1. Val. Thr.Ala. Ma. His. Cys. -39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 5T 58Gly. Val. Thr.Thr.Ser . Asp.Va1. Val. Val. Ala. Gly. Glu. Phe.Asp.Gln. Gly . Ser . Ser , Ser . Glu. -59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78Lys.Ile . Gln.Lys.Leu.Lys.11e. Ala.Lys.Val.Phe.Lys.Asn.Ser. Lys.Tyr.Asn.Ser.hu.Thr. -79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98Ile . Asn .Asn .Am .Ile . Thr .Leu .Leu.Lys . Leu.Ser . Thr . Ala. Ala . Ser . Phe .Ser . Gln . Thr.Va1. -99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118Ser .Ala . Val. Cys . Leu.Pro. Ser . Ah. Ser . Asp. Asp .Phe.Ala . Ala . Gly . Thr . Thr . Cys. Val. Thr . -119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138Thr.Gly.Try.Gly. Leu.Thr.Arg.Tyr.-Thr.Asn.-Alrt , Asn.Thr.Pro. Asp.Arg.Leu.Gln. -139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156Gln. Ala . Ser . Leu.Pro. Leu.Leu .Ser . Asn.Thr.Asn .Cys. Lys. Lys.Tyr.Tyr. Gly . Thr.Lys.Ile . -157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176Lys. Asp. Ala . Met .Ile . Cys. Ala . Gly . Ala . Ser . Gly . Val. Ser . Ser . Cys. Met .Gly . Asp .Ser . Giy . -177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 392 193 194 195 196Gly.Pro.Leu.Va1.Cys.Lys.Lys.Asn.Gly.Ala.Try.Thr.Leu.Va1. Gly.Ile . Val. Ser. Ser .Try. -197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216Gly. Ser . Ser . Thr. Cys. Ser . Thr . Ser . Thr . Pro. Gly . Val. Tyr . Ala . Arg .Val. Thr . Ala. Leu.Va1. -217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236Asn.Try.Va1. Gln. Gln. Thr.Leu.Ala . Ala . Asn.237 238 239 240 241 242 243 244 245 246Disulphide bridges: 1-122; 42-58. 23c1-?01; 168-152: 191 -221.FIG. 3. Amino-acid sequence of bovine chymotrypsinogen-A. 1 In a-chymotrypsin, theA-chain w w k t s of residues 1-13, the B-chain of residues 16-146, and the C-chainof residues 149-246.peptides, tyrosine, and an insoluble " core " of aggregated peptides whichwas fractionated by chromatography in 8M-Urea. The composition andpurity of each of the resulting soluble peptides was established by quantita-tive amino-acid analysis.Large tryptic peptides containing up to 43 amino-acid residues were further degraded by chymotrypsin, pepsin, subtilisin, orpapain, or by partial acid hydrolysis, to yield small peptides amenable todetermination of sequence. The C-chain (149-246) was digested withtrypsin and gave four soluble peptides and a core of three insoluble peptides.Successful fragmentation of the core was achieved by prolonged exposure tochymotrypsin or by dissolution in 98% formic acid and dilution into aqueouspepsin. In general, small peptides were separated by paper electrophoresis,and all sequences were determined by qualitative or semiquantitativemethods.6SThe pairing of the disulphide bridges was solved by a " dia,gonal " paper** W.R. Gray and B. S. Hartley, Biochem. J., 1963, 89, 379SNYTH: PROTEINS AND PEPTIDES 515technique.64 Peptides obtained by peptic digestion of chymotrypsinogenwere separated by electrophoresis on paper, oxidized in situ, then submittedto electrophoresis under the same conditions in B perpendicular direction.Peptides not containing cystine exhibited the same mobility in each directionand appeared on a diagonal line; each cystine peptide, on the other hand,yielded a parallel pair of cysteic acid peptides displaced from the diagonal.Pairs of cysteic acid peptides were thus obtained free from all others in onestep, advantage being taken of their change in mobility after oxidation.The sequence work of the Prague group lb has taken place along similarlines.The method of Hoang et aL65 was used for the separation of the threechains of chymotrypsinogen, though there has been some question of hetero-geneity of S-sulpho-chains prepared by this method.66 Again, chromato-graphy in dissociating solvents was extensively employed for the separationof insoluble aggregates of peptides. A procedure for converting cystineresidues into S-( 2-aminoethy1)cysteine residues 67 was particularly successful :CH,*S-S*CH, CH,-S*SO,- CH,*SH CH,*S*[CH,],-NH,I I I I INH,*CH CH*NH2 + CH-NH, + CHNH, --+ CH*NH,I 1 I I IC0,H C0,H C0,H C0,H C0,HX-Sulphocysteine residues were converted into a basic form susceptible toattack by trypsin ; the resulting peptides provided valuable information onoverlapping sequences. Two valuable additions to techniques of specificcleavage deserve mention. The specificity of trypsin was increased by theuse of a specific inhibitor of chymotrypsin, chloromethyl N-tosylphenyl-alanyl ketone,68, 69 and the specificity of chymotrypsin was favoured by theaddition of a trypsin inhibitor. Some cystine residues were reductivelycleaved with Raney nickel to form alanine residues, and tryptophan residueswere stabilized by hydrogenation to form octahydro-derivatives.In general, both qualitative and quantitative methods were used by thetwo groups.When a knowledge of precise composition was required,quantitative amino-acid analyses were employed.Column chromatographywith 8M-urea as eluant was used to separate mixtures of aggregated peptides.For final purification of small peptides, electrophoresis on paper has beenemployed, and sequences of small peptides were deduced rapidly by qualita-tive techniques. Although those parts of the sequence deduced in these wayswill no doubt prove correct, detailed information on the isolation of individualpeptides and on their sequence-determination has not so far been described.The diiliculties involved in repeating these skilled operations are inevitablyincreased in comparison with the purely quantitative approach where thefull details of isolation and degradation of each peptide are published.64 J. R.Brown and B. S. Hartley, Biochem. J., 1963, 89, 69P.66 Dinh van Hoang, M. Rovery, A. Guidoni, and P. Desnuelle, Biochim. Bwphys.6 6 B. S. Hartley, Brookhaven Symp. Biol., 1962, 15, €45.6 7 1%. A. Raftery and R. D. Cole, Biochem. Bioplays. Res. Comm., 1963, 10, 467.68V. Kostka and F. H. Carpenter, J . BioZ. Chem., 1964, 239, 1799.Acta, 1963, 69, 188.G. Schoellmann and E . Shaw, Biochemistry, 1963, 2, 252516 BIOLOGICAL CHEMISTRYReliance has been placed on multiplicity of experiments, and confidencehas been drawn from the identity of results obtained by different groups.Activation of Chymotrypshogen.-Activation results from trypsincleavage at the carboxyl group of Arg-15, releasing n-chymotrypsin.Chymotryptic attack may follow at Leu-13, Tyr-146, and AspNH,-148 toyield a-chymotrypsin, with B- and C-chains remaining anchored to eachother and to the A-chain through disulphide bonds.When these chymo-tryptic cleavages precede the tryptic cleavage, inactive neochymotrypsino-gens are formed which can then give rise to a-chymotrypsin. It is interestingto note that the activity of n-chymotrypsin, and presumably the criticalconfiguration at the active centre, are almost unaffected by completeremoval of the dipeptide from positions 147 and 148. The sites involvedin the enzymic activation of chymotrypsinogen are probably on the surfaceof the protein and would therefore be expected to be accessible to chemicalreagents. Thus Ala-149 7 0 and Tyr-146 71 readily undergo chemical modifica-tion; the products retain enzymic activity.The Active Centre of Chymotrypsin.-The special reactivity of one serineresidue with di-isopropyl phosphofluoridate (DFP) 72 is well known, and thesequence of amino-acid residues around this serine has been thoroughlyinvestigated in chymotrypsin and in a number of other enzymes.73 Thesame serine residue may be acylated by N-acetyl-~tryptophan,?~ and car-bamoylation of the serine-hydroxyl group with cyanate has also beenreported ;75 in this case, carbamoylation of tyrosine-hydroxyl groups 76 mayhave occurred competitively.Diphenylcarbamoyl chloride also inhibits themolecule specifically and stoicheiometrically at the same site." The pos-sibility existed that the loss of enzymic activity associated with all thesereactions a t the serine-hydroxyl group might be due to the bulk of themodifying group, for this might present steric hindrance to the approachof substrate, but conversion of the blocked serine residue into a residue ofdehydroalanine fails to restore activity.78 Thus direct participation of theserine-hydroxyl group in the action of the enzyme seems certain.Several investigations have implicated histidine residues in a possiblecatalytic role in the mechanism of action, Direct evidence was providedby Schoellmann and Shaw 69 who reported a specific reaction betweenchloromethyl N-tosyl (phenylalanyl) ketone and a single histidine residueof chymotrypsin, resulting in inactivation; no reaction took place when theenzyme was previously incubated with DFP.A peptide containing thereactive histidine was isolated 79 and the residue has been assigned to70 V. Massey and B. S. Hartley, Biochirn. Biophys. A&, 1955, 21, 361.71 A. N. Glazer and F. Sanger, Biochem. J., 1963, 90, 92.72 A. K. Balls and E. F. Jansen, Adv. Enzymol., 1952, 18, 321; N. K. Schaffer,S. C. May, and W. H. Summerson, J. Biol. Chem., 1953, 202, 67.78 F. Sanger, Proc. Chem. Soc., 1963, 76; R. A. Oosterbaan and J. A. Cohen," Structure and Activity of Enzymes ", Academic Press, Inc., London, 1964, p. 87.74 F. J. Kezdy and M. L. Bender, J . Amr. Chem. Soc., 1964, 86, 938.?&D. C. Shaw, W. H. Stein, and S. Moore, J. Biol. Chem., 1964, $339, PC671713 D. G. Smyth, J . BiOl. Chern., in the press.77 B. F. Erlanger and W.Gohen, J . Arner. Chem. SOC., 1963, 85, 348.78D. H. Strumeyer, W. H. White, and D. E. Koshland, Proc. Nat. Acad. Sci.E. B. Ong, E. Shaw, and G. Schoellmann, J . Amer. Chem. Soc., 1964, 86, 1271.U.S.A., 1963, 50, 931SMYTH: PROTEINS AND PEPTIDES 517position 57 in the total sequence (see Fig. 3). This finding has been con-firmed19 80 and further inspection of the location of histidine residues in anumber of proteolytic enzymes has revealed a common structural featureof two histidine residues adjoining a disulphideOther modifications of chymotrypsin cause inactivation by alterationof the active conformation of the molecule. The methionine residue (192)near the active serine undergoes preferential oxidation by hydrogen peroxidewith loss of activity.81a The same methionine residue undergoes specificreaction with 2-phenoxymethyloxiran, again with total inhibition of theenzpe.*lb In a careful study by Glazer and Sanger,71 iodination of tyrosine146 was shown to occur without loss of activity, but further iodination leadsto ina~tivation.7~, S2Final elucidation of the overall structure of chymotrypsinogen maydepend on X-ray crystallographic studies but the present work does notyet permit delineation of the peptide chain within the three-dimensionalstructure .s3Glycerddehyde 3-Phosphate Dehydrogenase.-h a large protein contain-ing a number of similar polypeptide chains, a special reactivity associatedwith one amino-acid sequence can be expected to be exhibited by identicalsequences if they occur elsewhere within the same molecule. Glyceraldehyde3-phosphate dehydrogenase, isolated from rabbit muscle, appears to containfour similar polypeptide chains held together in a specific manner by non-covalent bonds.@ Within the tetramer, each chain possesses the necessaryamino-acid sequence and three-dimensional configuration required forcatalytic activity. The active enzyme contains up to 16 thiol groups permolecule but only four of these undergo reaction with the substrate p -nitrophenyl acetate or with an inhibitor iodoacetate; each of the reactivecysteines is present in a unique octadecapeptide sequence, which occurstherefore four times in the enzyme protein:Lys.Ileu.Val.Ser.AspNH,.Ala.Ser.Cys*.Thr.Thr.~pNH,.Gys.Leu.Ala.Pro.Leu.-A1a.Ly-sIdentification of a small fragment of the sequence has also been reportedfrom two other laboratories.85 Further studies have confirmed this sequenceas common to the enzyme isolated from rabbit, pig, and yeast ; the correspond-ence between areas of individual chains from the rabbit and the pig enzymehas now been extended to include 68 amino-acid residues.g6* Reactive cysteineL. B. Smillie and B. S. Hartley, J . Mol. Biol., 1964, 10, 183; D. Popisilova,B. Meloun, and F. gorrn, 1964, Abs. 1st Meeting Fed. European Biochem. SOC., A31,The Whitefriars Press Ltd., London, p. 27.( a ) H. Schachter and G. H. Dixon, J . Biol. Chem., 1964,239, 813; ( b ) J. R. Brownand B. S. Hsrtley, 1964, A h . 1st Meeting Fed. European Biochem. SOC., A29, TheWhitefriars Press Ltd., London, p.25.82 S. K. Dub, 0. A. Roholt, and D. Pressman, J . Biol. Chem., 1964, 239, 1809.83 J. Kraut, D. F. High, and L. C. Sieker, Proc. Nat. Acad. Sci. U.S.A., 1964,61, 839.84 J. I. Harris, B. J. Meriwether, and J. H. Park, Nature, 1963, 197, 154.as H. L. %gel and A. H. Gold, J . Biol. Chem., 1963, 238, 2689; L. Cunninghamand Schepman, Bkhim. Biophys. Acta, 1963, 73, 406.86 R. N. Perhsm and J. I. Harris, J. Mol. Biol., 1963, 7, 316518 B I 0 L 0 GI C 9 L CHEMISTRYThe molecular weight of the subunit (324 amino-acid residues) of therabbit enzyme is 35,000, calculated from the results of amino-acid analysison the basis of four residues of cysteine per chain; a higher value (46,000)has been proposed for the subunit of the pig enzyme 87 but this was basedon the assumption that the complete enzyme is a trimer and not a tetramer.The size of the subunit of the rabbit enzyme is greater than the largestprotein of which the total amino-acid sequence has yet been determinedand is near the limit set by currently available methods.The two cysteine residues in each '' active centre " peptide are capableof being linked through a disulphide bond, forming a ring containing fiveamino-acid residues, with total loss of activity.88 The ring is easily openedby reduction and activity is restored.It was suggested that this reversibleoxidation-reduction of the thiol groups which form a part of the activecentre may play an important role in controlling the activity of the enzymeunder physiological conditions.Alcohol Dehydrogenase Enzymes.-In mammalian alcohol dehydro-genase the amino-acid sequence in the " active centre " peptide is totallyWerent from the sequence in glyceraldehyde 3-phosphate dehydrogenase ;moreover, some differences in this region occur among the alcohol dehydro-genase enzymes isolated from different sources :(a) Val. Ala.Thr.Gly.Ileu.~s.Arg.Ser.Asp.Asp.His.V~l.Thr.Ser.Gly.LeuAmino-acid sequences in the " active centre '' peptides of alcohol dehydrogennses fi-omhowe liver (a) and yeast (b).S0It has been suggested that in the course of evolution an enzyme undergoeschanges only if these are compatible with the maintenance of structuralintegrity at an active centre.The observed differences in this region betweenthe yeast and the horse-liver enzyme involve replacement of certain amino-acid residues by structurally rela,ted residues, threonine, isoleucine, andserine in the mammalian enzyme corresponding with serine, valine, andthreonine, respectively, in the yeast enzyme; outside the heptapeptide area,the sequences appear to be unreleated.In both enzymes, however, thefundamental structural unit appears to consist of a polypeptide chain ofmolecular weight about 36,000 which binds one mole of NAD and one atomof zinc, and in which a rather similar sequence of amino-acids occurs in theregion of the active thiol group.Blocked Terminal Amino-Residues.-Seven proteins and polypeptideswith no free a-amino-group and with an acetyl group covering the terminushave been positively identified : melanocyte-stimulating hormones ;go cyto-T.Devenji, M. Sajgo, E. Horvuth, and B. Szorenyi, Biochim. Biophys. Acta88 J . I. Harris, '' Structure and Activity of Enzymes ", Academic Press, Inc.,1963, 77, 164.London, 1964, p. 97; E. J. Olson and J. H. Park, J . BWZ. Chem., 1964, 239, 2316.J. I. Harris, Nature, 1964, 203, 30.J. I. Harris, Biochem. J., 1959, 71, 451SMYTH: PROTEINS AND PEPTIDES 519chrome c ;91 some hiemoglobins (fetal F 92 and chicken 93); egg albumin;g*histones ;95 some viral proteins (tobacco mosaic 96 and turnip yellow mosaic 97) ;and ovine luteinizing hormone.98 The classical method of detection is thatof hydrazinolysis g9 to form acetylhydrazide, and a development of thismethod involves a more accurate measure of the hydrazide by formation ofits dinitrophenyl derivative.loO A highly sensitive method for determinationof the blocking group involves hydrolysis of the protein under standardconditions to release the volatile acid which is identified and measured bygas chr~matography.~* Evidence is accumulating that the acetyl groupbecomes attached to the terminal amino-group of the protein by an enzymeafter synthesis of the polypeptide has been completed on the ribosome.lOl, lo2New Frsctionation Pmcedures.-For the separation of proteins, poly-acrylamide gels have been very successfully applied in molecular-sieve discelectrophore~is.~~~ On an analytical scale, the electrophoretic patterns havebeen scanned automatically and permanent records 0btained.10~ On apreparative scale, the apparatus of Jovin, Chrambach, and Naughton 1°5is the most promising, permitting the separation of up to 50 mg.of proteinwith high resolution. For the separation of peptides, the use of organicsolvents in partition chromatography on Sephadex 106 has permitted purifica-tion of oxytocin analogues with success comparable with that obtained bycounter-current distribution.Omocin.-A critical spatial requirement in the region of the terminalamino-group has been confirmed by the finding that 1-hemi-D-cystine oxy-tocin possesses very little activity.lo7 To reduce complications related tosteric hindrance, replacement of amino-acid side chains by hydrogen hasbeen effected in the synthesis of 2-, 3-, and 4-glycine 0xytocin;~08 only the3-derivative showed detectable activity.An interesting series of analogueshas been prepared by modification of the side chain in position 2, tyrcsinebeing replaced by p-methylphenylalanine, p - ethylphenylalanine , 0- ethyl-tyrosine, leucine, or a-aminoadipic a~id.10~ Under certain specialized*l E. Margoliash, E. L. Smith, G. Kreil, and H. Tuppy, Nature, 1961, 192, 1125.a* W. A. Schroeder, J. T. Cua, G. Matsuda, and D. Fenninger, Biochirn. Biophys.Q3 K. Satake, S. Sasakawa, and T. Maruyama, Biochemistry, 1963, 53, 516.Q4 R. D. Marshall and A. Neuberger, Bwchem. J., 1961, 78, 31P.95 D. M. P. Phillips, Biochem. J . , 1963, 87, 258.Q* K. Narita, Biochim. Biophys. Acta, 1958, 28, 184.Q7 J.I. Harris and J. Hindley, J . Mol. Biol., 1961, 3, 117.Q8D. N. Ward and J. A. Coffey, Biochemistry, 1964, 3, 1575.Q s K. Narita, Biochim. Biophys. Acta, 1958, 28, 184.loo D. M. P. Phillips, Biochem. J., 1963, $6, 397.lol R. Pearlmann and K. Bloch, Proc. Nat. Acad. Sci. U.S.A., 1963, 50, 533.loa V. G. Allfrey, R. Faulkner, and A. E. Mirsky, Proc. Nut. A d . Sci. U.S.A.,1964, 51, 786.lo3 B. J. Davis and L. Ornstein, paper presented at The Society for the Study ofBlood, New York Acad. Sci., 1959, March 24th.lo4 D. A. Burns and 0. J. Pollak, J . Chromatography, 1963, 11, 559.Io5 T. Jovin, A. Chrambach, and M. Naughton, Analyt. Chena., 1964, 9, 351.losD. Yamashiro, Nature, 1964, 201, 76.lo' D. B. Hope, V. V. S. Murti, and V. du Vigneaud, J .Anzer. Chem. Soc., 1963.lo8 S. Drabarek, J . Amer. Chem. SOC., 1964, 86, 4477.lo9 A. L. Zhuge, K. Jost, E. Kasafkek, J. Rudinger, Colt. Czech. Chem. Conzm., 1961Acta, 1962, 63, 532.85, 3686.29, 2648520 BIOLOGICAL CHEMISTRYconditions of the bioassay, the normal action of oxytocin is inhibited bysome of these analogues, but weak intrinsic activity may be seen. The in-hibitory properties are graded and arise, not from the absence of a functionalhydroxyl group, but from replacement of this group by larger substituents.1 2 3cys--*-- iLeu/ S IIS\ 6 5 1 4 Cys-hpNH~-GluNHgIP;o-Leu-Glym,7 8 9FIU. 4. Oxytocin.Analogues exhibiting protracted action, leucylglycyloxytocin, glycyl-glycyloqtocin, and glycylglycyl-lysine vasopressin have been used in thesuccessful alleviation of hemorrhagic shock in experimental animaIs.l1° Aslow release of hormone from these weakly active analogues has been attri-buted to a weak glycine aminopeptidase activity in mammalian tissue.Inplace of the undefined levels of a tissue enzyme, a chemically unstableanalogue could be employed which would undergo hydrolysis at pH 7.4and 37", to generate oxytocic activity over a period of time. A derivativewith this potential is O-carbamoyldeamino-oxytocin,7~ which would releasethe highly active deamino-oxytocin under physiological conditions.It has been suggested by Schwarz et aZ.lll that the disulphide bridge ofoxytocin participates in a disulphide-exchange reaction with correspondinggroups in a protein receptor, and this interesting hypothesis has provokeddiscussion as a general basis for biological action among polypeptides.Thecomplete absence of activity in dethio-oxytocin,ll2 in which each half cystineresidue has been replaced by an alanine residue, is consistent with thehypothesis. Rudinger and Jost,ll3 however, have reported a new analogue inwhich one of the sulphur atoms is replaced by a methylene group, maintainingan intact ring; this analogue is biologically active. Using a different assay,Schwarz and Rasrnussen1l4 have confirmed the activity of Rudinger'sanalogue. The considerable stability of the sulphide linkage in this moleculeexcludes the possibility of ring opening in oxytocin with subsequent couplingof the hormone to the receptor as part of the mechanism of action.Thus,each of the potentially reactive functional groups of oxytocin, the tyrosine-J. H. Cort, J. Hammer, M. Ubrych, 2. Pisa, T. DOW, and J. Rudinger, Lancet,ll1 I. L. Xchwartz, H. Rasmussen, 36. A. Schoeseler, L. Silver, and C. T. 0. Fong,llg K. Jost, G. Debabov, H. Neavadba, and J. Rudinger, Coll. Czech. Chem. Comm.,11* J. Rudinger and K. Jost, Ezperientia, 1964, 20, 570.ll4I. L. Schwarz, H. Rasmussea, and J. Rudinger, Proc. Nat. Acud. Sci. U.S.A.,1964, ii, 840.Proc. Nat. Acad. Sci. U.S.A., 1960, 46, 1288.1964, 29, 419.1964, 52, 1044SMYTH: PROTEINS AND PEPTIDES 52 1hydroxyl the terminal amino-group,l16 and the disulphide group,l13has been eliminated in turn with the formation of derivatives Bhowing someretention of activity.Oxytocin must thus be considered as a chemieaEZyinert substance and its function as a hormone must depend on the physicalshape of the molecule. The availability of spatial models 56 may facilitateexamination of these properties.Further understanding of the mode of biological action will come frominvestigations on the structural features necessary for the binding of thehormone to its receptor, as distinct from features necessary for overallactivity. A specific inhibitor of oxytocin with no intrinsic activity, obtainedby carbamoylation of oxytocin, has been identified as NO-dicarbamoyloxy-t o ~ i n . ~ * The inhibitor may be tested for its ability to block the action of awide variety of synthetic analogues, and information can be obtained onthe binding affinity of these analogues for the receptor compared with thatof oxytocin.The O-carbamoyltyrosine group in NO-dicarbamoyloxytocinundergoes slow hydrolysis at pH 7.4 and 37 O affording N-carbamoyloxytocin,an almost inert analogue with no inhibitory properties.Some progress has been made on the isolation of proteins of the uterinecontractile mechanism.ll7 The convergence of such studies on receptorswith the studies by peptide chemists of analogues holds promise for futureunderstanding of the mode of action of oxytocin at the molecular level.Vasopressin.-Lysine vasopressin, or oxytocin, forms a 1 : 1 complex withcopper (Fig. 5) with full retention of activity.118,119 That the terminalamino-group may be one of the binding sites is supported by the inabilityH O ( 3 C H 2" IHN - CH - co - NHH2N s H6-[CH2],.CO*NH21 coIHC-NH-CO-CH - N HH27y 2I co1 CO.NH2Flu.5. Proposed structure of mpic ions-lysine vasoprestGn complex.115 P. A. Jacquenod and R. A. Boissonas, Helv. Chirn. Acta, 1959, 42, 788; M.117 D. M. Needham and J. M, Williams, Biochem. J., 1963, 89, 552.11* B. J. Campbell, F. S . Chu, and 8. Hubbard, Bi~~herni~bry, 1963, 2, 764.Bodanszky and V. du Vigneaud, J . Arner. Chrn. SOC., 1959, Sl, 6072.D. B. Hope and V. du Vigneaud, J . Biol. Chern., 1962, 237, 3146.E. Breslow, Biochim. Bbphys. Acta, 1961, 58, 606522 BIOLOGICAL CHEMISTRYof N-acetyl-lysine vasopressin or deamino-oxytocin to form a similar com-plex.ll8 Phenylalanine oxytocin, on the other hand, which lacks a tyrosine-hydroxyl group, participates in complex formation.ll9 The four ligands ofthe cupric ion appear to be attached to the terminal amino- and threepeptide or amide-bonds.A dimer of vasopressin has been isolated 12* and was noted as retainingsome biological activity in vivo.The absence of free thiol groups from theh e r is consistent with a ring of twelve amino-acids, but the proposedstructure requires confirmation. The possibility exists, also, that enzymesmay generate active monomer from inactive dimer during the bioassay invivo.Bradykinin.-A comprehensive review of synthetic analogues hasappeared.l21 The question of whether there is a requirement for a positivecharge at each end of the molecule was investigated by t'he replacement ofArg .Pr o .Pr 0.Gly .Phe . Ser .Pro .Phe . ArgBradykininboth arginine residues by lysine;122 this resulted in considerable loss ofactivity. l-Glutamic acid bradykinin 123 exhibits slight activity but brady-kinin lacking the carboxyl-terminal arginine residue is completely inactive.1246-O-Carbamoyl-~-serine bradykinin and 6-~-serine bradykinin 125 are ofinterest in that their very low activity contrasts with the high activity ofthe natural hormone, 6-~-serine bradykinin.A new and important method pioneered by Merrifield 126 for the synthesisof peptides involves attachment of the peptide-carboxyl group to a resin.Coupling reactions are performed in sequence a t the amino-terminus of theinsoluble peptide by the carbodi-imide method.The p-nitrophenyl esterrnethod,l2' however, has previously been preferred to t,he carbodi-imidemethod 128 in classical syntheses of many of the peptide hormones becauseof the reduced incidence of racemization. Bodanszky and Sheehan 129 havedescribed a technique employing different solvents which permits use of thep-nitrophenyl ester method in solid-phase peptide synthesis.Complete synthesis of the nonapeptide, bradykinin, was achieved byMerrifield in 8 days with an overall yield of 31 yo of pure hormone, andsynthesis of a precursor peptide methionyl-lysylbradykinin has also beenreported.130 The method has been applied in the synthesis of a number ofthreonine analogues ;131 of these, the 6-threonine,8-leucine octapeptide and120 A. V. Schally and R. Guilleman, J. Biol. Chem., 1964, 239, 1038.121 E. Schroder and R. Hempel, Ezperientia, 1964, 20, 529.122 E. Wunsch, H. G. Heidrich, and W. Grassmann, Chem. Ber., 1964, 97, 1818.123 E. D. Nicolaides, H. A. de Wald, and 35. K. Craft, J. Medicin. Chem., 1963,124 D. F. Elliott, G. P. Lewis, and E. W. Horton, Biochem. Biophys. Res. Comm.,126 K. A. de Wald, M. K. Croft, and E. D. Nicolaides, J. Medicin. Chem., 1963, 6, 741.126 R. B. Merrifhld, J . Amer. Chem. SOC., 1964,86,304; R. B. Merrifield, Biochemistry,12' M. Bodanszky, Nature, 1965, 175, 685.128 J. C. Sheehan and G. P. Hess, J. Amer. Chem. Soc., 1955. 77, 1067.12DM .Bodanszky and J. C. Sheehan, Chem. and Ind., 1964, 1423.130 R. B. Memifield, J. Org. Chem., 1964, 29, 3100.131 J. I\I. Stewart and D. W. Woolley, Biochemistry, 1964, 3, TOO.6, 739.1960, 3, 87.1964, 3, 1385SMYTH: PROTEINS AND PEPTIDES 523the 5 -1 eucine ,6 - t hr eonine ,8 -1eucine nonapept ide possess weak in hi bit oryproperties against bradykinin. &Leucine, O-acetylthreonine, 8-leucinebradykinin methyl ester was found to give some specific inhibition againstbradykinin at a 1:1 ratio, but complete inhibition could not be obtainedand the conditions of the isolated uterus assay were non-physiological. Thediscovery of a specific inhibitor of bradykinin with no intrinsic activity isstill awaited.The involvement of bradykinin in the mechanism of inflammation hasbeen d0~umented.l~~ The first disease state in which bradykbh has beenshown to play an important role is that of the carcinoid flush,133 and someevidence has also been presented for a role in experimental aaaphy1a~is.l~~Gastrin.-Isolation of the pure hormone from hog antrum has recentlybeen achieved.5 Its action at physiological concentrations is to stimulategastric acid secretion, but at high concentrations secretion is inhibited. Theamino-acid sequence has now been determined 6 and total synthesis hasbeen acc~mplished.~P yr . Gl y .Pro .T yr .Met. [ Glu], . Ala. Tyr . Gl y .Try.Met .Asp .PheNH,GastrinIn common with eledoisin and physalsmin is the absence of both amino-and carboxyl-terminal groups, a feature which may protect the hormonesfrom degradation by physiological enzymes. The amino-terminal pyrrol-idone residues probably arise by intramolecular cyclization from amino-terminal glutamine.A synthetic carboxyl-terminal tetrapeptide derivative, used in thesynthesis of gastrin, was found to possess considerable gastrin activity;135the amino-terminus of the molecule is less important. That the synthetic17-residue peptide exhibits the high bioactivity of the natural hormone is,therefore, not in itself proof of structural identity, in this case carefullyestablished by physical and chemical methods. In general, structuresdetermined by degradative experiments have awaited confirmation bysynthesis to yield the full bioactivity of the naturally occurring compound.WiOh the finding, however, that some analogues of oxytocin 116 exhibit thefull bioactivity of oxytocin and that fragments of ribonuclease lacking 8amino-acid residues can form an active enzyme,52 this single approachrequires support from other methods.The hormone, as isolated, was found in two active forms which differedonly in a tyrosine O-sulphate residue of gastrin I1 in the place of the tyrosineresidue of gastrin I. Tyrosine O-sulphate has previously been noted infibrinopeptides from fibrinogen 136 and can be isolated and determined fromalkaline hydrolysates.136~ 137lsa G. P. Lewis, Ann. New York Acad. Sci., 1964, 11%, Art. 3, 847.lSs J. A. Oates, K. Melmon, A. Sjoerdsma, L. Gillespie, and D. T . Mason, Lancet,18* W. E. Brockleshurst rtnd S. C. Lahiri, J . Physiol., 1962, 165, 39P.135 H. J. Tracy and R. A. Gregory, Nature, 1962, 204, 935.lS6 F. R. Jevons, Biochem. J., 1963, 89, 621.lS7 H. H. Tallan, S. T. Bellg W. H. Stein, and S. Moore, J . Biol. Chem., 1955,1964, i, 514.217, 703524 BIOLOQICAL CHEMISTRYPhysalaemin.-This new peptide hormone, isolated from amphibian skin,has been identified and total synthesis has been completed:Pyr.Ala.Asp.Pro.AspNH,.Lys.Phe.Tyr.Gly.Leu.Met.N€€2As a vasodilator and hypotensive agent, it is 3-4 times as effectiveas eledoisin and 100-700 times as effective as bradykinin.Angiotensin II.-The effect, on biological activity, of alteration of asingle residue of a peptide hormone may differ from the effect resultingfrom the same change in an analogue of the hormone. Thus, l-D-aspartyl-Asp .Arg.Val .T yr.Val .His .Pro .Pheangiotensin is 50 yo more active than the natural hormone l-1;-aspartylangio-tensin ; 1 -~-aspartyl-8-phenylalanineamide angiotensin, on the other hand,has one-tenth of the activity of the L-aspartyl isomer.138 Similarly,deamino-oxytocin is more active than oxytocin but as active as deamino-deoxy-oxytocin. The doubly altered molecule may undergo an unpredictablechange in configuration, leading to a different mode of combination with areceptor, or in wivo have an altered transport to the receptor site. In thepressor assay, both the D-iS0nm-S exhibit protracted action whereas theL-isomers have a normal duration of action.13* This evidence supports theproposal that the enzyme which inactivates angiotensin in serum is anarnino-peptida~e.~~~ High levels of natural circulating angiotensin couldbe due to low levels of angiotensinase, but in a clinical investigation on theactivity of blood angiotensinase in hypertension no difference from thenormal levels was found.140The new technique of thin-film dialysis 1*1 has been applied by Craiget al. to the study of favoured conformations of peptide hormones in aqueouss01ution.l~~ The octapeptide, angiotensin 11, appears to exist in a coiledform of low axial ratio, whereas the nonapeptide, oxytocin, is more compact,with the tripeptide tail held close to the ring. The highly active deamino-oxytocin and the almost inactive N-carbamoyloxytocin dialyse a t similarrates, which suggests that the ring of six amino-acids may be the principlerateziietermining unit. Vasopressin dialyses more slowly than oxytocin atacid pH, possibly because of a difference in conformation caused by electro-static repulsion between the positively charged arginine residue and theNH,+-group of the terminal cystine residue. The unusually low pK value(6.3) of this amino-group in oxytocin and vasopressin would render itnucleophylic at pH 7.4, and the proposed difference in favoured conformationwould not be expected to occur under physiological conditions.It has been suggested that angiotensinamide may exist as an extendedmolecule at alkaline pH because the escape rate of the peptide in ammoniasolution was reduced to one-quarter of that a t neutral pH. A strikingparallel has been reported in the biological activity of angiotensinamideJ. A. Hess and J. W. Constantine, J. Medicin. Chem. 1964, 7, 602.H. Brunner and D. Regoli, Experientia, 1962, 18, 604; P. A. Khairallah, F. M.140 P. Biron, R. Laudesman, and J. C. Hunt, Nature, 1964, 204, 1096.L. C. Cr+g and W. Konigsbrg, 3. Phys. Cizem., 1961, 65, 166.L. C. Craig, E. J. Harfenist, and A. C . Paladini, Biochemistry, 1964, 8, 754.Bumpus, I. H. Page, and R. R. Smeby, Science, 1963, 140, 672SMYTH: PROTEINS AND PEPTIDES 525when tested at neutral and at alkaline pH ~a1ues.l~~ The expansion of themolecule was postulated as resulting from removal of the charges on theterminal amino- and imidazole groups, and as a result of decreased aromaticinteraction between the phenylalanine and tyrosine residues, associated withionization of the tyrosine-hydroxyl group.It appears that a small peptide may prefer one of a number of random con-formations through which it passes in solution, but this preference may notbe related to the " preferred conformation " taken up at the receptor site.149 A. C. Paladini, A. E. Delius, and F. de Fernandez, Biochinz. Biophy8. Acta,1963, 74, 168; H. V. Huidobro and A. C. Paladini, Experientia, 1963, 19, 572

ISSN:0365-6217    

DOI:10.1039/AR9646100459

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

J. B. Headridge, T. B. Pierce, and ID. M. W. Anderson(J.B.H. : Department of Chemistry, The University, Shefield, 10; T.B.P. : AnalyticalCzbemistry Group, A.E.R.E., Hamell; and D.M.W.A. : Department of Chemistry, Univer-sity of Edinburgh, Edinburgh, 9)1. Introduction.-As in other branches of chemistry, the number of paperspublished annually on analytical chemistry continues to increase andapproximately 8000 were abstracted in Chemical Abstracts 1964.l If it isassumed that a similar number of papers was published in 1964, it is obviousthat only a small fraction of them could be mentioned in this article, andin fact, regretfully, only about 7% of them have been cited.As expected, a diminishing proportion has been devoted in recent yearsto classical analysis and this trend was continued in 1964.However, thenumber of publications appearing on wet-chemical qualitative, gravimetric,and titrimetric analysis is still considerable, and some excellent papers havebeen published, particularly in the field of titrimetric analysis. The effortapplied to instrumental analysis is increasing, as it should, especially in thehighly industrialised countries.Many of these instrumental methods, such as reaction-rate and electro-chemical methods and plasma emission spectrophotometry, require for theirfurther advancement front-line research involving analytical and physicalchemistry and electronics, and it is to be regretted that there is so littleencouragement in Britain for this type of analytical research, particularlyin the universities, where the creation of more posts in analytical chemistryis overdue.It was noticeable that an increasing number of papers in 1964 was devotedpartly or entirely to automatic methods of analysis and this trend is likelyto continue in the future.It was also encouraging to find that computersare being used more in analytical chemistry, especially in association withX-ray fluorescence and direct-reading emission spectroscopy. One strikingfeature was the very large number of publications on. gas-phase chromato-graphy, which reflects the great usefulness of this technique as a method ofseparation.Chalmers and Dick 2 have describedan interesting method of qualitative analysis based on a series of systematicsolvent extractions.Et,hylammonium N-ethyldithiocarbamate has beenproposed 3 as an alternative to hydrogen sulphide in group separation analysis,and Henry has suggested a scheme in which the reducing action of silverpowder in the presence of iodine and hydrochloric acid plays a prominentpart.Spot tests for chlorate, bromate, and iodate in admixture have been2. Qualitative Analysis.--lnorganic.Chemical Abstructs, 1964, 60 and 61.R. A. Chalmers and D. M. Dick, Analyt. Chim. Acta, 1964, 31, 620.K. K. Hart, A. G . Hill, and B. Savage, J . Roy. Inst. Chem., 1964, 88, 418.A. J. Henry, A?anZyst, 1964, 89, 242, 255528 ABALYTICAL CHEMISTRYde~ised,~ but the major advance in the identification of anions lies in theinfrared methods described for polyatornic species by C.L. Wilson and hiscolleagues.Interest in chemical microscopy-often neglected-is revived by a paperdescribing the use of violuric acid for the identification of twelve cations.The customary large number of new spot tests included reactions foruranyl ions,* mercury(1) and g ~ l d ( m ) , ~ vanadium,l* and cobalt.ll Acker-mann l2 discussed the use of phthalocyanin in inorganic analysis, andBeamish l3 reviewed the methods of separating and identifying the noblemetals.Organic. Feigl and his co-workers14 have contributed new tests fordistinguishing the isomers of nitrophenol, anisidine, and phenylenediamine.Glutaconic anhydride was proposed15 as a reagent for hydrazine and itsorganic derivatives, for aromatic amines, vinylamines, and derivatives ofindole. Sodium pent a cyanonit r osoferr at e ( ~[II) and t e franit romet hane 7have been used as reagents for thiols, thiocyanates, sulphides, and disulphides.Carbonyl groups attracted considerable attention.Taborsky l* describeda useful general test for organic acids; the formation of salts of 5-methoxy-tryptamine is stated to be easier than that of the more customary esters oramides. A new test for barbituric and thiobarbituric acid involves heatingwith pyridylpyridinium chloride.l9 Anger and Ofri reported a number ofselective tests for specific ketones 20 and aldehydes;21 the latter group wasalso the subject of other communications.22In an important investigation, Shapiro 23 identified organo-derivativesof boron hydrides and carboranes with the aid of mass spectroscopy, infra-red spectroscopy and nuclear magnetic resonance.3. Methods of Sepanltion.-DistiZlcttion.Distillation methods have beenthe subject of a, comprehensive review,24 but very few original papers wereE. Jungreis and L. Ben-Dor, TaZanta, 1964, 11, 718.IJ R. J. Magee, S. A. F. Shahine, and C. L. Wilson, Mikrochim. Ichnoana2yt. Acta,1964, 479; F. R. Haba and C. L. Wilson, Talanta, 1964, 11, 21.5. W. L. van Ligten and H. van Velthuyzen, Mikrochim. Ichnoanalyt. Acta,1964, 759.E. Jungreis and L. Ben-Dor, Analyt. Chim. Acta, 1964, 30, 405.M. Qureshi, N. A. Abraham, and K. G. Vaxshney, Analyt. Chem., 1964,36,2040;A. Alexandrov and P. V. Alexandrova, Mikrochim. Ichnoanalyt. Acta, 1964, 774.lo S.G. Tandon and S. C. Bhattacharyp, Analyt. Chem., 1964, 36, 1378.l1 M. H. Hashmi, A. A. Ayaz, and A. Rashid, Talanta, 1964, 11, 1121.1 2 G. Ackermann, Mikrochim. Ichnoandyt. Acta, 1964, 222.l3 F. E. Beamish, Milcrochim. Ichnoanalyt. Acta, 1964, 349.l4 F. Feigl, E. Jungreis, and S. Yariv, 2. analyt. Chem., 1964, 200, 38; F. Feigl1 5 V. Anger and S. Ofri, Mikrochim. Ichnoanalyt. Acta, 1964, 626, 770.Is R. Pohloudek-Fabini and K. Papke, Mikrochim. Ichnoanalyt. Acta, 1964, 876;l7 J. Kawanami, Mikrochim. Ichnoanalyt. Acta, 1964, 106.l8 R. G. Taborsky, Analyt. Chern., 1964, 36, 1663.l9V. Anger and S. Ofri, Talanta, 1963, 10, 1302.aoV. Anger and S. Ofri, 2. analyt. Chem., 1964, 206, 185.21V. Anger and S. Ofri, 2. analyt. Chem., 1964, 203, 422.z2M.H. Hashmi, A. A. Ayaz, and H. Ahmad, Andyt. Chem., 1964, 36, 2029;*sI. Shapiro,. Taknta, 1964, 11, 211.and A. Del’Acqua, 2. analyt. Chem., 1964, 204, 421.R. Pohloudek-Fabini and K. Papke, 2. analyt. Chem., 1964, 206, 28.F. Feigl and E. Libergott, {bid., p. 132.R. T. Leslie and E. C. Kuehner, A d y t . Chem., 1964, 36, 56RHEADRIDGE, PIERCE, AND ANDERSON 529published in the past year. A single-stage centrifugal molecular ~ t i l l , 2 ~ andan appmatus facilitating the separation of thermally sensitive liquids havingmolecular weights of up to 2000,26 have been described.Morrison27 has reviewed the progress made in thisfield in 1962-63. Several theoretical papers have been published: theseinclude a, simplified theory by Schweitzer 28 and applications of the regularsolution theory to solvent extra~tion.~S Ruzicka30 suggested a system ofextractive titrations in which metallochromic indicators are used, and thisappears to make possible new types of selective determination.Uranium and titanium each attracted several investigators. Theextraction of maniunr?(v~) from sulphuric acid solution was achieved withc y clohexylalkylamines and N- alkyl benz ylamines ,31 with benz o yltrifluor o-acetone,32 and with the synergic effect of tri-n-butyl phosphate on ex-traction by dL(2-ethylhexyl) hydrogen phosphate ;33 the mechanism of thissynergic effect is discussed on the basis of the results obtained.A spectro-scopic method34 for the determination of the water content of tri-n-butylphosphate has been described.Titanium was determined by extraction ofthe oxinate into chloroform 35 at pH 3-8-5-0, or at pH 7-9-9-0 if EDTAwas added. In other methods for titanium, cupferron at pH 6 in the presenceof EDTA,36 and extraction with the symmetrical dioctyl ester of methylene-diphosphonic acid into octane, were used,3' although this method failed ifuranium, molybdenum, vanadium, or iron was present,Extractants used for the platinum metals have included antipyrinederivatives,38 NN-dibenzyldithiocarbamic acid,39 and triphenylisopropyl-phosphonium ions in presence of an excess of thi~cyanate.~~ Palladium hasbeen very efficiently extracted 41 from weakly acidic solution containingiodide by a solution of triphenylstibine in cyclohexane. The liquid anion-exchanger LA-1 has been used in a two-stage extraction system whichseparated osmium from ruthenium.42Liquid-liquid extraction was also used43 in a new method, applicableto alloy steel, for the rapid extraction of tungsten(v1) with tri-n-butyl phos-phate.In another selective method 44 for tungsten, with niobium maskedSolvent extraction.25 W. L. Thomas, Analyt. Chern., 1964, 36, 1047.26 W. A. Frank and H. D. Kutsche, Analyt. Chem., 1964, 36, 2167.2 7 G. H. Morrison, Analyt. Chem., 1964, 36, 93R.28 G. K. Schweitzer, Analyt. Chirn. Acta, 1964, 30, 68.2Q T. Wakahayashi, 5. Oki, T. Omori, and N. Suzuki, J . Inorg. Nuclear Chem.,30 J. RbiiEka, Talanta, 1964, 11, 887.81 T. Sato, J . Inwg. Nuclear Chem., 1964, 26, 171, 181.32 T. Shigematsu, M.Tabushi, and M. Matsui, Bull. Chern. SOC. Japan, 1964, 37,s3 T. Sato, J. Inorg. Nuclear Chem., 1964, 26, 311.saA. V. Karyakin and A. V. Petrov, Zhur. analit. Khim., 1964, 19, 1234.36 C. L. Chakrabarti, R. J. Magee, and C. L. Wilson, Talanta, 1963, 10, 1201.$ t ~ J. A. Corbett, AnaZyt. Chirn. Acta, 1964, 30, 126.37 H. Gorican and D. Grdenic, Analyt. Chem., 1964, 36, 330.A. 'I. Busev and V. K. Akimov, Talanta, 1964, 11, 1657.89 J. T. Pyle and W. D. Jacobs, Analyt. Chern., 1964, 38, 1796.40 P. Senise and L. R. M. Pitombo, Talanta, 1964, 11, 1185.41 P. Senise rtnd F. Levi, Analyt. Chim. Acta, 1964, 30, 422.42 G. Dinstl and F. Hecht, Ni?crochim. Ichnoanalyt. Acta, 1963, 895.43 A. I(. De and M. S. Rahamm, Talanta, 1964, 11, 601.r r H . E.Affsprung and J. W. Murphy, Analyt. Chim. Actcc, 1964, 30, 501.1964, 26, 2255, 2265.1333530 ANALYTICAL CHEMISTRYby fluoride, tetraphenylarsonium chloride reacts with the tungsten-thio-cyanate complex to give an ion-pair which is extracted into chloroform.Yoshida 45 has examined the solvent-extraction behaviour of thelanthanides in perchloric acid-tri-n-butyl phosphate systems, and Moore 46suggested liquid-liquid extraction with tridecylmethylammonium thiocyanateas a new approach t o the separation of actinides from lanthanides. Tri-n-octylamine was used by Ko47 in determining tantalum in plutonium.tri-iso-octylamine ” in xyleneeffectively separated 48 0 6 pg. of zinc from 300 mg. of nickel, and is thereforeuseful for determinations of zinc in electrolytic nickel.Determination ofiron in nickel has been based49 on the complex formed between ferricthiocyanate and three molecules of tri-n-butyl phosphate. Another methodfor iron involved 50 extraction of ferric anthranilate with penfanol; copper,cobalt, nickel, cadmium, and iron(@ did not interfere. Lead and zinc canbe separated from alkaline earth metals by complex-formation 51 withdiphenylarsinic acid and extraction with chloroform.Dagnall and West 6* contributed a highly selective extraction systemfor traces of silver, and another interesting paper reportedb3 a study ofthe extraction of metal ions by monoacidic orthophosphate esters in analcoholic diluent, so that the extraction was made to follow a monomericmechanism.Thin-lnyer chrmnatography. Porous glass (200-250-mesh sieve) mixedwith plaster of Paris in the ratio 87:13 gave better separations than silicagel or alumina.64 In a continuous separation system,S6 two solvent systemswere supplied to two sides of a coated triangular plate, the mixture to beseparated being placed near the apex. Markl and Hecht 56 reported thatimpregnation with a complex-forming agent gave the thin layer a capacitygreater than can be achieved with ion-exchange paper.Few papers oninorganic separations 5‘ were published, but many interesting organicapplications were described, e.g., molecular-weight estimations 58 of proteinson thin layers of Sephadex G-100 and 6-200, and ‘‘ quenchofluorimetric ”analysis of aromatic hydrocarbon~.~9 “ Multiple runs,” Le., repeated solventTo revert to more common elements,45 H.Yoshida, J . Inorg. Nuclear Ohm., 1964, 26, 619.4 6 F. L. Moore, Analyt. Chem., 1964, 36, 2158.4 7 R. KO, Analyt. Chem., 1964, 36, 1290.48 W. L. Ott, H. R. Macmillan, and W. R. Hatch, Analyt. Chem., 1964, 36,M E. Jackwerth, 2. analyt. Chern., 1964, 286, 335.50 D. L. Dinsel and T. R. Sweet, Analyt. Chenz., 1963, 35, 2077.51 R. Pietsch and G. Nagl, 2. analyt. Chem., 1964, 203, 253.68 R. M. Dagnall and T. S. West, l’alanta, 19G4, 11, 1627.53 G. W. Mason, S. Lewey, and D. F. Peppard, J. Imorg. Xuclear Chem., 1964,5 4 J. K. G. Kramer, E. 0. Schiller, H. D. Gesser, and A. D. Robinson, Analyt.65 S . Turina, V. Marjanovic-Krajovan, and M. Obradovic, Analyt. Chem., 1964,ii6 P.Markl and F. Hecht, Mikrochim. Ichnoanulyt. Acta, 1963, 970..w K. Kawanabe, S. Talritani, M. Miyazaki, and Z . Tamura, Japan Analyst, 1964,5 8 C . J. 0. R. Morris, J . Chromatog., 1964, 16, 167.59 E. Sawicki, T. W. Stanley, and W. C. Elbert, Talanta, 1964, 11, 1433.363.26, ‘2271.Chem., 1964, 36, 2379.56, 1905.13, 376HEADRIDUE, PIERCE, AND ANDERSON 53 1passes, were used to separate some isomeric ionones,6* and a two-dimensionaltechnique was usedPaper chromatography. Brodasky 132 examined the reproducibility ofpaper and thin-layer chromatograms and found paper to be the more reliablesystem. Vink 63 devised a rate theory of partition chromatography basedon a simple physical model, and Lowery and Cassidy 64 proposed the use ofcentrifugal paper chromatography to reduce the development time required.Replacement of paper by a support made from vinyl chloride-vinyl acetatecopolymer has been recommended 65 for reversed-phase chromatogmphy andfor electrophoresis.Ganchev and Koev 66 used paper impregnated with silver salts for theanalysis of CN-, SCN-, and S2032d, and a method 6 7 of separating uranium(v1)as a carbonate complex has been described. A two-dimensional systemhas been used 68 in a separation scheme for cations. Organic applicationshave included the analysis of antibiotics,69 and studies of the relation 70between molecular structure and chromatographic behaviour. Amino-acids were analysed by a technique 7 l involving paper chromatography ofthe eluate from a column.Adsorption and partition chromatography on columns.Heftmann 72 pub-lished a very useful review. Several papers of a theoretical nature have beenpublished, e.g., those on a theory of the column fractional-precipitationtechnique 73 (application of simultaneous solvent and temperature gradientsto a column), a theory of gel filtration,7* and a comparison 75 of zone meltingand chromatography as separation methods.A column of Raney cobalt 76 gave efficient chemisorption of sulphurcompounds without causing desulphurisation. Starch columns have beenused 77 for separations of amino-acids and other acids containing nitrogen.Applegarth and Dutton’s method 78 of chromatography on DEAE-cellulosein the presence of urea holds considerable promise for useful polysaccharideseparations.Other papers of interest in the chemistry of natural productsincluded a method of salting-out chromatography for serum proteins,7Q andto separate the methyl esters of fatty acids.8o J. H. Dhont and G. J. C. Dijkman, Analyst, 1964, 89, 681.61 L. D. Bergelson, E. V. Dyatlovitslraya, and V. V. Voronkova, J . Chromatog.,62 T. F. Brodasky, AnaEyt. Chem., 1964, 36, 996.63 H. Vink, J . Chromatog., 1964, 15, 485.64 J. A. Lowery and J. E. Cassidy, J . C?hromatog., 1964, 13, 467.65 T. B. Pierce and P. F. Peck, Analyst, 1964, 89, 662.66 N. Ganchev and K. Koev, Mikrochim. Ichnoanalyt. Acta, 1964, 87, 92, 97.6 7 E. Hayek and H. D. Torre, Mikroclzim. Ichnoanalyt. Acta, 1963, 1078.68A. Schneer-Erdey and T. T6th, Talanta, 1964, 11, 907.70 L.S. Bark and R. J. T. Graham, Tahnta, 1964, 11, 539; R. J. T. Graham and71 P. Wierzchowski and D. Kruze, J . Chromatog., 1964, 14, 194.72E. Heftmann, Anulyt. Chem., 1964, 36, 14R.79 W. W. Schulz and W. C. Purdy, Analyt. Chem., 1963, 35, 2044, 2222.74 T. C. Laurent and J. Killander, J . Chromatog., 1964, 14, 317.75 W. G. Pfann, Analyt. Chem., 1964, 36, 2231.7 7 T. H. Farmer, J . Chromatog., 1964, 16, 264.78 D. A. Applegarth and G. G. S. Dutton, J. Chromatog., 1964. 15, 246.7sR. N. Sargefit and D. L. Graham, Analyt. Chim. Acta, 1964, 30, 101.1964, 15, 191.V. Betina, J . Chromatog., 1964, 15, 379.C. W. Stone, ibid., p. 947.G. M. Badger, N. Kowanko, and W. H. F. Sasse, J . Chromatog., 1964, 18, 234532 ANALYTICAL CHEMISTRYa reversed-phase technique 8o on Fluoropak 80, impregnated with iso-octane, for vitamins A and D.Reversed-phase methods were also usedfor inorganic analyses, e.g., the separationElectrophoresis. An exhaustive review of electrophoretic work publishedbetween 1961 and 1963 was undertaken by Strickland.82 A number ofvaluable advances have been made in this field; several theoretical papers 83have explored the factors influencing mobility and relative thermodynamicactivity, and the application of an analogue computer to analytical separa-tions has been described.84High-voltage electrophoresis received attention, papers describing theadvantages of agar-agar layers 85 and a novel technique for the non-destructivefractionation 86 of mixtures of powdered solids.Other innovations included the use of thin films 87 for separation of foodcolours, a modified disc method 88 for obtaining the electrophoretic patternsfrom 4-pl.samples of blood, and the buffer requirements for separation ofnucleotides and phosphoric esters ; 89 some inorganic applications,QO includingthe use of glass-fibre paper,gl were also reported.Ion exchange. General reviews,92 and reviews of liquid ion-exchangersY93have been published. There were also some interesting advances in bothorganic and inorganic problems.Centrifugal acceleration 9* was applied to separations of the rare earths,gjand paper impregnated with ion-exchange resins was used g6 in separationsof cations. Other anion-exchange methods included (a) the separation ofmicrograms of osmium from large amounts of base metals,g7 (b) the separationof titanium, zirconium, niobium, tantalum, molybdenum, and tungsten forthe analysis of alloys,98 and (c) the separation of magnesium, calcium, andstrontium.99 Organic applications worthy of mention included methods forof molybdenum in steels.8* P.S. Chen, A. R. Terepka, and N. Remsen, Analyt. Chem., 1963, 35, 2030.*l J. S. Fritz and C. E. Hedrick, Analyt. Chem., 1964, 36, 1324.8a R. D. Strickland, Analyt. Chem., 1964, 36, 80R.8a J. C. Giddings and J. R. Boyack, Analyt. Chem., 1964,36, 1229; R. H. Hackmanand M. Goldberg, ibid., p. 1220; V. JoM, J . Chromatog., 1964, 13, 451; J. Vacik andM. Jakoubkova, ibid., p. 456.a4 K. Abel and F. W. Noble, Analyt. Chem., 1964, 36, 1855.B6 K.Dose and S. Risi, 2. analyt. Chem., 1964, 205, 394.a6 G. Todd and G. A. Wild, Analyt. Chem., 1964, 36, 1025.87 W. J. Criddle, G. J. Moody, and J. D. R. Thorn=, J. Chromatog., 1964, 16,88 K. A. Narayan, S. Narayan, and F. A. Kummerow, J . Chromatog., 1964,16,8@ E . Recondo, I. R. J. Gongalves, and M. Dankert, J . Chromatog., 1964, 16,90 M. Giustiniani, G. Famglia, and R. Barbieri, J . Chromahg., 1964, 15, 207.9lG. Alberti, S. Allulli, and G. Modugno, J . Chmmatog., 1964, 15, 420.9 1 R. Kunin and I?. X. McGasvey, Analyt. Chem., 1964, 36, 142R; H. F. WaXton,93 H. Green, Tahnta, 1964, 11, 1561; E. Cerrai, Chromatog. Rev., 1964, 6, 129.B4 C. Heininger, Jr., and F. M. Lanzafame, AnaZyt. Chim. Acta, 1964 30, 148.@5 J. Alexa, Coll.Czech. Chm. Cmm., 1964, 29, 2851; J. Korkisch and I. Hazan,06 J. Sherma, Talanta, 1964, 11, 1373; M. Lederer and L. Ossieini, J . Chromatog.,97 J. C. van Loon and F. E. Beamish, AnaEyt. Chm., 1964, 86, 1771.@8 E. J. Dixon and J. B. Headridge, Analyst, 1964, 89, 185.80 J. S. Fritz, H. Wrtki, and B. B. Garralda, Analyt. Ohem., 1964, 86, 900.350.187.415.&bid., p. 51R.Talanta, 1964, 11, 1167.1964, 18, 188HEADRIDGE, PIERCE, AND ANDERSON 533the separation of amino-acidsy1Oo amino-specific ribonucleic acids,l01 andsugars. lo2A very large number of papers on this subjectcontinue to appear, and some of the important advances have been selectedfor mention. A useful review 103 and a symposium report 104 have beenpublished. Several theoretical papers dealt with the analytical potential loSof gas-solid chromatography, the use of combination and thedigital search method 107 for minimising the time taken for the separationof complex mixtures.Roesler described the sensitive characteristics of a photo-ionisationdetector,lO* and methods of measuring peak areas were investigated.lMKeller and Stewart l10 contributed an interesting paper on methods of usingmixed solvents.The use of inorganic salts as column-packing materi-als ll1 was investigated by several workers; separations appeared to begreatIy influenced by interaction between the metal ion of the absorbentand the melectrons or non-bonded electrons of the adsorbate.ll2 Othernovel packing materials included nichromc helices 113 and porous glassbeads.l14Gas chromatography of the pyrolysis products of polymers attractedconsiderable attention ;115 the technique has been used for the qualitativeidentification of more than 150 polymers.116Beroza described a method 117 for trapping small amounts of volatilefractions, and Ryhage 11* used a mass spectrometer for the identification offatty acids and C19-C30 hydrocarbons.A capillary column was used 119 for the analysis of aromatic hydro-carbons, and McEwan l 2 0 described a two-stage technique that incorporatedback-flushing .Inorganic applications included the analysis of volatile inorganic fluorides 121Gas chromatography.loo J.Hartel and A. J. G.Pleumeekers, AnaZyt. Chem., 1964,36,1021; P. B. Hamilton,1olK.B. Jacobson and S. Nishimura, J . Chromatog., 1964, 14, 46.lo2 B. Arwidi and 0. Samuelson, Analyt. Chim. Acta, 1964, 31, 462.103 R. 8. Juvet and S. D. Nogare, AmZyt. Chem., 1964, 36, 36R.104 Analyt. Chem., 1964, 36, 1410.l o 5 J. C. Giddings, Analyt. Chern., 1964, 36, 1170.lo6 G. P. Hildebrand and C. N. Reilley, Analyt. Chem., 1964, 36, 47.lo' T. B. Rooney and W. Aznavourian, Analyt. Chem., 1964, 36, 2112.lo8 J. F. Roesler, AnaZyt. Chem., 1964, 38, 1900.log R. P. W. Scott and D. W. Grant, Analyst, 1964, 89, 179.R. A. Keller and G. H. Stewart, Analyt. Chem., 1964, 36, 1186.ll1 J. A. Fane and L. R. Kallenbach, Analyt. Chem., 1964,36, 63; P. W. Solomon,1laA. G. Altenau and L. B. Rogers, AnaZyt. Chem., 1964, 36, 1726.113 J.-F. T. Kung and R.J. Romagnoli, AnaZyt. Chm., 1964, 36, 1161.114 I. HalBsz and C. HorvBth, Anulyt. Chem., 1964, 36, 2226.l15 B. C. Cox and B. Ellis, Analyt. Chem., 1964,36, 90; C. C. Luce,'E. F. Humphrey,116 B. Groten, Analyt. Chem., 1964, 36, 1206.117 M. Beroza, J . Gas Chromatog., 1864, 2, 330.118 R. Ryhage, Analyt. Chem., 1964, 86, 759.l 1 0 J. A. WaIker and D. L. Ahlberg, A d y t . Chm., 1963, 35, 2022.ItOD. J. Meswan, Awlyt. Chem., 1964, 36, 279.l * l A . G. Hamlin, G. Iveson, and T. R. Phillips, Analyt. Chem., 1963, 8S,ibid., 1963, 35, 2055.ibid., p. 476.L. V. Guild, H. H. Norrish, J. CoulI, and W. W. Castor, ibid., p. 482.2037534 ANALYTICAL CHEMISTRYand the determination 122 of aluminium, gallium, indium, and beryllium asfrifluoroacetylacetonates.“ Multicolurm.1 spectrograms,” obtained by thesimultaneous use of five parallel columns containing stationary phases ofdiffering chromatographic characteristics, were used l 2 3 for the analysis ofchlorinated pesticides, and they should be useful also for the solution ofother complex separations.Electrolytic separations. A review of this subject was published byBard 124 but very few papers were considered to make any significant advance.A simple apparatus for the quantitative analysis of a flowing solution wasdescribed,Iz5 the sensitivity at low concentrations approaching that of acontrolled potential device. Hiclding and Ingram contributed an interest-ing paper on contact glow-discharge electrolysis, in which the chemicaleffects are similar to those of a-radiolysis of water.4.Gravimetric An@sis.-Gravimetric 127 and thermogravimetric 128methods have been the subject of very comprehensive reviews. Piel l29 hasdescribed a method of “ gravimetric gas chromatography ” in which thechromatographic fractions are collected and weighed. The method will beof limited application : it gives accurate results, but comparatively largesamples are required and analyses are limited to mixtures giving clearlyseparated components.Precipitation from homogeneous solution has been applied to the deter-mination of indium as the 8-hydroxyquinaldate l30 and t o the determinationof iron(m) as the tri-(2-thiopyridine N-oxide) c0mp1ex.l~~The use of diantipyrinylpropylmethane 132 as a precipitant for osmium(Iv),and of diantipyrinylmethane for osmium plus iridium, has been proposed;although the selectivity is low, all platinum-group metals interfering, theauthors claim that their method is superior to those previously available.Dalziel and Kealey 133 report that 8-mercaptoquinoline is more sensitiveas a reagent for nickel and palladium than is its hydroxy-analogue, whilstMathur and Narang 133 propose bis( biacetyl monoxime) ethylenedi-imine[NN’-di-( 2-hydroxyimino- 1 -methylpropylidene)ethylencdiamine] and its o-phenylenedi-imine analogue.Other new gravimetric procedures include theuse of benzenetricarboxylic acids 135 for zirconium and hafnium, 1 ,Z-di-4’-morpholinylethane l36 for zinc, and N-phenylanthranilic acid l37 for thorium.Iz2 J.E. Schwarberg, R. W. Moshier, and J. H. Walsh, Talanta, 1964, 11, 1213.lZ3 R. Goulden, E. S. Goodwin, and L. Davis, Analyst, 1963, 88, 941, 951.lZ4 A. J. Bard, Analyt. Chern., 1964, 36, 70R.126 W. J. Blaedel and J. H. Strohl, Analyt. Chem., 1964, 36, 1245.la6 A. Hickling and M. D. Ingram, Trans. Faraday SOC., 1964, 60, 783.12’ W. H. McCurdy and D. H. Wilkins, Analyt. Chem., 1964, 36, 381R; W. T.128 C. B. Murphy, Analyt. Chem., 1964, 36, 34712; A. W. Coats and J. P. Redfern,E. V . Piel, Analyt. Chem., 1964, 36, 696.130 J. P. Jones, 0. E. Hileman, Jr., and L. Gordon, Tdanta, 1964, 11, 861.131 J. A. W. Dalziel and M. Thompson, Analyst, 1964, 89, 707.132 A. I. Busev and V. K. Akimov, Talanta, 1964, 11, 1657.133 J. A. W. Delziel and D. Kedey, Analyst, 1964, 89, 411.13* N.K. Mathur and C. K. Narang, Talanta, 1964, 11, 647.136 A. K. Mukherji, Analyt. Chem., 1964, 38, 1064.136 E. Asmus and J. Peters, 2. analyt. Chem., 1964, 203, 409.13’ D. Banarjea and S. V . Suryanarayana, 2. analyt. Chem., 1964, 202, 161.Smith, Jr., W. F. Wagner, and J. M. Patterson, ibid., p. 391R.Analyst, 1963, 88, 906HEADRIDBE, PIERCE, AND ANDERSON 535There were very few papers on gravimetric procedures for organic 13*species or anions, although a modified buffer system was proposed139 forthe gravimetric determination of fluorine in organic samples after sodiumperoxide fusion.Electrodeposition. Donnan and Dukes l40 contributed an interestingpaper on the use of a carrier technique for the quantitative electrodepositionof actinides, and conditions for the electrodeposition l4l of protactinium weredescribed.The conditions for quantitative deposition on graphite electrodes inanodic stripping analyses were investigated,**2 and the application of con-trolled-potential electrodeposition to neutron activation analyses wasconsidered.143Hibbs and Nation l44 discussed the use of an electrolytic hygrometer,and the conditions for the electrolytic deposition of cobalt on a, rotatingplatinum electrode were investigated.1455. Visual Titrations.-In the last year most of the progress in visualtitration has involved redox and complexometric reactions, and relativelyfew papers on acid-base and precipitation titrations have been published.The titrimetric determination of quinol has been reviewed.14*Sulphanilamide, sulphaguanidine, and sulphacetamide have been determinedin aqueous acetic acid by titration with a standard solution of N-bromo-succinimide and Methyl Red as indicator.The sulphonamides werebrominated quantitatively to the 3,5-dibromo-derivatives while the titrantwas reduced to s~ccinimide.~~~ Methyl ketones and acetaldehyde have beensatisfactorily determined in alkaline solution by titration with standardhypobromite solution and Bordeaux indicator 9 4 8CH,*COR + 3NaOBr 4 CHBr, + R*CO,Na + 2NeOHThe determination of oxide ( S O 0 p.p.m.) in uranium compounds hasbeen accomplished by reaction with sulphur monochloride passed over theheated compound. Oxide was bound as sulphur dioxide which was separatedfrom the excess of sulphur monochloride by a selective absorption-desorptionprocess involving activated charcoal.The sulphur dioxide was finallydetermined by titration with standard iodine solution.149Malachite Green has been shown to be a better indicator than starch forthe thiosulphate titration of iodine in very dilute solutions, or in solutionscontaining large amounts of electrolytes or ethanol.150 A new method forRedox.lS8 Z. Gregorowicz and J. Ciba, Milcrochim. Ichnoanalyt. Acta, 1964, 601.13* R. A. Bournique and L. H. Dahmer, Analyt. Chem., 1964, 36, 1786.140 M. Y. Donnan and E. K. Dukes, Analyt. Chem., 1964, 36, 392.141 H. Shimojima and J. Takagi, J . Inorg. Nuclear Chern., 1964, 26, 253.148 S. P. Perone and T. J. Oyster, Analyt.Chem., 1964, 36, 235; H. Specker andlQ3 H. B. Mark, Jr., and F. J. Berlandi, Analyt. Chem., 1964, 36, 2062.144 J. M. Hibbs and G. H. Nation, AnaZyst, 1964, 89, 49.146 H. Siebert, 2. analyt. Chem., 1964, 206, 20.146U. A. T. Brinkman and H. A. M. Snelders, Talanta, 1964, 11, 47.14' M. Z. Barakat and M. Shaker, Analyst, 1964, 89, 216.Ir8M. H. Hashmi and A. A. Ayaz, Analyt. Chem., 1964, 36, 384.14* 0. Baudin, J. Besson, P. L. Blum, and T. V. Danh, AnaZyt. Chim. Acta, 1964,u0 J. 0. Meditsch, Analyt. Chim. Acta, 1964, 31, 286.G. Schiewe, 2. analyt. Chem., 1964, 204, 1.30, 443536 ANALYTICAL CHEMISTRYthe precise determination of ascorbic acid in urine has been described;151the method is based on the quantitative reduction of mercuric chloride tomercurous chloride, which is separated by centrifugation and dissolved inan excess of standard iodine-potassium iodide solution; unused iodine isthen back-titrated with thiosulphate solution.Solutions containing uranium, plutonium, iron, nitrate, and many otherforeign ions have been satisfactorily analysed for uranium by a titrimetricmethod.Uranium(vr) in a concentrated phosphoric acid solution containingdphamic acid was reduced t o uranium(rv) with an excess of iron@); theunchanged iron(=) was then oxidised by nitric acid in the presence ofmolybdenum(v1) as catalyst; and finally the uranium(Iv) was titrated withdichromate s01ution.l~~ Microgram quantities of arsenite have been deter-mined with good precision by titration with standard cerium(Iv) solutionin presence of osmium tetroxide a's catalyst and tri-(4,4'-dimethyl-l-2,2'-bipyridyl)ruthenium(rr) as fluorescent indicator ; the ruthenium(=) complexhas an orange-red fluorescence, but the ruthenium(m) complex does notfluoresce .l53It has been stated that in >6~-hydrochloric acid solutions tin(=) is notappreciably oxidised by atmospheric oxygen and can, therefore, be determinedby titration with standard ferricyanide solution, 3,3'-dimethylnaphthidineor di-o-anisidine being used as indicator;15* saturating the solution withcarbon dioxide is unnecessary.Sodium dithionite has been satisfactorilydetermined in oxygen-free ammonia-ammonium chloride buffer by titrationwith ferricyanide solution in presence of bis(dimethylglyoximato)iron(n) asindicator : the dithionite is quantitatively oxidised to sulphite.155Manganese ores have been analysed for manganese by converting themanganese quantitatively into the 33- state by treating the ore withequal volumes of concentrated perchloric and phosphoric acid and thentitrating the manganese(@ with iron@) solution ; the manganese(@phosphate complex or 1 ,lo-phenanthroline can be used as indi~at0r.l~~Rhenium(vn) in 5~-hydrochloric acid has been determined by titration withstannous chloride solution and Indigo Carmine as indicator: the rheniumis reduced to the 5+ state.157 Dicyanodi-( l,lO-phenanthroline)iron(~~),which reacts reversibly with nitrous acid to give the corresponding iron(@complex and nitric oxide, is a reliable indicator in titrations of sulphamatesand azides, as well as of certain aromatic amine derivatives, with sodiumnitrite solution.158Complexmetric.A further contribution to the theory of indicatortransition in complexometric titrations has been published.l59Milligram amounts of aluminium from a wide variety of alloys havebeen determined by adding an excess of cyclohexane- 1,2-diamine-NNN'N'-lS1 L. Kum-Tatt and P. C. Leong, CZ&aic&! Chem., 1964, 10, 575.lS2 W. Davies and W. Gray, TaEanta, 1964, 11, 1203.lSaB. Kratochvil and D. A. Zatko, AncrZyt. C h . , 1964, 36, 527.16'H. Basifiska and W. Rychcik, Talanta, 1963, 10, 1299.16s W. Wawrzyczek and W. Rychcik, 2. analyt. Chem., 1964, 202, 21.lS6 K. Nagmhima, M. Codell, and S.Fbjiwara,, Japan Analyst, 1964, 13, 261.l57 Gt. Hen20 and R. Geyer, 2. d y t . Chrn., 1964, 200, 434.16* A. A. Schilt and J. W. Sutherland, AnaZyt. Chem., 1964, 36, 1805.lSQ G. Nakagawa and M. Tanaka, BUZZ. Chern. SOC. Japan, 1964, 87, 27HEADRIDGE, PIERCE, AND ANDERSON 537tetra-acetic acid (DCTA) to the aluminium solution and back-titrating itwith standard zinc solution in presence of Xylenol Orange as indicator ;Is0before the titration, niobium, tantalum, tungsten, and silicon are removedas oxides along with manganese as manganese dioxide, most other interferingelements by mercury-cathode electrolysis, and finally titanium and zirconiumby solvent extraction. Since DCTA forms, in cold solution, a complex withaluminium almost instantaneously, the addition of an excess of standardDCTA solution to a solution of aluminium and chromium(m), and the back-titration of unchanged DCTA with standard lead or zinc solution, withXylenol Orange as indicator, allows aluminium to be determined in thepresence of chromium(m) .161 Indium in cyanideindium plating solutionshas been determined by adding an excess of standard EDTA solution to asuitable aliquot part of plating solution and back-titrating the unchangedEDTA with standard magnesium solution after addition of ammonia-ammonium chloride b d e r solution and Eriochrome Black T as indicator ;leacopper(n), zinc, silver, cadmium, and gold(m) did not interfere in thetitration.Germanium(rv) has been determined by adding an excess of EDTA to thegermanium in 0*02-0~05~-hydrochloric acid, boiling the mixture for tenminutes to form the germanium-EDTA complex, and back-titrating theunused EDTA with standard zinc solution, using Chromogen Black ET-00as indicator, after making the solution alkaline with ammonia.l63 Bismuthions in solutions of pH 1-3 have been satisfactorily determined by cornplexo-metric titration with standard EDTA solution and 4-(2-N-methylana-basineazo)resorcinol as indicator ;16* there is no interference from calcium,magnesium, lead, cadmium, manganese, zinc, and aluminium, or from iron(n1)and mercury(@ if these are reduced before the titration with ascorbic andformic acid, respectively.It is reported that 3 -hydroxy - 1 - ( p-sulphonatophenyl) -3 -phenyltriazene issuperior to other metal indicators for the direct complexometric titration ofiron(=) : the sharp colour change is from bluish-black to pale lemon-~ell0w.l~~Niobium(v) in the presence of an excess of hydrogen peroxide forms astable 1 : l complex with nitrilotriacetic acid (NTA); this forms the basisfor a titrimetric method for niobium(v) which consists in adding an excessof standard NTA solution to a solution of the niobium(v)-hydrogen peroxidecomplex and back-titrating the unused acid with standard copper sulphatesolution, Methylcalcein being used as metallofluorescent indicator.166Acid-base.Eydroxyl groups in alcohol systems have been determinedby titration in ether under nitrogen with p-anilinoazobenzene as indicatorand lithium aluminium amide solution as titrant ; aldehydes, ketones, esters,amines, and alkoxyl groups do not interfere.ls7 a-Epoxy-compounds havelaOK.E. Burke and C. N. Davis, Analyt. Chem., 1964, 36, 172.lal R. Pfibil and V. VeselJi, Tahnta, 1963, 10, 1287.lU2 J. Metcalfe and C. J. Knowles, Analyst, 1964, 89, 293.la3 V. A. Nazarenko, N. V. Lebedeva, and L. I. Vinarova, Zhur. analit. Khim.,lu4 Sh. T. Talipov and K. G. Nigal, Zhur. analit. Khim., 1964, 19, 851.la6 E. Lassner, Talanta, 1963, 10, 1229.ls7D. E. Jordan, Andyt. Chim. Ada, 1964, 30, 297.1964, 19, 87.J. P. C. Jaimni, D. N. Purohit, and N. C. Sogani, Z . analyt. Chem., 1964,288, 181538 ANALYTICAL CHEMISTRYbeen determined by dissolving them in glacial acetic acid, adding an excessof cetyltrimethylammonium bromide, and titrating the solution withstandard acetous perchloric acid and Crystal Violet as indicator.l6*Precipitation.A critical review on the use of adsorpt'ion indicators inprecipitation titrations has been p~b1ished.l~~ Fluoride in inorganic materialshas been determined by steam-distillation as fluorosilicic acid followed byreaction of the acid with an excess of silver(1) oxide: the fluorosilicic acidreacts with the oxide to produce an equivalent amount of silver(1) ion, whichis determined by titration with standard thiocyanate solution, iron(m) beingused as indicator.l706. Instrumental Titrations,-In 1964, many papers involving potentio-metric titration were published, and the Reporter has had to be very selectivein his choice of material for presentation in this sub-section.In contrast,only a few publications on conductometric, thermometric, and coulometrictitration have appeared. Continuing interest is being shown in ampero-metric titration, and the steady output of papers on photometric titrationis being maintained.Potentiometric titrations. Meites and Goldman 171 have reported furthertheoretical treatment of potentiometric acid-base and precipitation-titrationcurves. The effect of input resistance on potentiometric titrations in non-aqueous solvents has been studied. when the cell resistance including theglass electrode is very large (>lo7 ohms), then the input resistance shouldalso be large (1010-1014 ohms) in order to obtain a large change in potentialat the end-point.172 A continuous automated titrator that uses a tubularplatinum electrode has been described. The measured quantity is the pump-ing rate of a reagent solution stream, when it is just equivalent to the samplestream pumped at a constant rate.lV3 An inexpensive, but sensitive,indicating unit for Karl Fischer titrations has been described: the unit in-corporates a transistorised voltmeter and is placed in parallel with the cell tomeasure the potential difference across it during the course of the titration.17*Perchloric acid in acetic acid has been used as a titrant for the determina-tion by potentiometric titration of the primary explosive, Tetracene(4-guanyl- 1 -tetrazoL5'-yltetracene], dissolved in formic-acetic acid mix-ture ;l75 and of bis(disubstituted phosphiny1)alkanes and trisubstitutedphosphine oxides dissolved in acetic anhydride.l'e Ketones have beendetermined by potentiometric titration of their semicarbazones and phenyl-,p-nitrophenyl-, and 2,4-dinitrophenyl-hydramzones dissolved in acetic an-hydride or acetic anhydride-chloroform mixture, with a, standard solutionof perchloric acid in acetic anhydride-acetic acid rni~ture.~'~16* R.Dijkstra and E. A. M. F. Dahmen, Andyt. Chim. Acta, 1964, 31, 38.l*Q R. C. Mehrotra and K. N. Tandon, Talanta, 1964, 11, 1093.l70 F. Seel, E. Steigner, and I. Burger, Angew. Chem., 1964, 76, 532.171 L. Meites and J. A. Goldman, Analyt. Chim. Acta, 1964, 30, 18; J. A. Goldmanand L. Meites, ibid., p. 28; L. Meites and J. A. Goldman, ibid., p.200.17* M. L. Cluett, Analyt. Chem., 1964, 36, 2199.173 W. J. Blaedel and R. H. Laessig, Analyt. Chenz., 1964, 36, 1617.174 A. E. Hawkins, Analyst, 1964, 89, 432.175J. S. Hetman, Chem. and Ind., 1964, 232.1713 J. R. Parker and C. V. Banks, Analyt. Chem., 1964, 36, 2191.17' D. B. Cowell and B. D. Selby, Analyst, 1963, 88, 974HEADRIDGE, PIERCE, AND ANDERSON 539Differential electrolytic potentiometric titration (constant -currentpotentiometric titration) with electrically generated hydroxyl ions has beenapplied to the determination of as little as 10-7 mole of strong or weak acidsa t concentrations of 5 x l o - 5 ~ with good accuracy and precision.l7* Con-stant-current potentiometric titration also afforded precise determinationof tertiary amines and salts of organic acids in a mixture of acetic acid andacetic anhydride when perchloric acid in acetic acid was used as tit~ant.l:~A potentiometric-titration method has been described for the determina-tion of vanadium in iron and steel containing chromium and tungsten, inwhich slight interference from chromium (found with most other methods)is eliminated.ls0 Manganese@) can be satisfactorily determined in thepresence of most ions that are not obvious reducing agents by potentiometrictitration in 12~~phosphoric acid solution with a standard solution of di-chromate ; manganese(@ is oxidised to manganese(m) ; photometric end-point detection can also be used for this titration.lSl A critical examinationhas been made of the accuracy of the potentiometric titration of cobalt,(rr)with ferricyanide in ammoniacal solution : with careful working, the meanerror was only 2 parts in 10,000.lS2CERIUM(III) has been determined with good accuracy and precision in13~-phosphoric acid by direct potentiometric titration with a standardsolution of dichromate.ls3 Potentiometric and photometric end-pointdetection have been employed for the determination of oxygen in organicsolvents by titration with a standard solution of 2,4,6-tri-t-butylphenoxy-radicals.ls4 Ascorbic acid (15-45 ,ug./ml.) has been determined by constant-current potentiometric titration with standard solutions of 2,6-dichlorophenol-indophenol or N-bromosuccinimide as titrant.ls5Magnesium and alkaline-earth ions have been determined at pH 9.0-10-5by potentiometric titrations a t a silver indicator electrode, with standardEDTA solution as titrant ; a trace of siIver(1) was added before the titration ;many other ions could be determined by a back-titration procedure.186Orthophosphate has been determined in a borate-buffered solution bypotentiometric titration at a silver electrode with standard silver nitrate astitrant ; there was no interference from nitrate, sulphate, acetate, or halide.lB7Potentiometric titration with standard silver nitrate solution involving arotating silver sulphide-silver indicator electrode has been used for the preciseand accurate determination of sulphide (0.24 mg.) in strongly alkalineammoniacal solution.lg8Elementa,ry sulphur in benzene-acetone solution has been determinedby potentiometric titration with a standard solution of potassium cyanide178 E.Bishop and G. D. Short, Analyst, 1964, 89, 587.179 V. Vajgand and T. Pastor, J . Electroanalyt. Chem., 1964, 8, 40.180 A. Claassen and L. Bastings, 2. analyt. Chem., 1964, 202, 241.lS1 G. G. Rao and P. K. Rao, Talanta, 1963, 10, 1251.lBa J. J. Lingane, Analyt. Chim. Ada, 1964, 30, 319.lE3 G. G. Rao, P. K. Rao, and S. B. Rao, Talanta, 1964, 11, 825.lS4 J. P. Paris, J. D. Gorsuch, and D. M. Hercules, Analyt. Chem., 1964, 36, 1332.lB5 C. 0. Huber and H. E. Stapelfeldt, AnaZyt. Chem., 1964, 36, 315.lS6 J. 5. Fritz and B. B. Garralda, Analyt. Chem., 1964, 36, 737.lS7 D. H. McColl and T. A. O'Donnell, Analgt. Chem., 1964, 36, 848.lB8 C.H. Liu and S. Shen, Analyt. Chem., 1964, 36, 1652.540 ANALYTICAL CHENISTRYin isopropyl alcohol. Visual end-point detection with Bromothymol Blueindicator is also possible. Elementary selenium can also be determined bydissolving it in an excess of potassium cyanide solution and back-titratingthe whole with a standard solution of sulphur. Thiocyanate and seleno-cyanate are formed in each case.189 8-Hydroxyquinoline in 2~x-perchloricacid containing bromide ion has been determined with excellent accuracyand precision by direct constant-current potentiometric titration withstandard bromate.lgO This technique has also been applied to the precisedetermination of naphthols, naphthylamines, aminonaphthols, pyrazolones,and acetoacetanilide by titration with standard solutions of diazo-com-pounds .lglGoldman and Meites lo2 have discussed the theory ofthe location of end-points on conductometric (and also amperometric andspectrophotometric) titration curves.Square-wave conductometric end-point detection for acid-base titrations has been investigated and shown topossess certain advantages when compared with sine-wave conductometricend-point detection.lg3 A simple cell for high-frequency titrations of air-sensitive substances has been described.194High-frequency titration with phosphates as titrants has been appliedto the determination of thorium and zirconium.lQ5 Fluorine in fluoridesand fluoro-complexes has been determined by precipitation as thoriumfluoride by the addition of an excess of thorium nitrate in acid solution, anda back-titration of unchanged thorium ion with mdium fluoride solutioninvolving conductometric end-point detection : $here is a rapid decrease inhydrogen-ion concentration after the equivalence point.lg6 Microgram andmilligram amounts of single alkali-metal halides can be determined withgood accuracy and precision by high-frequency titration in methanol witha standard solution of silver nitrate in methanol. Mixtures of alkali-metal.halides can also be analysed by this procedure, but then the results are lessaccurate.lD7Arnperometric.A review of amperometric titration of organic compoundshas been pubIiished.lg8 Tertiary amines and salts of organic acids have beendetermined in acetic acid-acetic anhydride mixtures with good precisionby amperometric titration (dead-stop) with a standard solution of perchloricacid in acetic acid; pairs of antimony or quinhydrone electrodes wereernployed.l99 Low concentrations of nitrite in 0.05~-stdphuric acid have beendetermined with a precision (relative standard deviation) of 1 yo by ampero-metric titration at a rotating plakinum microanode with standard sulpharnic189 L.Erdley, 0. Gimesi, and G. RQdy, Talanta, 1964, 11, 461.190 C. 0. Huber, J. B. Doe, and H. E. Stapelfeldt, Analyt. Chim. Acta, 1964, 31,191 W. Biichler, Helv. Chim. Acta, 1964, 47, 639.192 J. A. Goldman and L. Meites, AnaZyt. Chim. Ada, 1964, 30, 280.193 M. D. Wijnen, A. B. Ijzermans, and J. H. Schmieman, Rec. Trav. china., 1964,1 9 4 R.E. Cuthrell and J. J. Lagowski, Analyt. Ckem., 1964, 36, 2382.A. N. Kumaz and R. P. Singh, Indian J . Chem., 1968, 1, 814.1 9 6 E. Allenstein and F.-W. Kampmann, 2. analyt. Chem., 1964, 208, 43.197 P. Grey and G. C. B. Cave, Can&. J . Chem., 1964, 42, 770, 980.l 9 8 A. Berka, J. Doleial, and J. Zjrka, Chemist-Analyst, 1964, 53, 122.199V. Vajgand and T. Pastor, J . Electroanalyt. Chem., 1964, 8, 49.Conductometric.452.83, 21HEADRIDGE, PIERCE, AND ANDERSON 541acid solution.200 Amperometric end-point detection by means of a saturatedcalomel reference electrode and a mercury indicator electrode has beenemployed for the determination of mixtures of calcium and magnesium ions;the titrants were standard solutions of EGTA [ethyleneglycol bis-(paminoethyl ether)-NNN"'-tetra-acetate] and EDTA for calcium andmagnesium, respectively; 0.01 pg./ml.of magnesium can be determined inthe presence of 0.1 mg./ml. of calcium and vice versa, and the accuracy andprecision of the method are good.201 This method has also been appliedto the determination of calcium and magnesium in waters, cements, andsoils.202 Calcium and magnesium in waters have also been determined byamperometric titration in which a platinum electrode and a silver amalgamelectrode are used, with EDTA as titrant.203 When amperometric end-pointdetection was used, potassium tetracyano-(1,lO-phenanthroline)ferrate(n)was superior to hexacyanoferrate(n) as a reagent for the titrimetric deter-mination of zinc204 Finally, cyanate ion in aqueous methanol solutions,0 .1 ~ with respect to potassium nitrate and at <5", has been determined byamperometric titration with standard silver nitrate solution a t a rotatingplatinum electrode.2o5The whole field of photometric titrations has been criticallyreviewed by Underwood.206 Submicrogram amounts of cobalt@) inammoniacal solution have been determined by ferricyanide titration withphotometric end-point Primary aliphatic amides have beensatisfactorily determined by spectrophotometric titration in aqueous bromidesolution at pH 10 with a standard solution of calcium hypochlorite as titrant ;amide reacts quantitatively with the hypobromite thus produced, to formthe N-bromo-amide ; the end-point is determined from the ultravioletabsorbance of the excess of hypobromite.20*Kotrly 209 has obtained theoretical equations to predict the shapes ofphotometric titration curves for metal ions titrated with a complexan, whena metallochromic indicator is used which forms a step-wise system of com-plexes.Traces of lead (2-20 pg. per 10 ml.) have been determined withreasonable precision by spectrophotometric titration with standard 0-001~-EDTA solution and dithizone as indicator.210 Cadmium and zinc in solutionhave been determined by consecutive photometric titration with standardEGTA solution in the presence of murexide 211 and zincon 212 as indicator.Turbidimetric (precipitation) and nephelometric titrations have beenconsidered from both the practical and the theoretical standpoint.ThePhotometric.2oo J. T. Stock and R. G. Bjork, Talanta, 1964, 11, 315.201D. Monnier and A. Roukche, Helv. Chim. Ada, 1964, 47, 103.202 A. Roubche and D. Monnier, Analyt. Chim. Acta, 1964, 31, 426.SO3 D. S. Rao, C. S. Sudheendranath, S. K. Rao, M. B. Rao, and C. P. Anantakrishnan,204 A. A. Schilt and A. V. Nowak, Analyt. Chem., 1964, 36, 845.205 S. Ikeda and G. Nishida, Japan Analyst, 1964, 13, 433.SO6 A. L. Underwood, Adv. Analyt. Chem. Instrumen., 1964, 3, 31.207 H. Poppe and G. D. Boef, Taktnta, 1963, 10, 1297.2 0 8 W. R. Post and C. A. Reynolds, Analyt. Chem., 1964, 36, 781.2oe S. Kotrlf, Analyt. Chim. Acta, 1963, 29, 552.210 S. Kotrlf, Mikrochim. Ichnoanalyt. Acta, 1964, 407.211 H. Flaschka and F. B. Carley, Talanta, 1964, 11, 423.Analyst, 1964, 89, 608.H.Flaschka, and J. Butcher, Mikrochim. Ichnoanalyt. Acta, 1964, 401542 ANALYTICAL CHEMISTRYprecision and accuracy of these titrations are only moderate.213 Blakeleyand Ryan 214 have also carried out a photometric investigation of precipita-tion titrations ; they state that quantitative analysis in the concentrationrange 10-2-10-4~ is possible with a precision of about 1%. The rapiddetermination of calcium in limestone by photometric precipitation titrationwith standard sodiuni oxalate solution has been described. Agreement withthe values of certified samples is better than 1%.2lS Phenols and un-saturated compounds in non-aqueous solvents have been determined withgood precision and accuracy by spectroplzotometric titration with a standardsolution of pyridinium tribromide.Zl6Copper@) has been determined with reasonable accuracyand precision by adding an excess of iodide ions to the copper@) solutionand titrating the resulting iodine with standard thiosulphate solution inan automatic thermometric t i t r a t ~ r .~ ~ ' Many amines and organic acidshave been determined in acetonitrile as solvent by automatic thermometrictitration. Acids are titrated with a standard solution of diphenylguanidine,bases with hydrogen bromide solution.218 Weak organic bases in glacialascetic acid have been determined by automatic differential thermometrictitration, with a standard solution of perchloric acid in acetic acid as titrant;under strictly anhydrous conditions even the very weak bases, diphenylamine,urea, acetamide, and acetanilide are readily titrated.219 Butyl-lithium inhydrocarbon solution has been determined with good accuracy and precisionby thermometric titration with a standard hydrocarbon solution ofbutan- I-01.220Coulometric.Boron in steel (0-0002-0-01 yo) has been accuratelydetermined by converting the boron into boric acid pyrohydrolytically andtitrating the boric acid in the presence of mannitol with electrically generatedhydroxide ions.221 Weak acids in propan-2-01 and propan-2-ol-ketone sol-vents have been satisfactorily determined by titration with electricallygenerated isopropoxide ion. Visual end-point detection with Thymol Blueas indicator was suitable.222 Ammonia has been determined by directamperometric titration with electrically generated hyp~bromite.~~~ Coulo-metric titration with electrically generated iodine has been applied to thedetermination of total arsenic and arsenic(111),224 and total antimony andantimony(m), in glasses.2251-50 pg.of sulphur as hydrogen sulphide in IO-ml. samples have beenaccurately determined in an automatic coulometric titrator through oxidationThermometric.213 E. J. Meehan and G. Chiu, Alzalyt. Chem., 1964, 36, 536.214 St. J. H. Blakeley and D. E. Ryan, Analyt. Chim. Acta, 1964, 30, 346.215 St. J. H. Blakeley and D. E. Ryan, Analyst, 1964, 89, 721.216 T . Williams, J. Krudener, and J. McFarland, Andyt. Chirn. Acta, 1964, 30, 155.2 1 7 E. J. Billingham, Jr., and A.H. Reed, Andyt. Chem., 1964, 36, 1149.218 E. J. Formaii and D. N. Hume, Talanta, 1964, 11, 129.219 H. J. Keily and D. N. Hume, Analyt. Chem., 1964, 36, 543.220 W. L. Everson, Analyt. Chem., 1964, 36, 854.221 T. Yoshimori, T. Miwa, and T. Takeuch, Talanta, 1964, 11, 993.222 G. Johansson, Talanta, 1964, 11, 789.223 A. F. Krivi, G. R. Supp, and E. S. Gazda, Analyt. Chem., 1963, 35, 2216;G . D. Christian, E. C. Knoblock, and W. C. Purdy, ibid., p. 2217.224 W. M. Wise and J. P. Williams, Analyt. Chem., 1964, 36, 19.*25 W. M. Wise and J. P. Williams, Analyt. Chem., 1964, 36, 1863EEADRIDGE, PIERCE, AND ANDERSON 543with iodine. The method is suitable for the determination of sulphur inhydrocarbons after hydrogenation.226 Differential electrolytic potentio-metric titration (constant-current potentiometric titration) with an electric-ally generated titrant of silver ions has been applied t,o the determinationof nanogram quantities of halides.mole of chloride or bromide canbe satisfactorily determined.227Schoniger 228 has reviewedthe progress achieved overthe past decade. The recent trends towards morerapid 229 and so-called '' automatic " analysers 230 have received comment,and Russian workers 231 have described the simultaneous microdetermhationof carbon, hydrogen, and sulphur.Modifications to methods for determining ca'rbon and hydrogen stillcontinued to appear.232-234 The more novel approaches included (a) the con-version of water into an equivalent amount of carbon dioxide, determined 235by non-aqueous titration, ( b ) a precise manometric method 236 involving aphotoelectric level indicator, ( c ) conductonietric determination of carbondioxide and coulometric determination of and ( d ) diffusion ofhydrogen through the walls of a silica pyrolysis b ~ l b .~ ~ 8 Submicro-methodswere also des~ribed.~~S~ 240Automation has been extended 241 to oxygen determinations, and Fraser 242described a method based on conversion into carbon monoxide in a bombcontaining a reducing agent. The use of a Hersch cell may prove to be ofi~terest.2~3 Anders and Briden 244 described a rapid, non-destructive neutronactivation method; 100 p.p.ni. of oxygen can be determined with a relativeerror of &2 %, but fluorine and fissionable materials interfere.Williams 245 proposed an improved Nessler-type reagent for determiningnit,rogen in Kjelda'hl digests; rapid and automatic 246 techniques have alsobeen described.An ultramicro-method 247 for 5-20-pug samples dependson the conversion of nitrogen into ammonia on pyrolysis in hydrogen a t> 1000".7. Q-santitative Organic Analysis.-EZernentaZ.226 31. PEibyl and Z. Slov&k, Mikrochim. IcJmoanalyt. Acta, 1963, 1119.2 2 7 E. Bishop and R. G. Dhaneshwar, Analyt. Chein., 1964, 36, 726.228 W. Schoniger, 2. analyt. Chem., 1964, 205, 13.229 J. F. Arens, 2. analyt. Cihern., 1964, 205, 1.230 H. Weitkamp, R. Msyntz, and F. Korte, 2. anaZyt. Chenz., 1964, 205, 81.231 A. A. Abramyan and A. A. Kocharyan, Izvest. Akad. Nauk Armyan. S.S.R.232 W.J. Kirsten, Mikrochim. Ichnoanalyt. Acta, 1964, 487,233 H. J. Francis, Jr., and E. J. Minnick, Microchem. J., 1964, 8, 245.234 G. Kainz and F. Scheidl, Milcrochim. Ichnoanulyt. Acta, 1964, 641.235 L. Horn and Icil. H. Kraus, 2. analyt. Chem., 1864, 205, 50.236H. C. E. van Leuven and P. Gouvernour, Analyt. Chim. Acta, 1964, 30, 328.237 F. Selger, 2. analyt. Chenz., 1964, 205, 66.238 E. Ma19 and J. Krsek, Mikrochim. Ichnoamdyt. Acta, 1964, 778.239 W. Pfab and W. Merz, 2. analyt. Chem., 1964, 200, 385.240 K.-H. Ballschrniter and G. Tolg, 2. analyt. Chem., 1964, 203, 20.241 3%. Ebeling and D. Marcinkus, Microchenb. J., 1964, 8, 213.242 J. W. Fraser, Mikrochint. lclznonnalyt. Acta, 1964, 679.p 4 3 T. R. Phillips, E. C. Johnson, and 13.Woodward, Analyt. Chent., 1964, 36, 450.244 0. U. Anders and D. W. Briden, Analyt. Chem., 1964, 36, 287.2 4 5 P. C. Williams, Analyst, 1964, 89, 276.246 K. A. Potrefke, M. Kroll, and L. Blom, Analyt. Chim. Acta, 1964, 31, 128; 0.Hsteman, L. L. M. Willemsen, J. B. G. Wijenberg, and P. J. Stornebrink, ibid., p. 139.247 G. Tolg, 2. analyt. Chem., 1964, 205, 40.khim. Nauk, 1964, 17, 301544 ANALYTICAL CHEMISTRYAs a preliminary to the determination of metallic elements in organicmaterials, G. F. Smith 248 now proposes digestion with a mixture of nitricand hydrochloric acid. Saliman 249 described a new digestion procedure,based on hydriodic acid, for the microdetermination of phosphorus withMolybdenum Blue. Methods for sulphur use the chloroadate250 andturbidimetric barium 251 procedures.The oxygen flask was used in methodsfor mercury 252 and and specific submicro-methods for chlorine 254and bromine 255 have been described. More novel determinations of fluorinehave been made by nuclear magnetic resonance 256 and by fast-neutronat present the latter is faster but less accurate than somechemical methods.Funetiona2 Groups. Veibel 258 has discussed current methods, andMitchell 259 has surveyed non-acidimetric titrimetric procedures in functional-group analysis. Fluorosulphuric acid 260 and perchloric acid in aceticanhydride 261 have been proposed as titrants for organic bases, and pyridiniumtribromide is recommended 262 as a titrant for phenols.A most interesting advance is the method of “syringe reactions ”proposed by Hoff and Feit.263 Reactions are carried out in a gas-chromato-graph injection syringe ; great sensitivity is possible, and many applicationsalready exist.Ma and his colleagues 264 have used gas-liquid chromatographyin the microdetermination of carboxyl groups.Also of interest is the application of nuclear magnetic resonance to (a) thedetermination of active hydrogen 2135 after exchange with deuterium oxide,and (b) the determination 266 of primary, secondary, and tertiary functionalgroups in aliphatic monocarboxylic acids and monohydric alcohols.Considerable attention has been given to hydroxyl determinations, con-ventional methods based on direct titration with lithium aluminium arnide,z67and on esterification with 3-nitrophthalic anhydride 268 or p-nitrobenzoylchloride,269 being proposed.Infrared methods have been prominent formonohydric alcohols, the procedures involving the use of deterrninant~,~‘~248 (3. F. Smith, Talanta, 1964, 11, 633.249 P. M. Saliman, Analyt. Chem., 1964, 36, 112.2 5 O P . Stoffyn and W. Keane, Analyt. Chem., 1964, 36, 397.z 5 l M. L. Garrido, Analyst, 1964, 89, 61.2 5 2 P . Gouverneur and W. Hoedeman, Analyt. Chim. Acta, 1964, 30, 519.253 J. Petranek and 0. Ryba, Coll. Czech. Chem. Comm., 1964, 29, 2847.254 G. Schwab and G. Tolg, 2. analyt. Chem., 1964, 205, 29.255 T. R. F. W. Fennell and J. R. Webb, 2. analyt. Chern., 1964, 205, 90.258 P. J. Paulsen and W. D. Cooke, Analyt. Chem., 1964, 36, 1713.z5’ R. Blackburn, Analyt.Chem., 1964, 36, 669.z58 S. Veibel, 2. analyt. Chem., 1964, 205, 94.259 J. Mitchell, Jr., Analyt. Chem., 1964, 36, 2050.260 R. C. Paul and S. S. Pahil, Analyt. Chim. Acta, 1964, 30, 466.g61 D. B. Cowell and B. D. Selby, Analyst, 1963, 88, 974.262 T. Williams, J. Krudener, and J. MoFarland, Analyt. Chim. Acta, 1964, 30, 155.s6s J. E. Hoff and E. D. Feit, Analyt. Chem., 1964, 36, 1002.264 T. S. Ma, C. T. Shang, and E. Msnche, Mikrochim. lchnoanalyt. Acta, 1964, 571.Z 6 5 P. J. Paulsen and W. D. Cooke, Analyt. Chem., 1964, 36, 1721.266 N. van Meurs, 2. analyt. Chem., 1964, 205, 194; A. Mathias, Analgt. Chim. A&,267 D. E. Jordan, Analyt. Chim. Acta, 1964, 30, 297.268 J. A. Floria, I. W. Dobratz, and J. H. McClure, Anaclyt. Chem., 1964, 36, 2053.269 M.W. Scoggins, Analyt. Chem., 1964, 36, 1152.270 H. Specht, 2. analyt. Chern., 1964, 199, 201.1964, 31, 598HEADRIDGE, PIERCE, AND ANDERSON 545differential reaction rates 271 with phenyl isocyanate, and conversion into thecorresponding iodides.2'2 Infrared spectroscopy has also been widely usedfor determining hydroxyl groups in polymers, e.g. oxidised polyethylene 273(after acetylation), phenolic resins 274 (differential method after titrationwith sodium methoxide), and epoxy resins 275 (in pyridhe solution).The behaviourof propoxyl and butoxyl groups in the Zeisel reaction has been studied 277by vapour-phase infrared spectroscopy, and a modified Zeisel reaction,involving extraction of the iodides into benzene followed by non-aqueoustitration, is described 27g for higher alkoxyl groups (C4-C26).8.Spectroscopic Analysis.-X- Ray fluorescence spectroscopy and relatedtechniques. Powder samples of very variable composition containing widelydiffering amounts of zinc have been analysed for zinc by an X-ray fluorescencemethod, which consists of binding together the powder in paraffi wax toobtain a film of known thickness and using the fluorescent intensity fromthe film alone, from a zinc disc, and from the zinc disc covered with thisfilm, to correct for absorption effects and to simplify corrections for enhance-ment due to other elements in the powder sample. The method, whichinvolves certain simple mathematical manipulations, enables the zinc to bedetermined with an accuracy of within &5%.The method can be appliedto the quantitative determination of many other elements.279 Continualcorrection and recalibration are unnecessary in this method.Luke 280 has determined as little as 0.01 pg. of many metals by isolatingthe metals, present as cations or anions in 1 ml. of solution, by absorption ontiny discs of cation- or anion-exchange resin sheet. The metals on thesesheets are then determined by X-ray fluorescence analysis on a curvedcrystal X-ray milliprobe.A series of rocks and refractories of diverse chemical composition hasbeen analysed for magnesium, aluminium, silicon, phosphorus, potassium,calcium, titanium, manganese, iron, and strontium by using vacuum X-rayfluorescence spectroscopy. Matrix effects were practically eliminated byusing a borax dilution method when the concentrations exceeded 2% ofoxide in the rock.The analyses were much quicker and more accurate formost elements than routine gravimetric and emission spectrographic analysesperformed by the average analyst.Z81X-Ray fluorescence spectroscopy has also been applied t o the determina-tion of zirconium and molybdenum in uranium-molybdenum-zirconiumcarbide, with a precision (relative standard deviation) of 1-2 yo ;282 of ironAlkoxyl determinations continue to receive attenti0n.27~271 F. Willeboordse and F. E. Critchfield, Analyt. Chm., 1964, 36, 2270.2 i 2 D. 35. W. Anderson and S. S. H. Zaidi, Analyt. Chim. Acta, 1964, 30, 303.273 D. E. Kramm, J. N. Lomonte, end J. D.Moyer, Analyt. Chem., 1964, 36, 2170.274 N. Yoshimi, M. Yamao, and S. Tanaka, Talanta, 1964, 11, 901.276 M. R. Adaas, Analyt. Chem., 1964, 36, 1688.276 A. Pietrogrande, Mikrochim. Ichnoanalyt. Acta, 1964, S91.277 D. M. W. Anderson and S. S. H. Zaidi, Talanta, 1963, 10, 1235.278 X. Ehrlich-Rogozinski and A. Patchornik, Analyt. Chem., 1964, 36, 840.279 K. G. Carr-Brion, Analyst, 1964, 89, 346.280 C. L. Luke, Analyt. Chem., 1964, 36, 318.a81 P. R. Hooper, Analyt. Chem., 1964, 86, 1271.282 E. A. Hakkila, R. G. Hurley, and G. R. Waterbury, Analyt. Chem., 1964, 36,2094546 ANALYTICAL CHEMISTRYin iron ores, with a precision of 2 % ;283 of lead and zinc automatically in thetailings of an ore-dressing plant;284 of traces of nickel (0.2-10 p.p.m.) incatalytic cracking feedstock oil, with a precision of 0.1 p.p.m.;285 of platinum,gold, and iridium in matte solutions from mines, with a precision of <1 yoand 1-3 % for platinum, and for gold and iridium, respectively;286 of seleniumin tellurium where the precision of the method was 6, 3, and 1% for theconcentration levels of 0.05, 0.5, and 2.5% of selenium, respectively;28' andof low concentrations of cobalt, zinc, and iron in organic matrices.288 Inthe last case the accuracy and precision were good and limits of detectionwere 10 p.p.m. for cobalt, 5 p.p.m. for zinc, and 5 p.p.m. for iron. AutomaticX-ray methods in which both X-ray emission and scatter are used havebeen described for the determination of elements in organic materials,particularly petroleum and petrochemicals.2*DThe " Bremsstrahlung '' radiation (3-12 k.e.v.) from tritium absorbedin zirconium has been used to excite the characteristic fluorescent X-rays ofelements of atomic numbers 16-35.For quantitative determinations themethod has onlymoderate precision, but the apparatus can be containedin a volume of less than 1 c~.ft.~90An electron probe analysis has been used with a barium stearate soap-film crystal (d spacing -50 8) to detect carbon in alloys.291 Ziebold andOgilvie 292 have presented an empirical method which, they claim, providesa more rapid conversion of X-ray data obtained with an electron microprobeto chemical composition than any previous procedure. It has been statedthat elements from lithium to magnesium can be determined by an electronmicroprobe analyser incorporating an X-ray grating and windowless electron-multiplier detect0r.2~3A simplified routine method for X-ray absorption-edge spectrometricanalysis has been described for use on standard flat crystal X-ray spectro-meters with only minor modifications.No standard or calibration isrequired and matrix effects are usually absent. The precision of the methodis good and the accuracy reasonable, the relative error averaging Atheoretical approach to the problems of obtaining optimum conditions forchemical analysis by X-ray absorption-edge spectrometry has beenreported . 29X-Ray diffraction methods have been described for the quantitativeZ s 3 H. Goth, K. Hirokawa, and F. Maeda, Japan Analyst, 1964, 13, 402.884 G.J. Sundkvist, F. 0. Lundgren, and L. J. Lidstrom, Analyt. Chem., 1964.285 E. L. Gunn, Analyt. Chem., 1964, 36, 2086.286 A, Strasheim and F. T. Wybenga, Appl. Spectroscopy, 1964, 18, 16.287 T. Mima and K. Tsutsumi, Japan Analyst, 2964, 13, 768.288 S. A. Bartkiemicz and E. A. Hammatt, Analyt. Chem., 1964, 36, 833.289 C. TN. Dwiggins, Jr., Analyt. Chem., 1964, 36, 1577.2 9 0 J. 0. Karttunen, H. B. Evans, D. J. Henderson, P. J. Markovich, and R. L.29l J. Merritt, C. E. Muller, W. M. Sawyer, and A. Tefler, Analyt. Chem., 1963,292 T. 0. ZieboId and R. E. Ogilvie, Analyt. Chern., 1964, 30, 322.203 A. Franks, Nature, 1964, 201, 913.294 E. P. Berth, R. J. Longobucco, and R. J. Carver, Analyt. Chem., 1964, 36,Zs5 C.G. Dodd and D. J. Kaup, Analgf. Chem., 1964, 36, 2325.36, 2091.Niemann, Analyt. Chem., 1964, 38, 1277.35, 2209.641HEADRIDGE,determination of minerals indetermination of the amountcatalysts comprising -0.5 yoalumina.297A preliminary account ofPIERCE, AND ANDERSON 547kaolin-bearing r0cks,~96 and for the directand crystallite size of metallic platinum inof total platinum supported on activatedthe application of electron spectroscopy tochemical analysis has been published. This technique consists of irradiatinga sample with monochromatic X-rays and recording the photoelectronspectrum. Both qualitative and quantitative information can be obtainedfrom such a spectrum. The method is of particular interest for fluorine andelements of lower atomic weight.a98The performance of pyrolytic graphite spectro-graphic electrodes has been assessed.299 A Fortran computer programmehas been developed, which calculates and reports the results for the common-matrix method of emission spectrographic analysis.300In order to suppress CN emission, which seriously interferes with thespectrographic determination of strontium and barium, Wilson and Chester 301have constructed a fully enclosed d.c.arc chamber incorporating a modifiedSmallwood gas-jet operated with carbon dioxide or oxygen. With thisapparatus and oxygen, parts per million of strontium and barium havebeen determined with precisions of 2.5% and 11-9%, respectively. Inter-ference from the SiO band on the spectrographic determination of 0-100p.p.m.of boron in silicate rocks, when the boron 2496.8 and 2497.7 A linesare used, has been eliminated by adding to the rock sample an equal amountof magnesium oxide containing 0.1 % of stannic oxide and arcing the mixtureas anode in a nitrogen atmosphere in a graphite cup.302 After a detailedinvestigation, it has been shown that the most useful lines in the region1250-2000 A for the determination of carbon, arsenic, and tin in iron andsteel are carbon 1657.0 and 1930.9, arsenic 1806.2 and 1972.6, and tin1811.3 A.3Q3Direct-reading spectrographic procedures have been described for thedetermination of calcium, magnesium, copper, and zinc in red blood cells, witha precision of -10 o/o ;304 and of nanograms of nickel, copper, vanadium, andiron in catalytic cracking feed stocks with good accuracy and a precisionbetter than 10y0.305Emission spectrography has also been applied to the determination ofhafnium in zirconium oxide with a precision of 1.0-1*3% ;306 of5-500 p.p.m.of strontium and 100--1500 p.p.m.of rubidium in minerals;307 of americiumEmission spectroscopy.2Q6 E. Niskanen, Analyt. Chem., 1964, 38, 1268.297 R. A. Van Nordstrand, A. J. Lincoln, and A. Carnevale, Analyt. Chem., 1964,238 C. Nordling, S. Hagstrom, and K. Siegbahn, 2. Phys., 1964, 178, 433.239 J. B. Mooney, C. E. Schoder, and L. J. Garbini, Aizalyt. Chem., 1964, 36, 703.300 D. D. Tunnicliff and J. R. Weaver, Analyt. Chem., 1964, 36, 2318.F. Wilson and R. Chester, Analyt. Cltim. Acta, 1964, 31, 493.302 J.R. Sewell, Appl. Spectroscopy, 1963, 17, 166.30s H. Got6, S. Ikeda, K. Hirokawa, H. Seno, and A. Raya, Japan Analyst, 1962,304 L. S. Valberg, J. M. Holt, and J. Szivek, Ancrlyt. Chem., 1964, 36, 790.305 D. Hoggan, C. E. Marquart, and W. R. Battles, Analyt. Chem., 1964, 36, 1955.306 W. J. Naudh and P. B. Zeeman, EJpectrochim. Acta, 1963, 19, 2075,307 A. A. Mills, Canad. J . Chem., 1964, 42, 73.36, S19.13, 661548 AN AL Y TICAL C H E MIS TRYin plutonium after separation from plutonium by anion-exchange in 8M-nitricacid, with a precision of 6% and a lower limit of detection of 0.03 ,ug.;308 ofboron in plutonium and uranium nitrate solutions, with a precision of 12%and a lower limit of detection of 0.001 pg.;309 and of zirconium, hafnium,thorium, and titanium in silicate and niobium-tantalum ores, with anaccuracy of & 10 y0.310Quantitative analysis of water-deuterium oxide mixtures containing0.01-1*0 mole yo of deuterium oxide has been achieved by using the lineintensities of the 0D-Ql(5) and the OH-R2(16) lines of the 0-0 vibrationtransition in the OH or OD electronic band spectrum (A2Z+ - X2n).311Emmott and Wilson 312 have determined 0-2% of nitrogen in heliumwith a precision of 3% by using their Tesla-luminescence spectra.A suit-able calibration curve is obtained by plotting the ratio of the intensity ofthe nitrogen line at 358 mp (or 337 mp) relative to that of the helium lineat 502 mp, against nitrogen content; the oxygen content must be less than0.04 % .A radiofrequency plasma emission spectrometer has been described andthe detection limits of 21 elements in aqueous solution are reported.Theselimits are much lower than are obtained by ordinary flame spectrophoto-metry. Because the “ temperature ” of the plasma is much higher thanthat of chemical flames, compound formation resulting in decreased volatilityof an element is practically elimi11ated.~13 Beryllium in oil-field waters(down to 1 : 109) has been determined by emission spectrometry with a plasmaarc. The beryllium was extracted from the water with chloroform andacetylacetone, the extract being aspirated directly into the plasma arc.314The d.c. arc-type and high-frequency induction-type high-pressure plasmashave also been investigated as spectroscopic emission sources.315Pneumatic, electrostatic, and ultrasonic methods ofatomisation of solutions in flame photometry have been compared.Thebest results, especially the highest sensitivity, were obtained by ultrasonicat0misation.~16 A theoretical study on the effects of various experimentalfactors on the limit of detectability in flame photometry has beenObservation of the atomic line spectra emitted in the interconal zone ofa premixed, fuel-rich, oxyacetylene flame has made it possible to detect, forthe first time, analytically useful lines for cerium, hafnium, tantalum,thorium, uranium, and zirconium. It should now be possible to detect theseelements by atomic absorption procedures as ~ e l l . ~ l 8 The analyticalpotentialities of the simple spectra emitted by the rare-earth elements whenethanol solutions of their perchlorates are aspirated into fuel-rich, oxyacety-Plume photometry.308 C.E. Pietri and A. W. Wenzel, Analyt. Chem., 1964, 36, 1937.30Q A. W. Wenzel and C. E. Pietri, Aizalyt. Chem., 1964, 36, 2083.310 T. M. Moroshkina and M. N. Srnirnova, Zhur. analit. Khim., 1964, 19, 325.311H. Dunken, W. Mikkeleit, and G. Haucke, 2. Chem., 1963, 3, 477.312 P. Emrnott and R. E. Wilson, Talantu, 1964, 11, 1011.31s C. D. West and D. N. Hume, Analyt. Chem., 1964, 38, 412.314A. G. Collins and C. A. Pearson, AnaZyt. Chem., 1964, 36, 787.315 S. Greenfield, I. L. Jones, and C. T. Berry, Analyst, 1964, 89, 713.a16 H. Dunken, G. Pforr, W. Mikkeleit, and K. Geller, Spectrochlim.Actu, 1964,317 J. D. Winefordner and T . J. Vickers, Analyt. Chern., 1964, 38, 1939.318 A. P. D’Silva, R. N. Kniseley, and V. A. Fassel, Analyt. Chem., 1964, 36, 1287.20, 1531HEADRIDGE, PIERCE, AND ANDERSON 549fene flames, have been thoroughly evaluated. Complex rare-earth mixturesare analysed satisfactorily by this technique.319Phosphorus in a wide range of organic and inorganic compounds hasbeen determined flame-photometrically with good accuracy and precisionby using the flame emission continuum centred at 540 mp and an oxygen-hydrogen flame.320 Phosphate in rock phosphate has also been determinedflame-spectrophotometrically, by first determining the calcium concentrationby means of an acetylene-oxygen-air flame, at which temperature phosphatehad no depressive effect, and then determining the calcium :phosphate ratioby means of the cooler propane-air flame.3218pectrojiuorimetry.The effects of the position and dimensions of thesample cell on the fluorescence intensity-concentration curve for perpendicu-lar-type fluorimeters have been reported.322 To assist in the identificationand quantitative determination of polycyclic hydrocarbons, an oscillographictechnique in fluorhetry has been developed for recording excitation wave-length, emission wavelength, and emission inten~ity.~Z~Spectrofluorimetry has been applied to the determination of indium byusing the fluorescent Rhodamine 3B-bromoindate complex extracted intobenzene from aqueous solution ;324 of selenium in plant materials after anoxygen-flask combustion, with naphthalene-2,3-diamine as fluorimetricreagent;325 of uranium as a Rhodamine B complex, with a lower detectionlimit of 0.012 p.p.m.;326 of urea in blood with biacetyl monoxime as fluori-metric reagent ;327 of naturally occurring indoles in plants ;328 of microgramsof streptomycin and dihydrostreptomycin with sodium 1,Z-naphthaquinone-4-sulphonate as fluorimetric reagent ;329 of submicrogram amounts of pheno-thiazine drugs in aqueous solution after reaction with potassium perman-ganate and of ethynylcestradiol in methyl chloroacetate after reactionwith anhydrous aluminium chloride, with a precision of 4% at a concentra-tion of 2 ,ug./m1.331 Parts per 1000 million of cobalt@) can also be determinedwith good accuracy and precision by the decrease in fluorescence intensityof the Aluminium Chrome Blue Black Extra complex on the addition ofthe metal ion; the decrease is linear over at concentration range of 0-001-0.02 pg.per ml. of final solution.332A new analytical method, atomic fluorescence spectrometry, has beenintroduced. Atoms in a flame are excited by absorption of radiation of81g A. P. D’Silva, R. N. Kniseley, V. A. Fassel, R. H. Curry, and R. B. Myers,Analyt. Chem., 1964, 36, 532.320 A. Davis, F. J. Dinan, E. J. Lobbett, J. D. Chazin, and L. E. Tufts, Analyt.Chem., 1964, 36, 1066.321 R. Ratner and D. Scheiner, Analyst, 1964, 89, 136.322 W. E. Ohnesorge, Analyt. Chim. Acta, 1964, 31, 484.323 M. M. Schachter and E. 0.Haenni, Analyt. Chem., 1964, 36, 2045.324 Ya. Glovadsky, A. P. Golovina, L. V. Levshin, and Yu. A. Mittsel, Zhur. analit.325 P. Cukor, J. Walzcyk, and P. F. Lott, Annlyt. Chim. Acta, 1964, 30, 473.826 N. R. Anderson and D. M. Hercules, AnaZyt. Chem., 1964, 36, 2138.327 J. E. McCleskey, AnaZyt. Chem., 1964, 36, 1646.328 D. Burnett and L. J. Audus, Phytochemistry, 1964, 3, 395.s29 F. Faure and P. Blanquet, CZinica Chim. Acta, 1964, 9, 292.830 T. J. Mellinger and C. E. Keeler, AnaZyt. Chem., 1964, 36, 1840.s31 J. Meier and A. Becker, 2. analyt. Chem., 1964, 204, 427.332 S. B. Zamochnick and G. A. Rechnitz, 2. analyt. Chem., 1964, 199, 424.Khim., 1964, 19, 693550 ANALYTICAL CHEMISTRYthe proper frequency, and the intensity of the fluorescent emission, comingoff at right angles to the exciting radiation, is measured.333 Zinc, cadmium,and mercury have been determined by this technique, working curves forzinc 2139 8, cadmium 2288 A, and mercury 2537 A being linear over a largeconcentration range.=* A study of experimental parameters for thistechnique has also been made.335With a view to the possible application of phosphorimetry to the traceanalysis of drugs in biological fluids, the phosphorescence excitation andemission spectral peaks, life-times, working curves, and limits of detectionof 22 organic compounds of pharmacological importance, in rigid (77 OK),ethanolic solution have been reported.336Atonaic absorption spectroscopy.Recent developments in atomic absorp-tion spectroscopy have been reviewed by David 337 and by Lockyer.338 Atheoretical study on t'he effect of various experimental factors on the limitsof detectability in atomic absorption spectroscopy has been rep0rted.~39 Adouble-beam atomic absorption spectrometer to compensate for fluctuationsof the light source has been described; with this instrument the limits ofdetection for magnesium and calcium are 0.005 p.p.m.(2852 A) and 0.8 p.p.m.(4227 A), respectively.=O1-10 p.p.m. of silver in aqueous solution have been satisfactorilydetermined by atomic absorption spectroscopy. Only thorium, iodate,tungstate, and permanganate caused interference when present in 1000-foldmole-ratio excess. After a solvent extraction procedure 0.01-1 p.p.m. ofsilver in aqueous solution can also be determined.341It has been stated that in the determination of lead, as tetraethyl-lead,in petrol, by means of atomic absorption spectroscopy at 2833 A and anair-propane flame, satisfactory results are obtained only when the calibrationgraph is also prepared for solutions of tetraethyl-lead; use of other leadcompounds in the standard solutions produces erroneous results.342Atomic absorption spectroscopy has also been applied to the determina-tion of manganese in high-alloy irons and steels ;343 copper (0.001-0.30 yo) ,344manganese (0.OOl-2 y0)345 and nickel (0.005-2 %)346 in low- and high-alloyirons and steels; of silver in aluminium all0~7~;347 of silver, gold, platinum,palladium, and rhodium in non-ferrous alloys ;34* of palladium in alloys ;349333 J.D. Winefordner and T. J. Vickers, Analyt. Cliem., 1964, 36, 161.334 J. D. Winefordner and R. A. Staab, Analyt. Chenz., 7964, 36, 165.335 J. D. Winefordner and R. A. Staab, AnaTyt. Ci~em., 1964, 36, 1367.336 J. D. Winefordner and M. Tin, Analyt. Chim. Acta, 1964, 31, 239.337 D. J. David, Spectrochim. Acta, 1964, 20, 1155.338 R. Lockyer, Adv. A.iznTyt. Chent. Instrumen., 1964, 3, 1.339 5. D. Winefordner and T. J. Vickers, Analyt. Ci~ena., 1964, 36, 1947.340 W. H. Hinson and R. Kitching, Spectrochim. Acta, 1964, 20, 248.3 4 1 R. Belcher, R. M. Dagnall, and T. S. West, Talanta, 1964, 11, 1257.342 R. M. Dagiiall and T. S. West, Tuluntw, 1964, 11, 1553.343 M. Suzuki and T. Takeuchi, J . Chem SOC. Japan, I n d . Chem.Sect., 1964, 67,3 4 4 I<. Kinson and C . B. Belcher, AnaEyt. China. Acta, 1964, 31, 1SO.345 K. Kinson and C . B. Belcher, Analyt. Chim. Acta, 1964, 30, 483.346 K. Kinson and C. B. Belcher, Analyt. Chim. Acta, 1964, 30, 64.347 L. Wilson, Analyt. Chim. Acta, 1964, 30, 377.348 V. L. Ginzburg, D. M. Livshits, and G. I. Satarina, Zhur. anaEit. Khim., 1964,349 G. Erinc and R. 3. Magee, Analyt. Chim. Acta, 1964, 31, 197.1207.19, 1089HEADRIDGE, PIERCE:, AND ANDERSON 551of sodium, potassium, magnesium, and manganese in cement;350 of smallamounts of zinc, lead, and calcium in polyvinyl chloride after dissolution inNN-dimethylacetamide ;351 and of magnesium in biological materials.352Ultraviolet and visible spectrophotmnetry. Several important theoreticalpapers were published last year.Maurice 353 proposed a statistical test forthe detection of deviations from Beer’s law during the preparation of calibra-tion curves and described a procedure for the analysis of calibration data.Higgins 354 pointed out the errors which may result from subtracting ablank value,” and suggested that a statistical approach should be used.Herschberg 355 described a “ spectrocolorimetric method ” for the analysisof multicomponent mixtures ; absorbance measurements of reference andsample solutions are carried out simultaneously to achieve independence ofcalibrations ; measurements are made at many (20-40) wavelengths, andthe system of equations so obtained is solved by a computer; up to sixcomponents can be involved, and the accuracy claimed is a factor of 10 betterthan that given by ordinary methods.A general method 356 for eliminatinginterference in multicomponent coloured systems was also proposed, withexperimental evidence for its efficiency. A similar, but more mathematical,approach was described by Glasner and Avinur 357 for the determination ofimpurities in reagents ; the manipulation of algebraic formula? requiresabsorption measurements on the solution a t two wavelengths, together witha knowledge of the absorption coefficients of the ions to be determined; thetheory does not require information about the nature or concentration ofthe interfering ions. Mention must also be made, in this theoretical section:,of the timely suggestions made 358 by Belcher and Betteridge regarding theneed for an acceptable convention for representing the “ selectivity index ”of a reagent.In addition to these important advances, the following were consideredto be the most significant of the usual large number of new, or modified,colorimetric methods that were described.Xylenol Orange 359 and N -benzoyl-o-tolylhydroxylamine 360 were used as reagents for vanadium, andthe use of formaldoxime 361 was extended to the determination of cerium,iron, manganese, nickel, and vanadium. Dagnall and West 362 described aselective and sensitive colour reaction for silver and suggested that the colouraction of many adsorption indicator systems may be explained on the basisof charge-transfer mechanisms rather than on the currently acceptedadsorption-electronic distortion theory.Other interesting papers dealt350T. Takeuchi and M. Suzuki, Talanta, 1964, 11, 1391.351 S. Musha, M. Munemori, and Y. Nakanishi, Japan Analyst, 1964, 13,352 D. B. Horn and A. L. Latner, clinica Chim. Acta, 1963, 8, 974.353 M. J. Maurice, 2. analyt. Chem., 1964, 204, 401.354 J. Higgins, Analyst, 1964, 89, 211.355 I. S. Herschberg, 2. analyt. Chem., 1964, 205, 181.356 L. B. Kulichenco and E. Z . Espinosa, 2. analyt. Chem., 1964, 206, 249.357 A. Glasner and P. Avinur, Talanta, 1964, 11, 679, 761, 775.358 R. Belcher, Talanta, 1965, 12, 129; D. Betteridge, ibid., p. 129.3 5 9 0. Budevsky and R. Piibil, Talanta, 1964, 11, 1313.360 A. K. Majumdar and G. Das, Analyt. Chim. Acta, 1964, 31, 147.361 Z.Marczenko, Analyt. Chim. Acta, 1964, 31, 224.362 R. M. Dagnall and T. 8. West, Talanta, 1964, 11, 1533.330552 ANALYTICAL CHEMISTRYwith the determination of palladium with 2-mercaptobenzoxazole 363 andwith the simultaneous determination of palladium and platinum 364 by meansof quino~aline-2~3-dithiol. 8-Hydroxyquinoline was used in methods fortitanium 365 and magnesium.366 Procedures for the determination of tracesof mercury in selenium,367 and for traces of iron and lead in copper,368 weredescribed.Methods for the determination of anions included the use of 2,6-xylenolfor nitrate:6g and methods for bromate,3?O iodate or iodide,37l and fluoride.372Organic applications 373 included the determination of catechols with.Q-aminoantipyrine, and of vitamin A with trifluoroacetic acid.In aninteresting paper on ninhydrin complexes of amino-acids, increasing analyticaluse of the spectral reflectance technique was advocated.374Infrared spectrophohetry. The increasing use of Fahrenfort's attenuatedtotal reflectance technique (A.T.R.) continued during the past year. Abrief review,375 and papers 376 describing the design of multiple reflectioncells, were published. An important contribution by Hannah and Dwyer 377showed how the collection of samples on millipore filters could be used inconjunction with the A.T.R. technique.Infrared spectroscopy continued to be used in functional-group analyses(see above) and for the identification of fractions from gas chromatography;Bartz and Ruhl 378 developed a rapid-scan spectrometer (complete spectrumin 16 sec.) for this purpose.There were many applications to the analysis of polymers,37Q e.g., thedetermination of (a) propene in ethylenepropene co-polymers,880 ( b )styrene : butadiene ratios s81 in co-polymers, (c) the ester content in oxidisedpolyethyleneFs2 and ( d ) the relative amounts of the four possible isomersresulting 383 from the polymerisation of chloroprene. Metzler 384 suggestedthe use of silver chloride discs for the examination of aqueous polymersuspensions.T.Arita and J. H. Yoe, Analyt. Chim. Acta, 1963, 29, 500.s64 H. F. Janota and G. H. Apes, Analyt. Chem., 1964, 36, 138.$86 C. L. Chakrabarti, R. J. Magee, and C. L. Wilson, Taksnta, 1963, 10, 1201.T. Y.Toribara, L. Koval, and J. F. P. Olive, Talanta, 1963, 10, 1277.s67 E. N. Pollock, Talanta, 1964, 11, 1548.868 R. P. Hair and E. J. N e m m , Analyst, 1964, 89, 42.s69 D. W. W. Andrews, Analyst, 1964, 89, 730.3 7 o M . H. Hashmi, H. Ahmad, A. Rashid, and A. A. Ayaz, Analyt. Chem., 1964,871 J. Fuchs, E. Jungreis, and L. Ben-Dor, Analyt. Chim. Acta, 1964, 31, 187.s72 J. G. Aldous, R. J. Hall, and P. Sapp, Analyt. Chem., 1964, 36, 335.878 T. A. LaRue and E. R. Rlakley, Analyt. Chim. Acta, 1964,31,400; R. E. Dugan,874 R. W. Frei and M. M. Frodyma, Analyt. Biochem., 1964, 9, 310.376 B. Sherman, Appl. Spectroscopy, 1964, 18, 7 .376 N. J. Harrick, Analyt. Chm., 1964, 36, 188; W. N. Hansen and J. A. Horton,377 R. W. Hannah and J. L. Dwyer, Analyt. Chem., 1964, 36, 2341.3 7 8 A .M. Baxtz and H. D. Ruhl, Analyt. Chem., 1964, 36, 1892.s79 P. W. 0. Wijga, 2. analyt. Chem., 1964, 205, 342.881 A. S. Wexler, Andyt. Chem., 1964, 36, 1829.883 J. N. Lomonte, Analyt. Chem., 1964, 36, 192.883 R. C. Ferguson, Anatyt. Chem., 1964, 36, 2204.w4 R. K. Metzler, Analyt. Chem., 1964, 36, 2378.36, 2028.N. A. Frigerio, and J. M. Siebert, Analyt. Chem., 1964, 36, 114.{bid., p. 783.J. E. Brown, M. Tryon, and J. Mandel, Analyt. Chern., 1963, 35, 2172HEADRIDGE, PIERCE, AND ANDERSON 553Dolinsky and Wilson used the liquid anion-exchanger L.A.2 in quantita-tive analysis of some water-soluble acids and salts.385 Aqueous solutions ofamino-acids were examined 386 as mounts on agar (100 ,u thick).Cavitycells, beam condenser, and scale-expansion devices were used for the examina-tion 387 of micrograms of organophosphorus pesticides.Inorganic applications included the use of a long-path-length cell forthe detection of impurities in silicon and germanium halides 388 and for thedetermination 389 of vanadium, molybdenum, and tungsten as their oxinederivatives.The uses of this technique in organicelemental and functional group analyses have already been considered (seeabove). Nuclear magnetic resonance (n.m.r.) spectra have proved of valuein structural studies of paraffinic chains 390 and chlorinated propanes;391 themethod is particularly powerful in the investigation and determination ofis0mers.~92There have been many applications to the study and analysis of polymersduring the past year.C. N. Reilley and his co-workers 393 investigatedchelating agents of the polyamine and amino-carboxylate types ; otherinvestigators determined the monomer content of co-polymers of vinylacetate with ethylene 394 and of styrene with buta-1,2- or 1,4-diene.395 Forn.m.r. analysis to be feasible, the polymer must have adequate solubilityin a suitable solvent, and it must yield spectral peaks narrow enough toallow differentiation between the monomers. Other polymer applicationshave included the identification of the acids and glycols present in polyesterr e ~ i n s , ~ Q ~ and the determination of the number-average molecular weight, byend-group analysis, of some polyalkylene glycols and glycol polyesters.397The determination is based on the complex formed between pyridine andOH groups, resulting in a separation of the CH,*OH resonance from theCH,*O resonance,9.Electrochemical ASethods.-As usual, a large number of papers werepublished in 1964 on the analytical applications of polarography and voltam-metry, and the Reporter has again been very selective in his choice of material.A few publications are continuing to appear on controlled-potential coulo-metry, but there seems to be less interest in the analytical aspects of chrono-potentiometry .Nuclear nmgnetic resonance.385 M. Dolinsky and C. H. Wilson, Analyt. Chrn., 1964, 36, 1383.386 M. L. Tarver and L. M. Marshall, Analyt. Chem., 1964, 36, 1401.387 N. T. Crosby and E. Q.Laws, Analyst, 1964, 89, 319.388 M. J. Rand, Analyt. Chem., 1963, 35, 2126.R. J. Magee and A. S. Witwit, Analyt. Chim. Acta, 1963, 29, 517.390 K. W. Bartz and N. F. Chamberlain, Analyt. Chem., 1964, 36, 2151.391 H. F. White, Analyt. Chcm., 1964, 36, 1291.392 G. Slomp, R. H. Baker, Jr., and F. A. MacKellar, Analyt. Chem., 1964, 36, 375;H. F. White, C. W. Davisson, and V. A. Yarborough, p. 1659; W. L. Senn, Jr., andL. A. Pine, Analyt. Chim. Acta, 1964, 31, 441.393 R. J. Day and C. N. Reilley, Analyt. Chem., 1964, 36, 1073; J. L. Sudmeierand C. N. Reilley, ibid., pp. 1698, 1707.304 H. Y. Chen and M. E. Lewis, Analyt. Chem., 1964, 36, 1394; 31. W. Dietrichand R. E. Keller, ibid., p. 2174.395 W. L. Senn, Jr., Analyt. Chim. Acta, 1963, 29, 505.396 D.F. Percival and M. P. Stevens, Analyt. Chew., 1964, 36, 1575.397 T. F. Page, Jr., and W. E. Bresler, AnuZyt. Chem., 1964, 36, 1981554 ANALYTICAL CHEMISTRYPolarography, voltummet y, and galvanic analysis. Davis 398 has reviewedrecent advances in differential cathode-ray (potential sweep) and pulsepolarography, and derivative cathode-ray polarography has been discussed.399Polarography in molten salts has also been reviewed.400The theory of stationary-electrode polarography for single-scan and cyclicmethods applied to reversible, irreversible, and kinetic systems has beenpresented.*Ol The factors affecting resistance compensation in polarographyapplied to high-resistance, non-aqueous systems and to high-current-densityaqueous systems have been studied in detail.402A polarographic cell incorporating a dropping-mercury electrode andwith a very small hold-up volume has been constructed of glass and Teflonfor the continuous analysis of flowing solutions.4o3 A polarograph has beendescribed, which permits d.c.polarograms to be obtained for solutions asdilute as 10-lO~ in reducible substance. The residual current of the cellis cancelled out by a bucking current supplied from a specially designedcircuit .*04 A.c. polarography with a pushed-out mercury-drop convectionelectrode has been investigated for cadmium ions in M-hydrochloric acid;summit current is directly proportional to concentration, and, in the presenceof dissolved oxygen at a stirring rate of 600 r.p.m., is about thirty times aslarge as the corresponding difision current obtained with a dropping-mercuryelectrode.405 A simple electronic-scan controlled-potential polarograph hasalso been described.406Polarography has also been applied to the determination of lead in steelsand copper-zinc alloys after the separation of lead from interfering elementsby ion-exchange;*07 of tin and lead in iron and steel in amounts in excessof 0.01 yo ;408 of lead and nicke1,409 and of manganese,4lo in uranium and itscompounds (square-wave) ; of plutonium(rv) after separation from interferingelements by ion-exchange (a.c.) ;all of antimony(m), tin(Iv), and arsenic(m)in ammonium oxalate-oxalic acid supporting electrolyte (derivative) ;4l2 ofmolybdenum(v1) by using its catalytic reduction wave in 2*4M-nitriC acid(limit of detectability 0.005 pg. of molybdenum per ml.);*la of oxygen inpetrol (cathode-ray) ;414 and of nitrite by reaction with 2,6-xylenol a.nddetermination of the resulting 4-nitroso-2,6-xylenol, which is reducible atthe dropping-mercury electrode.A 100-fold excess of nitrate can be tolerated398 H. 31. Davis, J . Roy. Inst. Chem., 1964, 88, 104.399 R. C. Rooney, J . Polarog. SOC., 1963, 9, 45.400 H. C. Gaur and R. S . Sethi, J . Electroanalyt. Chem., 1964, 7 , 474.(01 R. S. Nicholson and I. Shain, Analyt. Chem., 1964, 36, 706.4oa W. B. Schaap and P. S . McKinney, Analyt. Chem., 1964,36, 1251.403 W. J. Blaedel and J. H. Strohl, Analyt. Chern., 1964, 36, 445.404 G . W. Miller, L. E. Long, and G. M. George, Analyt.Chem., 1964, 36,*05 J. Suzuki and T. Ozaki, Bull. Chem. SOC. Japan, 1964, 37, 789.&06 R. A. Durst, J. W. Ross, and D. N. Hume, J . Electroanalyt. Chem., 1964, 7, 245.(07 J. R. Nash and G. W. Anslow, Analyst, 1963, 88, 963.408 S . H. Omang and C . U. Wetlesen, Analyt. Chim. Acta, 1964, 30, 60.F. Nakashima, Analyt. Chim. Acta, 1964, 30, 265.410 F. Nakashima, Analgt. Chim. Acta, 1964, 30, 167.411 G. W. C. Milner and A. J. Wood, J . Electroanalyt. Chern., 1964, 7, 190.R. Geyer and M. Geissler, 2. analyt. Chem., 1964, 201, 1.413 A. T. Violanda and W. D. Cooke, Analyt. Chem., 1964, 36, 2287.p14 G. L. Woodroffe, Tahnta, 1964, 11, 967.1143HEADRIDGE, PIERCE, AND ANDERSON 555without interferen~e.~’5 Thorium (0-043 mM) has been determined by itseffect on Solochrome Violet RS in OolM-SOdiUm potassium tartrate at pH 12.0 ;the height of the dye reduction wave is inversely proportional to the con-centration of thorium, while that of the dye-thorium complex reductionwave is directly proportional to the concentration of thorium.*16In organic systems, polarography has been used for the determinationof small amounts of p-chloroacetanilide in phenacetin ;4l7 of compoundscontaining dichloroacetamido-groups in medicinal products ;418 of benzo-diazepines in alcohol-water ;419 of carbon tetrachloride in chloroform, andof carbon tetrachloride and chloroform in methylene chloride ;420 of Thalido-mide in concentrations down to 2 pg./ml.(oscillopolarography) ;421 ofacetylcholine in biological rnaterials;422 and of the blowing agent, pp’-oxybis(benzenesulphony1hydrazide) in polyethylene blends by use of thereducible double hydrazone derivative formed between the agent andacetone.423The continuous determination of dissolved oxygen in flowing solutionshas been satisfactorily achieved by using a mercury-plated platinum-wireconvection electrode.424 Anodic stripping voltammetry with carbon pasteelectrodes has been employed for the determination of trace amounts ofsilver and gold; as little as p.p.m.ofsilver could be determh~ed.~~SGalvanic analysis has been reviewed by Hersch,426 who defines this termas “ ft method which makes the species of interest a reactant at one of a pairof electrodes, thereby generating an electrical current without the aid ofan external electromotive force.” In this commendable article, cells aredescribed €or the analysis of oxygen, hydrogen, halogens, ozone, oxides ofnitrogen, carbon monoxide, carbon dioxide, water vapour, reductants, andorganic compounds.Submicrograms of cyanide in hydroxide solution havebeen determined by measuring the spontaneous current flowing in a cellconsisting of a rotating gold-coil electrode as anode and a platinum-foilcathode; in the presence of cyanide and dissolved oxygen, the gold is oxidisedto a cyanide complex.427This technique has been applied to thedetermination of uranium in the presence of plutonium and iron afterreduction of plutonium to plutonium(rr1) with hydrazine;428 of N-substitutedp.p.m. of gold and 2.5 xControlled-potential coulometry.415 A.M. Hartley and R. M. Bly, Analyt. CJhem., 1963, 35, 2904.0115 D. S. Tnrnham, J . Electroanalyt. Chem., 1964, 7, 211.417 R. Jones and B. C. Page, AnaEyt+ Chem., 1964, 36, 35.418 C. A. Kelly, Talanta, 1964, 11, 175.419 B. Z. Senkowski, M. S . Levin, J. R. Urbigkit, and E. G. Wollish, Analyt. Chem.,4zoK. G. Berezina, L. K. Kutanina, and V. V. Katsion, Zavodskaya Lab., 1963,421 J. S. Hetman, Chem. Zvesti, 1964, 18, 422.4 2 2 A. F. Maslova, Voprosy Med. Khim., 1964, 10, 311.423 C. C. Budke, D. K. Banerjee, and F. D. Miller, Analyt. Cl~em., 1964, 36, 523.424T. Ozaki, J. Suzuki, and K. Izawa, Japan Analyst, 1964, 13, 107.425E. S . Jacobs, Analyt. Chem., 1963, 35, 2112.426P. Hersch, Adv. Annlyt.Cliem. Instrument., 1964, 3, 183.4a7 G. W. Miller, L. E. Long, G. &I. George, and W. L. Sikes, Analyt. Chem., 1964,aZ8G. C . Goode, J. Herrington, and G. Hall, Analyt. Chim. Acta, 1964, 30, 109.1964, 36, 1991.29, 1434.36, 980556 ANALYTICAL CHEMISTRYphenothia~ines;~~Q and of p-phenetidine in O*5~-sulphurk acid a t an anodepotential of + 1-25 v versus the saturated calomel electrode, the phenetidinebeing oxidised to a hydrazo-~ompound.~3OA cell has been described for the determination of oxygen in waterflowing at a controlled rate by means of constant-potential derivative coulo-r n e t r ~ . ~ ~ ~ Ncrograrns of lead have been determined by a selective method,in which the element is deposited as lead dioxide on a rotating platinummicroelectrode by anodic oxidation, and then determined by cathodicst ripping coulomet ry .432Chronopotentiometry . Mixtures of hydrazine and hydroxylamine havebeen analysed with fair precision by anodic chronopotentiometry. Hydrazinegives a four-electron wave (E,.25 = +0.36 v versus a saturated calomel elec-trode), and hydrozrylamine produces a six-electron wave (E,.25 = +043 v)in 0-1M-sulphuric acid at a platinum anode. Chloride ion interferes andmust be removed.43318. Radiochemistry.-For convenience this short article is divided intotwo sect,ions; the first is concerned with the use of isotopes irradiated beforethe analysis, the second with activation procedures. Both classes of nuclearmethod are considered in a comprehensive review covering the period late1961 to 1963.434Extensive use has been made of tracer methods toexamine the behaviour of two-phase systems and to develop separationprocedures.However, as separation procedures are discussed in an earliersection of this Report, they will not be considered here.Isotope dilution has been used to determine selenium down to sub-microgram levels in plant material 435 by using 75Se. Further applicationsof cobalt-labelled vitamin B 12 to isotope dilution have been discussed.436Under suitable conditions substoicheiometric determinations can be appliedto isotope dilution procedures with advantage, and the application of thetechnique to both isotope-dilution and activation analysis has been re-viewed;437 and a method has been published for the determination ofindi~m.~~8An isotope-exchange method has been developed for mercury in therange 10-7-10-2 g. The sample, in aqueous mineral acid, is shaken witha solution of mercuric di-n- butyl phosphorothioate in carbon tetrachloride,and the distribution ratio of the mercury is determined with 203Hg, eitherby adding it to the system as tracer or by using it to label the complex.439Radiorelease methods have been used to determine vanadium in waterat the 1 p.p.m.level. The acidified sample is passed through a columnIsotope methods.429 F. H. Merkle and C. A. Discher, Analyt. Chem., 1964, 36, 1639.430K. S. V. Santhanam and V. R. Krishnan, 2. ana.lyt. Chew&., 1964, 206, 33.431 E. L. Eckfeldt and E. W. Shaffer, Jr., Analyt. Chem., 1964, 36, 2008.43aT.Yoshimori, S. Kori, and T. Takeuchi, Japan Analyst, 1964, 13, 309.43sM. D. Morris and J. J. Lingane, J. Electroanalyt. Chem., 1964, 8, 85.434G. W. Leddicotte, Analyt. Chem., 1964, 36, 419R.e35P. Cukor, J. Walzcyk, and P. F. Lott, Analyt. Chim. Acta, 1964, 30, 473.436 C. Rosenblum, Talanta, 1964, 11, 255.487 J. Star4 and J. RBiiEka, Talanta, 1964, 11, 697.438 J. ROiiEka and J. Stae, Talanta, 1964, 11, 691.439 T. H. Handley, Anctyt. Chem, 1964, 36, 153HEADRIDGE, PIERCE, AND ANDERSON 557containing radioactive silver, and the silver, Liberated according to thereactionV(OH),+ + 2H+ + Ag --+ VO2+ + Ag+ + 3H,Ois measured.440Radiometric titrations have been reviewed 441 and indium determinedat the microgram level by titration with a, chelating radiometric technique.442A rapid method for the determination of sulphur in non-alloy steel, pigiron, and cast iron has been developed, the absorbant solution being labelledwith 115Cd,443 and sub-microgram quantities of calcium, strontium, barium,lead, beryllium, and zirconium have been determined either as 35S-labelledsulphates or as 32P-labelled phosphates after paper ~hromatography.~~~Liquid scintillation counting has again been the subject of many papers,and a review has been published covering the period 1957-1963.445 Abalanced quenching technique has been recommended for the determinationof 14C,446 and low levels of 14C have been counted after conversion intomethyl ben~oate.~~7 Statistical aspects of counting two isotopes by liquidscintillation have also been considered 448 and an extrapolation has beenthe method proposed for quenching correction of samples labelled with both1% and 3H.449 Glass vials have been coated with Silicone to reduce walladsorption,450 and a light filter has been used to decrease background.451The relatively high solubility of krypton, xenon, and radon in hydrocarbonsemployed as solvents for liquid scintillators permits liquid scintillationtechniques to be used to determine the activity of isotopes of these gases;452bioassay of promethium-147 has also been carried out by liquid scintillation.453Activation analysis.Activation analysis has received considerableattention throughout the year. Recent advances have been reviewed 454and a comprehensive bibliography p~blished.45~ A list of short-livednuclides with half-lives varying from 2-7 milliseconds to 20 minutes producedin activation procedures has been tab~lated,~5~ and cross-sections for 92,a reactions with 14 Mev neutrons have been listed457 A computer programmeto optimise irradiation and decay times in instrumental activation analysis440 A. S.Gillespie, Jr., and H. G. Richter, Analyt. Chem., 1964, 36, 2473.441 T. Braun and J. Tolgyessy, Tdanta, 1964, 11, 1277.44z J. Starg, J. RbiiEka, and A. Zeman, Talanta, 1964, 11, 481.449 S. Spauszus, 2. analyt. Chem., 1964, 206, 12.444 G. A. Welford, E. L. Chiotis, and R. S . Morse, Analyt. Chem., 1964, 36, 2350.446 E. Rapkin, Internat. J . Appl. Radiation Isotopes, 1964, 15, 69.446 H.H. ROSS, Internat. J . Appl. Radiation Isotopes, 1964, 15, 273.447 L. T. Freeland, Amlyt. Chem., 1964, 30, 2055.44sR. 5. Herberg, Analyt. Chem., 1964, 36, 1079; E. T. Bush, ibid., p. 1082.449 C. T. Peng, Analyt. Chem., 1964, 36, 2456.460 C. P. Petroff, P. P. Nab, and D. A. Turner, Intemat. J . Appl. Radiation Isotopes,461 H. A. Swartz, Analyt. Chem., 1964, 38, 2080.462 D. L. Horrocks and M. H. Studier, Analyt. Chem., 1964, 36, 2077.463 J. D. Ludwick, Analyt. Chem., 1964, 36, 1104.464 V. P. Guinn, " Third United Nations Conference on the Peaceful Uses of AtomicEnergy ", A/CONF.28/P/197, Pergamon, London, 1964.466 W. Bock-Werthmann, Zentralstelle fiir Atomkernenergie-Dokumentation beimGmelin-Institut, Bibliography AED-(3-14-03.466 M. Okada, Nucleonics, 1964, 22, No.8, 110.467 A. Chatterjee, Nucleonics, 1964, 22, No. 8, 108.1964, 15, 491558 ANALYTICAL CHEMISTRYhas been and nomographs for calculating induced activity anddecay have been published.459 Nomographs have also been used to determineinterferences and limits of dete~tion.~~O The role of second-order inter-ferences in activation procedures has been considered 461 and the errorsinvolved in activation analysis by direct calculation of weights from nuclearconstants have been studied.462Sum-coincidence spectrometry has been used to achieve higher selectivityfur the determination of antimony;463 but the high resolution attainablewith lithium drift germanium diodes 464 has not, as yet, been widely applied,largely because of the low sensitivity of the detectors available at present.Activation analysis has been extensively applied to the determination oftrace elements in biological materials.chromium,46' mercury and arsenic,46* and cobalt, copper, iron, and zinc 469being amongst the elements determined.The zinc-68:zinc-64 ratio in rocks has been found from the 6grnZn/65Znratio after acti~ation,4~~ and the value of zinc in the standard rocks GIand Wl is found to be 45.7 and 82.8 p.p.m., re~pectively.~7l Mercury hasbeen determined in G , and W, by using a NaI(T1) scintillator with a thinberyllium and a number of micronutrient elements have beenmeasured in s0i1.~'~A comparison has been made between results obtained by mass spectro-metry and activation analysis for rubidium and czesium in stonyHigh-purity beryllium, aluminium, and iron have been analysed fortraces of 62 irnp~rities,47~ and a method has been developed to determine30 elements in high-purityChemical yield has been measured by reactivation in methods for vana-dium 477 and mercury.47* The feasibility of determining deuterium in deu-terated organic compounds, by making use of the reaction 12C(d,n)13N in-duced by knock-on deuterons during reactor activation, has been asse~sed,4'~C0pper,*6~ calcium and458 T.L. Isenhour and G. H. Morrison, Analyt. Chem., 1964, 36, 1089.459 E. Ricci, Nucleonics, 1964, 22, No. 8, 106.460 W. Haerdi, Chimia (Switz.), 1964, 18, 138.461 E. Ricci and F. F. Dyer, Nucleonics, 1964, 22, No. 6, 45.462 F.Girardi, G. Guzzi, and J. Pauly, Analyt. Chem., 1964, 36, 1588.463 F. Adams and J. Hoste, Nucleonics, 1964, 22, No. 3, 55.464 G. T. Ewan, Atomic Energy of Canada Limited, Report AECL-1960,465 K. G. Kjellin, Interfiat. J . Appl. Radiation Isotopes, 1964, 15, 461.466 H. J. 39. Bowen, P. A. Cawse, and M. Daglish, Analyst, 1964, 89, 266.467 H. J. M. Bowen, Analyst, 1964, 89, 658.468 B. Sjostrand, Analyt. Chenz., 1964, 36, 814.46D R. M. Parr and D. M. Taylor, Biochenz. J . , 1964, 91, 424.470 R. H. Filby, Analyt. Chem., 1964, 38, 1597.471 R. H. Filby, Analyt. Chinz. Acta, 1964, 31, 557.4 i 2 D. F. C. Morris and R. A. Killick, Talanta, 1964, 11, 781.473 Y. Yamada, Radioisotopes (Tokyo), 1964, 13, 32.474 A. A. Smales, T. C. Hughes, D. Mapper, C.A. J. McInnes, and R. K. Webster,Qeochim. Cosmochim. Acta, 1964, 28, 209.475 W. J. ROSS, Analyt. Chem., 1964, 38, 1114.478 W. Gebauhr and J. Martin, 2. analyt. Chem., 1964, ROO, 266.477 Y. Kamernoto and S . Yamagishi, Talanta, 1964, 11, 27.478 Y. Kamemoto and 5. Yamagishi, Nature, 202, 487.479 E. Fabbri, E. Lazzarini, and V. Sangiust, Internat. J . AppL Radiation Isotopes,1964.1964, 15, 437HEADRIDGE, PIERCE, AND ANDERSON 559and the 1 8 0 content of water found by making use of the reaction l80(p,n)lsFinduced by secondary protons.480Interest has been maintained in neutron generators. A very convenientsealed-tube type of generator has been developed which can give a constantneut'ron output ,481 and equipment designed for the industrial application ofactivation analysis, with a neutron generator, has been de~cribed.~8~Reproducibility of oxygen determinations has been improved by spinningthe sample with a tangential air jett83 and errors in flux monitoring havebeen considered.484 Computer analysis of the y-ray spectra of lubricatingoils after irradiation with fast neutrons has been carried out and the methodfound to be suitable for barium, phosphorus, and chlorine.485cc-Particle activation has been considered for sub-microgram quantitiesof carbon and and 3He activation used to determine carbon byinducing the reaction 12C(3He,a)11C.487Arnericium-beryllium and plutonium-beryllium sources have been com-pared as sources for prompt-y-neutron activation,488 and prompt techniqueshave been used for analysis of coal 48g and to determine carbon in ~teels.~BO11.Mass Spectrometry.-The mass spectroscope has been used by severalinvestigators 491 in conjunction with gas chromatography (see above). Theapplication of mass spectroscopy to inorganic 492 and organic 4g3 analyseshas been discussed; the maximum number of hydrogen atoms that may bepresent for a given molecular weight is limited, and it has been cal~ulated.4~4The correlations and anomalies in the mass spectra of a la,rge number ofacetals have been studied; as a result the authors suggest 495 that certainof the re-arrangements detected may have useful analytical applications.Other systems that have been studied by mass spectroscopy include diary1~ u l p h o n e s , ~ ~ ~ N-substituted carbamates,49' and carbohydrates.498Mass spectrometry in conjunction with isotope dilution forms a useful480 D.C. Aumann and H. J. Born, Naturwiss., 1964, 51, 159.481 J. E. Bounden, P. D. Lomer, and J . D. L. H. Wood, Services Electronics Research482 A. L. Gray, Nuclear fingineering, 1964, 9, 205.483 0. U. Anders and D. W. Briden, Analyt. Clzem., 1964, 36, 287.484 0. U. Anders, Analyt. Chent., 1964, 36, 564.486 D. E. Hull and J. T. Gilmore, Analyt. Clbem., 1964, 36, 2072.486 C. Engelmann, Compt. rend., 1964, 258, 4279.487 J. D. Mahony, B. Parsa, and S. S. Markowitz, U.S. Atomic Energy Commission488 E. D. Jordan and H. E. Schierling, Internat. J . Appl. Radiation Isotopes, 1964,489 T. C. Martin, S. C. Mathur, and I.L. Morgan, Internat. J . Appl. Radiation490 T. B. Pierce, P. F. Peck, and W. M. Henry, Nature, 1964, 204, 571.491 J. T. Watson and K. Eiemann, Analyt. Chem., 1964, 36, 113.492 N. W. H. Addink, 2. analyt. Chem., 1964, 206, 81.493 E. Stenhagen, 2. analyt. Chem., 1964, 205, 109; R. J. C. KIeipool and J. T.494 J. Lederberg and M. Wightman, Analyt. Chem., 1964, 36, 2365.495 W. H. McFadden, J. Wasserman, J. Corse, R. E. Lundin, and R. Teranishi,4D6 S. Meyerson, H. Drews, and E. I<. Fields, Analyt. Chem., 1964, 36, 1294.497 C. P. Lewis, Analyt. Chem., 1964, 36, 176, 1582.498D. C. DeJongh, J . Amer. Chem. SOC., 1964, 86, 4027; 0. S. Chizhov, L. A.Laboratory (United Kingdom) Technical Journal, 1964, 14, No. 3, 44.Report UCRL 11213, 87.15, 427.Isotopes, 1964, 15, 331.Heins, Nature, 1964, 203, 1280.Analyt.Chem., 1964, 36, 1031.Poliakova, and N. K. Kochetkov, Doklady Akad. Naulc. S.S.S.R., 1964, 158, 685560 ANALYTICAL CHEMISTRYtechnique: it has been used for the determination 499 of carbon in sod-ium.have studied atmospheric pollution by massspectrometry, and Russian workers have published 501 a pulse method forstudying elementary reactions in the charge transfer of thermal ions ormolecules.A system of vaporising samples directly in the ion-source of any type ofmass spectrometer has been devised502 and this should extend the applic-ability of the method. The storage of large numbers of mass spectra onmagnetic tape, with retrieval by digital computer, has been proposed.50312.Thermal Methods.-During the last year interest in thermogravimetricanalysis has been maintained and an increasing number of publications ondifferential thermal analysis have appeared. Thermogravimetric analysishas been reviewed by Coats and Redfern 504 and the precautions to be takenin order to obtain reliable results with thermobalances have been discussedby D ~ v a l . ~ * ~ The application of differential thermal analysis to organicsubstances has also been reviewed.506An apparatus for micro and semimicro differential thermal analysis hasbeen described where samples as small as 1 pg. can be used and thermaleffects as small as 1 p a l . can be detected.507 The utility of low-temperaturedifferential thermal analysis and a simple apparatus for the range -78"to +25" have been described.50* An instrument for differential thermalanalysis has also been developed which directly measures the transitionenergy of the sample analysed.509 This differential scanning calorimeterperforms thermal analyses of milligram samples at high speeds and in atemperature range of -100" to +500".Analytical data are recordedgraphically rather as in traditional differential thermal analysis, but peakamplitude directly represents millical. per sec. of transition energy and peakarea directly represents total transition energy in millical.Thermogravimetric analysis and differential thermal analysis have beenused to study the thermal properties of 41 organic 26 ammoniumsalts,511 polyethylenes,5l2 and polypropene ;513 potassium, calcium, andlead fluorides and ammonium, sodium, magnesium, calcium, and zinc silico-Japanese investigators499K.Y. Eng, R. A. Meyer, and C. D. Bingham, Analyt. Chem., 1964, 36, 1832.500 H. Hoshino, N. Wasada, and T. Tsuchiya, Bull. Chem. Soc. Japan, 1964,37,1310.501 G. V. Karachevtzer, M. I. Markin, and V. L. Talrose, Kinetika i Kataliz, 1964,502 G. L. Kearns, Analyt. Chem., 1964, 36, 1402.503 S. Abrahamsson, S. Stiillberg-Stenhagen, and E. Stenhagen, Biochem. J., 1964,504A. W. Coats and J. P. Redfern, AnaZyst, 1963, 88, 906.506 R. Perron and A. Mathieu, Chim. analyt., 1964, 48, 293.507 C. Mazidres, Analyt. Chem., 1964, 36, 602.5 0 * 81. M. Markowitz and D. A. Boryta, Analyt. Chim. Acta, 1964, 31, 397.509 E. S. Watson, M.J. O'Neill, J. Justin, and N. Brenner, Analyt. Chem., 1964,510 W. W. Wendlandt and J. A. Hoiberg, Analyt. Chim. Acta, 1963, 28, 506; 1963,511L. Erdey, S. GAl, and G. Liptay, Tahnta, 1964, 11, 913.512 S. Igarashi and H. Kambe, Bull. Chem. SOC. Japan, 1964, 37, 176.618 T. Takeuchi and K. Saito, J . Chem. SOC. Japan, I d . Chern. Sect., 1964, 67, 906.5, 377.92, 2P.C. Duval, Analyt. Chim. Acta, 1964, 31, 301.36, 1233.29, 539HEADRIDGE, PIERCE, AND ANDERSON 561fluorides;514 copper(=), nickel(=), cobalt(@, magnesium, and cadmiumderivatives of salicylaldehyde, copper( 11) and nickel( 11) derivatives of salicylal-dehyde di-imines, and copper(=) and nickel(=)-salicylaldehyde ethylenedi-imine complexes ;515 and the metal chelates of N-benzoyl-N-phenylhydroxyl-amine with aluminium, cadmium, cobalt(=), chromium(m), copper(=),iron(=), manganese@), nickel(=), and zinc.516Differential thermal analysis with various dynamic gases has been usedto identify metal carbides, nitrides, and sulphides in residues extracted fromsteels ;517 preliminary experiments on detecting changes in the compositionof the effluent gas indicated that quantitative determination of inclusioncompounds extracted from steel should be possible.Differential thermal analysis has also been applied to the determinationof the specific heat and heat of fusion of both organic and inorganic com-pounds .51*The thermal stabilities of aluminium, gallium, indium, chromium(rn),and iron(m) 8-hydroxyquinolinates have been studied by thermogravimetric,differential thermal, and thermomanometric analyses and by a sealed-tubeextraction technique.519Finally, quantitative analysis by an interesting new technique, directinjection enthalpimetry, has been described.52* In this method a smallvolume of a relatively concentrated reagent is rapidly injected into a muchlarger volume of a dilute unknown solution, and mixed within 0.01 sec.When an excess of the reagent is employed, an increase or decrease in thetemperature of the system almost always occurs, and this change in tempera-ture is a linear measure of the quantity of the substance to be determined.The technique has been illustrated with acid-base and complexometricreactions.13.Reaction-rate lbthods.-The analytical applications of enzyme-catalysed reactions have been reviewed by Blaedel and Hicks.521An automatic, spectrophotometric, reaction-rate method for the ultra-micro-determination of iodide (0.015-0.45 pg.) has been described.Themethod is based on the catalytic effect of iodine on the reduction of cerium(rv)by arsenic(~a).~~2 Similar methods have been reported for the ultrarnicro-determination of iodide in natural waters 523 and common salt.524 A similarmethod has been employed for the determination of lactic dehydrogenasein blood; this is based on the reaction of lactic acid with diphosphopyridineThe precision and accuracy are reasonably good.51rE. S. Freeman and V. D. Hogan, Anaclyt. Chem., 1964, 36, 2337.515 W. W. Wendlandt, S. I. Ali, and C. H.Stembridge, Analyt. Chim. Acta, 1964,516 R. A. Meyer, J. F. Hazel, and W. M. McNabb, AnaZyt. Chim. A&, 1964,31,517 W. R. Ban&, H. S. Karp, TV. A. Straub, and L. M. Melnick, Talanta, 1964,518 D. J. David, Analyt. Chem., 1964, 36, 2162.51Q R. G. Charles, Analyt. Chirn. Ada, 1964, 31, 405.520 J. C. Wasilewski, P. T. Pei, and J. Jordan, Aizalyt. Chern., 1964, 36, 2131.5al W. J. Blaedel and G. P. Hicks, Adv. Analyt. Chem. Instrumen., 1964, 3,5 2 2 H. V. Malmstadt and T. P. Nadjiioannou, Analyt. Chern., 1963, 35, 2157.s23 T. P. I-Iadjiioannou, Analyt. Chim. Acta, 1964, 30, 488.524 T. P. Hadjiioannou, Analyt. Chim. Acta, 1964, 30, 537.30, 84.419.11, 1327.105562 ANALYTICAL CHEMISTRYnucleotide in the presence of lactic dehydrogenase, to form reduced diphospho-pyridine nucleotide.525A rapid method has been developed for the analysis of binary and ternarymixtures of alcohols, based on the rates of the reactions of the hydroxylgroups with phenyl isocyanate; the reaction is followed by the disappearanceof the NCO band at 4.42 mp from the infrared spectrum.52* Lipase, acylase,and chymotrypsin have been determined in the presence of other esterasesby a method which was based on the hydrolysis of non-fluorescent fluoresceinesters by these enzymes, the rate of change in the fluorescence of the solutiondue to fluorescein being measured and correlated with enzyme activity;sarin, systox, and Triton X-100, which inhibit the action of these enzymes,were also determined by this method.b2' Osmium tetroxide (0.2-12 ,ug./ml.)has been determined through its catalytic effect on the luminescence developedbetween hydrogen peroxide and lucigenin; interfering ions are masked withEDTA.528An automatic method for measuring the slopes of rate curves has beenapplied to the quantitative determination of parts per million of cystine,based on its catalytic effect on the rate of the reduction of iodine by azide,the iodine being determined potenti~metrically.~~~ An automatic methodfor the assay of glucose oxidase, based on its catalytic action on the oxidationof glucose, has been described; hydrogen peroxide produced by the enzymicreaction rapidly oxidises iodide to iodine in the presence of molybdenum(v1) ;the rate of oxidation of glucose and, therefore, the rate of productionof iodine, measured potentiometrically, is equal to the glucose-oxidasea~tivity.63~ A related method has been employed for the determination ofglucose in aqueous solutions in the concentration range of 2.5-250 p.p.m.,relative standard deviations being within 1 -5%.531 The concentration ofglucose (up to 1000 p.p.m.) in aqueous solution has been determined withexcellent precision by a differential amperometric procedure based on thecontinuous measurement of the rate of the glucose-oxidase reaction in aflowing system.The hydrogen peroxide produced by the reaction of oxygenwith glucose, reacted with an excess of ferrocyanide solution in the presenceof peroxidase to produce an equivalent amount of ferricyanide, which wasdetermined with a tubular platinum ele~trode.5~2The concentration of xanthine oxidase in solution has been determinedby a potentiometric reaction-rate method, which was based on the catalyticeffect of the enzyme on the aerobic oxidation of hypoxanthine; the concentra-tion of the thiol-attacking compounds, o-iodosobenzoic acid, p-chloromercuri-benzoic acid, and silver and mercuric ions, which act as inhibitors to thisreaction, was also deterrni11ed.5~~626 T.P. Hadjiioannou and P. L. Santos, Analyt. Chim. Acta, 1964, 31, 386.526 F. Willoboordse and F. E. Critclifield, Analyt. Chem., 19G4, 36, 2270.627 G. G. Guilbault and D. N. Kramer, Amlyt. Chem., 1964, 36, 409.5 2 8 J. Bognth and L. Sipos, Mikrochim. Ichnoanalyt. Acta, 1963, 1066.689 H.L. Pardue, Analyt. Chem., 1964, 36, 633.630 H. L. Pardue, R. K. Simon, and H. V. Malmstadt, Analyt. Chem., 1964,36, 735.631 H. L. Pardue, Analyt. Chem., 1964, 36, 1110.6 3 a W. J. Blaedel and C. Olson, Analyt. Chem., 1964, 36, 343.633 G. G. Guilbault, D. N. Kramer, and P. L. Cannon, Jr., Analyt. Chem., 1964, 36,606HEADRIDGE, PIERCE, AND ANDERSON 56314. Miscellaneous.-Kolthoff 534 has written an article on the status ofanalytical chemistry, and the teaching of analytical chemistry has beenreviewed by Bark.535 Hibbits and Kallmann 536 have reported preliminaryresults of an interesting study, where they examined the specificity andaccuracy of certain wet-chemical methods for the determination of micro-grams of a particular element in the presence of 10 mg.each of 71 otherelements ; methods, often simple, for iron, copper, molybdenum, cobalt,cadmium, niobium, tantalum, and nickel were examined, and the resultswere most encouraging ; the methods were frequently specific for the elementbeing determined and the recoveries were good.The use of solid oxidants in chemical analysis has been reviewed byPickering.537 Suitable conditions have been reported for the quantitativereduction on the silver reductor from bromide solutions of iron(m) to iron@),copper@) to copper(I), vanadium(v) to vanadium(rv), uranium(v1) touranium(Iv), and molybdenum(v1) to molybdenum(v) .538 The constructionand operation of a continuous electrolytic cell, designed for the quantitativeelectrolysis of material in a flowing stream, have been described.The cell re-sembles a metal reductor columninmany respects but ismuchmoreversatile.~39The errors to be expected in the sampling of silicate rock powders forchemical analysis have been calculated and suggestions for suitable samplingprocedures put f0rward.~40 Bromine pentafluoride has been used to extractoxygen quantitatively from minerals, the liberated oxygen being determinedin a manometer.541A review on radiometric titrations has been p~blished.~42 Heit andRyan 543 have determined nickel in hexamminenickel(I1) nitrate by magnetictitration with standard potassium cyanide solution ; the titrant and titrandwere both present in an enclosed apparatus (to prevent weight losses byevaporation), which was suspended in a magnetic balance; the weight of theapparatus in the magnetic field changed slightly up to the end-point, whichwas readily located from a plot of change in weight corrected for dilutionamgainst volume of titrant added; end-point location by this method should bepossible for any system where a change in orbital moment occurs on additionof a complex-forming ligand to the metal ion solution. A very rapid methodfor the determination of nitrogen in fertilisers and other compounds hasbeen described.544 The method involves the usual conversion of nitrogen com-pounds into ammonia, followed by distillation of the ammonia in one minute,and its subsequent determination by titration; the method has also beenautomated, the total time of analysis per sample not exceeding 3.5 minutes.545534 I.M. Kolthoff, Talanta, 1964, 11, 75.535 L. S. Bark, J . Roy. Inst. Chem., 1964, 58, 4.536 J. 0. Hibbits and S. Kallmann, Talanta, 1964, 11, 1443.537 W. F. Pickering, Chemist-Analyst, 1964, 53, 91.638 F. Pantani, Analyt. Chim. Acta, 1964, 31, 121.539 W. J. Blaedel and J. H. Strohl, Analyt. Chem., 1964, 36, 1245.540 A. D. Wilson, Analyst, 1964, 89, 18.541 T. Sharnia and R. N. Clayton, Analyt. Chena., 1964, 36, 2001.642 T. Braun and J. Tolgyessy, Talanta, 1961, 11, 1277.543 M. L. Heit and D. E. Ryan, Analyt. Chim. Acta, 1963, 29, 524.544 K. A. Potrafke, M. Kroll, and L. Blom, Analyt. China. Acta, 1964, 31, 128.645 G. Kateman, L. L. M. Willemsen, J. B. G. Wijenberg, and P. 3. Stornebrink,Analyt. Chim. Actu, 1964, 31, 139564 ANALYTICAL CHEMISTRYA molten mixture of potassium pyrosulphate and potassium chloridehas been shown to be an excellent medium for dissolving all the platinum-group metals and their alloys.546 Oxide in lead has been determined byhydrogen reduction with the subsequent use of an electrolytic hygrometerto determine the evolved water; the method should be applicable to thedetermination of other metallic oxides.547 An improved apparatus for thedetermination of gases in metals by the vacuum-fusion method has beendescribed; with it the total time required for a complete analysis is 7-9minutes.648 Oxygen, hydrogen, and nitrogen in tungsten, niobium, andtantalum have been determined by vacuum-melting at 1750-1800 O ; a cobaltbath was used for tungsten, and a nickel bath for the others.549A critical comparison of the results obtained for the determination ofnitrogen in steels by a modified platinum-bath, vacuum-fusion procedure,and by the Kjeldahl, isotope-dilution, caustic-fusion and arc-extractiontechnique has shown that quantitative recovery can be achieved with theplatin~rn-bath.~~O Barium hydroxide solution saturated with bariumcarbonate has been shown to be preferable to sodium hydroxide solutionas an absorbant for carbon dioxide in the conductometric determination oftraces of carbon in metals; the method showed a, standard deviation of0.0001% of carbon a t the 0.01% carbon level.551Traces of oxygen in non-combustible gases have been determined bypassing the gas over a wire of cobaltous oxide at 1000° and measuring theelectrical resistance of the wire, which is related to the oxygen content.Traces of hydrogen can also be determined by this method through theequilibrium H20 + H, + $02.652 A portable sulphur dioxide recorder hasbeen described for the continuous determination of sulphur dioxide in air(0-80 parts per hundred million by volume) ; a reagent containing hydrogenperoxide is exposed to the air and sulphur dioxide converted into sulphuricacid; a change in the conductivity of the reagent is proportional to theamount of sulphur dioxide ab~orbed.5~~ Conditions have been establishedfor the quantitative gasometric analysis of hydrazine sulphate, isonicotin-hydrazide, benzhydrazide, and semicarbazide hydrochloride when lend(rv)and lead(n,rv) oxides are used as oxidising agents.554Satisfactory results for the determination of phosphate in feeding stuffsand fertilisers have been obtained by precipitating the phosphate with anexcess of molybdate and determining the remaining molybdate polari-metrically with (+)-tartaric acid ; increasing quantities of molybdate causeda linear increase in the optical rotation of the acid solution.555 The opticalrotation of a solution of (+)-tartaric acid also increases linearly on addition646 D. R. Gabbe and D. N. Hume, AmZyt. Chim. Acta, 1964, 30, 308.647 J. M. Hibbs and G. H. Nation, AnaZyst, 1964, 89, 49.64a T. Somiya, S. Hirano, H. Kamada, and I. Ogahara, TaZanta, 1964, 11, 581.64sY. A. Klyachko, T. A. Izmanova, and E. M. Christyakova, Zav&hya Lab.,660 V. A. Fassel, F. M. Evens, and C. C. Hill, AnaZyt. Chem., 1964, 36, 2115.661 E. J. Violante, AnaZyt. Chem., 1964, 36, S56.652A. Duquesnoy and F. Marion, BuEZ. SOC. chim. France, 1964, 77.653 D. A. Lloyd and M. Madden, J . Sci. Instr., 1964, 41, 622.664A. Berka, E. Smolkova, and E. Bocanovski, 2. analyt. Chem., 1964, 204, 87.666 W. Haas, 2. analyt. Chem., 1964, 202, 407.1963, 29, 1425HEADRIDGE, PIERCE, AND ANDERSON 565of increasing amounts of tungstate or boric acid; this fact has been usedfor the polarimetric determination of tungsten in ferrotungsten, and of boronin glass.66Some analytical problems involved in determining the structure ofproteins and peptides have been reviewed.%' The Analytical MethodsCommittee of the Society for Analytical Chemistry have reported on thedetermination of various substances in diet supplements and compoundfeeding stuffs, namely : penicillin, chlortetracycline, and oxytetracycline ;5580stilbastrol and hexoestrol ;558b nitrofurazone ;558c water-soluble vitamins ;558aand fat-soluble ~itamins.558~556A. Musil and H. Faber, 2. anaZyt. Chern., 1964, 202, 412.657D. G. Smyth and D. F. Elliot, Analyst, 1964, 89, 81.668Analytical Methods Committee, Analyst, (a) 1963, 88, 835; ( b ) 1963, 88, 925;(c) 1963, 88, 935; (d) 1964, 89, 1; (e) 1964, 89, 7

ISSN:0365-6217    

DOI:10.1039/AR9646100527

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

CRYSTALLOGRAPHYBy H. M. Powell, C. K, Rout, and 8. C. Wallwork(H.M.P. & C.K.P. : Chemical Crystallography Laboratory, The University,South Parlcs Road, Oxford;and S.C. W. : Chemistry Department, The University, Nottingham)1. INTRODUCTIONMANY crystal structures have been determined during the period. Co-ordination and organometallic compounds have attracted a good deal ofattention. Among these there is a new type of seven-co-ordinated metalatom 1 and a complex molecule containing two metal atoms with a '' fly-over " rather than a bridged structure.2 Measurements have been made ofa few bond distances between dissimilar linked metal atoms. Full structuresof natural products include absolute configurations. Apart from detailsrevealed in particular investigat'ions, there are some observations of generalinterest.The behaviour of racemic mixtures which can co-ordinate to metal atomshas been noted in a few structures.In a series of copper amidines preparedfrom the racemic amidine, the crystal contains equal numbers of enantiorners,but these are attached in pairs to copper atoms such that any one copperatom has two molecules of the same optical form, not an enantiomorphouspair.here two tartaric acid residues, both of the same optical sign, together withtwo antimony atoms, form an (( island " round a two-fold rotation axis ofthe structure. Each antimony is linked to a hydroxyl-oxygen and a car-boxyl-oxygen of an '( upper " molecule and to a similar pair of oxygens ofthe " lower " molecule, these four links from the antimony atom forming apyramid.These " islands " are present in equal numbers each containing,however, only (+)- or (-)-molecules.A group of papers is concerned with the chemistry of solid-statereactions of organic compound^.^ They deal particularly with the effectof the three-dimensional regularity of the crystal rather than of latticeirregularities on reaction mechanism, rate, and products. The course ofa certain type of solid-state reaction may be determined by the geometryA similar result is found in the tartrate( k ) - 2CSb,(C'lH*O, )21,4H,O ;L. P. Dahl and P. W. Sutton, Inorg. Chern., 1963, 2, 1067.S. Mills and G. Robinson, Proc. Chem. SOC., 1964, 187.J. Iball and C. H. Morgan, Nature, 1964, 202, 689.4 G.A. Kiosse, N. I. Golocastikov, and N. V. Belov, Doklady Akud. Nauk X.S.S.R.1964, 155, 545.5 M. D. Cohen and G. M. J. Schmidt, J. Chem. SOC. 1964, 1996; M. D. Cohen,G. M. J. Schmidt, and F. I. Sonntag, ibid., p. 2000; G. M. Schmidt, ibid., p. 2014;J. Bregman, K. Osaki, G. M. J. Schmidt, and F. I. Sonntag, ibid., p. 2021 ; D. Rabinovichand G. M. J. Schmidt, ibid., p. 2030; 31. D. Cohen, G. M. J. Schmidt, and (in part)S. Flavian, {bid., p. 2041; M. D. Cohen, Y. Hirshberg, and C. M. J. Schmidt, ibid.,pp. 2051, 2060; J. Bregman, L. Leiserowitz, mdG. M. J. Schmidt, ibid., p. 2068; J . Bregman, L. Leiserowitz, and K. Osaki, ihid., p. 2086568 CRYSTALLOGRAPHYof the reactant lattice ; it may be said to depend on “ topochemical ” factors.Such reactions are controlled by the relatively fixed distances and orient-ations between potentially reactive centres.Bimolecular reactions maybe expected to take place between nearest neighbours, so that the mole-cular structure of the product could depend on the geometrical relation-ship in the crystal of the reactant molecules. Topochemical influences areexpected to be dominant only in certain types of reaction, being probablyof minor importance, for example, when the reaction mechanism involveslong-distance migration of electrons. The crystal structures of substitutedcinnamic acids can be divided into three types according to their celldimensions. In one type, nearest-neighbour contacts between ‘CS’groups occur between parallel molecules separated by a short distance ofabout 4 A.On photodimerisation these fwm exclusively p-truxinic acids(1). It is assumed that the structure of parallel molecules constrains the/ \reacting pa,ir of monomers to form a cyclobutane dimer in which the twounits are joined head-to-head while retaining the trans-configuration. Inanother type, nearest-neighbour contacts between ‘ C dabout 3.8 8. In this case the two molecules are related by a centre ofsyrnmetry. Since all give a-truxillic acids (2) on photodimerisation, it isassumed that the formation of the centrosymmetric dimer arises because thecrystal structure constrains the reacting monomers to form a cyclobutaneh e r in which two Units are joined head-to-tail while retaining the trans-configuration.In both types of structure, reaction occurs between nearestneighbours and without change of configuration of the reaction partners,except for an adjustment required by change from trigonal to tetrahedralbond angles at the reacting carbon atoms. In the third type of crystalthe nearest ‘C=C’ neighbours are more widely separated (4.7-5.1 A).The photostability of this form is attributed to lattice constraint, whichdoes not permit the potentially reactive centres to come sufficiently closetogether. In support of the general theory are observations that for anumber of these compounds polymorphic forms occur which belong struc-turally to two, or, in one case, three, different types. The photochemicalbehaviour depends without exception on the symmetry of the reactantcrystal.Since chemical behaviour is different for different polymorphsand also differs from that in the disperse phase, it is possible to foresee appli-cations in synthesis resembling the processes in which reacting moleculesare constrained, not by others of their own kind, but by an enclosing struc-ture such as a urea or a thiourea channel./ \ are/ 2. INORGANIC AND ORGANOMETALLIC STRUCTURESBinary Compounds and Their Derivatives.-Hydrides. Calcium hydridehas a hexagonal close-packed array of calcium atoms with one half of thehydrogen atoms in the octahedral interstices and the other half at the centresof triangles of calcium atoms that form the common base of a pair of tetra-hedral interstices.6 The lanthanon hydrides,' ME, and MH3 (M = Sm,Dy, Ho, Tm, or Nd), forin two isostructwal groups but the details of thestructures are not lmown.Tantalum deuteride, Ta,D, has a body-centredcubic arrangement of tar;tslum atoms with the deuterium atoms distributedover one half of the tetrahedral holes in an ordered fashion at low temper-atures but disordered at high ternperatures.8NiZrH, has an alloy-type arrangement (a distorted version of the knownNi-Zr alloy), but the hydrogen atoms have not been located.9 In contrast,K,TcH, lo and K,ReH, l1 contain discrete [ReH,]2- or[Tc&]2- anions; here,studies of the proton magnetic resonance indicate that all the hydrogens areequivalent, and neutron-diffraction results show that the steric arrangementof the hydrogens is that in illustration (3), d(Re-H) being 1-68A.The crystalline forms designated I1 and IV ofcalcium carbide have been examined;l2 form I1 has a, triclinic lattice resem-bling the well-known cubic superstructure, and IV is il, disordered version ofthe cubic structure ; relationships between the four known polymorphs arediscussed.Neutron-diffraction studies of the carbides, CaC2, YC,, Lac,,CeC,, TbC,, LuC2, and UC,, show that they are isostr~ctural.~~ The distanceC-C is usually about 1.28 A but is longer (1.34 8) in the uranium compoundand shorter (1.19 A) in the calcium compound. The carbides, La2C3,Ce2C3, PrzC3, and Tb2C3, all contain the discrete C-C group with dE(C-C)= 1-24 A (Ce salt, 1.28 8). In a re-examination 14 of the structure of UMoC,a previous suggestion of the presence of discrete C-C groups is rejected; inthe new structure, molybdenum and uranium atoms form a slightly puckered,Carbides and silicides.ti J.Bergsma and B. 0. Loopstra, Actu Cryst., 1962, 15, 92.A. Pebler and W. E. Wallace, J . Phys. Chern., 1962, 66, 148. * W. E. Wallace, J. Chm. Phy$., 1961, 35, 2156.W. L. Korst, J. Phys. Chern., 1962, 66, 370.l o A. P. Ginsberg, Inorg. Chern,, 1964, 3, 567.l1 S. C. Abraham, A. P. Guinsberg, and K. Knox, Iizorg. Chern., 1964, 3, 558.l2 N.-G. Vannerberg, Acta Chem. Scand., 1962, 16, 1212.l3 M. Atoji, J . Chern. Phys., 1961, 35, 1950.l4 D. T. Cromer, A. C. Larson, and R. 3. Roof, jr., Acta Cvyt?t., 1964, 17, 272670 CRY S T9L L 0 GRAPH Yhexagonal array and the carbon atoms lie above or below the centres oftriangles of metal atoms ; the shortest carbon-carbon contacts are 2.88 and3.24A.In M0,C each molybdenum atom of a hexagonal close-packedarray has three nearest-neighbour carbon atoms in the same plane withitself;15 the structure is not an anti-cadmium hydroxide type. The carbides,Zr,TlC, Zr,PbC, Hf,TlC, and Hf,PbC,16 are isotypic with Cr2AlC. Alum-inium forms a tetroxycarbide, Al,04C,17 based on AlO,C tetrahedra in un-usual chains in which the tetrahedra are linked alternately by sharing edgesand corners; it has d(A1-0) = 1.71-1-87, d(A1-C) = 1.91-1.98A. Thecarbonitrides,ls AI,C,N, Al,C,N,, Al,C,N,, and .Algc3N4, together with AINand A14C3, form two structurally related polytypic series based on hexagonalpacking with similar basal spacings and different c spacings.Althoughthroughout the structures the aluminium atoms are tetrahedrally 4-co-ordinated, in no case does the carbon atom form normal sp3 tetrahedralbonds; this is cited as an example of the Pauling principle that an electron-deficient atom, here aluminium, causes adjacent atoms to increase ligancyto a value greater than their orbital number.In the isostructural silicides and germanides,lQ KSi, RbSi, CsSi, KGe,RbGe, and CsGe, unusual isolated Si, and Ge, tetrahedra have been found.Each metal atom has four of these tetrahedra as nearest neighbours. Ofthe rare-earth disili~ides,~~ those of Y, Er, Tm, Yb, and Lu are dimorphic,being of the AlB, type at low temperature and of the ThSi, type at hightemperatures.Those of Th and Ho are of the ThSi, type at all temperaturesinvestigated. Thorium germanide, ThGe2,,1 is of the ZrSi, type. Thestructures of the silicides and germanides, Fe5Si3,23 P u , S ~ , , ~ ~ Sc,Si,,Sc5Ge3, La,Ge,, Ce,Ge,,25 Rh,Si,, and Rh,Si, have also been reported.26A remarkable, anomalous polytype of silicon carbide 27 has been observedin which, during the growth of the crystal, there has occurred a change in thestructure from one region of the crystal to another without change of space-group or cell dimensions. The silicide B2.,,Si 28 has a structure related tothat of B,C. Two silicon atoms take the place of groups of carbon atoms,and the rest of the silicon is statistically substituted for part of the boronin the boron icosahedra.There have been many new structure determinations and somere-examinations of known structures, resulting in a number of new andinteresting halide types.Halides.l5 E.Parthe and V. Sadagopan, Acta Cryst., 1983, 16, 202.l6 W. Jeitschko, H. Nowothy, and R. Benesovsky, J . Less-Common Metals, 1964,lS G. A. Jeffrey and V. Y. Wu, Acta Cryst., 1963, 16, 659.l9 E. Busmann, 2. anorg. Chem., 1961, 313, 90.2o I. P. Mayer, E. Banks, and B. Post, J. Phys. Chem., 1962, 66, 693.21 A. Brown, Acta Cryst., 1962, 15, 652.2 2 P. Lecocq and A. Michel, Compt. rend., 1964, 258, 1817.28 P. Lecocq and A. Michel, Compt. rend., 1964, 258, 5655.2* D. T. Cromer, A. C. Larson, and R. B. Roof, Jr., Acta Cryst., 1964, 17, 947.25 J. Arbuckle and E.Parthe, Acta Cryst., 1962, 15, 1205.2e I. Engstrom, Acta Chem. Scand., 1963, 17, 775.P. Krishna and A. R. Verma, Acta Cryst., 1964, 17, 51.2 s B. Magnusson and C. Brosset, Actu Chem. Scan,d., 1962, 18, 449.7, 133.G. A. Jeffrey and M. Slaughter, Acta Cryst., 1963, 16, 177POWELL, PROUT, AND WALLWORK 57 IBurbank 2o reported that the idealised molecular configuration of IF7has point symmetry mm, not 5/rn of the pentagonal bipyramid, and isderived from the trigonal dodecahedra1 type of 8-co-ordination by coalescenceof two positions at one end of the four-fold inversion axis. This is thesame configuration as is found in the ethylenediamminetetra-acetatoaquo-ferrate ion. According to this author the previous fhding of a pentagonalbipyramid was due to error8 in data and refinement strategy, but otherauthors have suggested that the present treatment is not able to distinguishbetween the two stereochemical forms.The pentafluorides of niobium, tantnl~m,~O and ruthenium 31 have beenobserved to be tetrameric (4).In the niobium and the tantalum tetramerFI / Fthe fluorine bridge is linear, with d(Nb-F) = 2-06 (bridging) and 1.77 A(terminal). However, in the ruthenium compound there are three distinctsets of d(Ru-F): bridging Ru(1) and Ru(2), d = 2.05; non-bridging bondedto Ru(l), d = 1.83; and non-bridging bonded to Ru(2), d = 1.97 A.The tetrafluorides of tin and lead 32 have structures essentially similarto that of K2&F4 without the metal ions, d(Sn-F) = 2-02 for four fluorinesand 1.88 A for two others. Uranium tetrafluoride 33 is not significantlydifferent from zirconium tetrafluoride ; the uranium co-ordination poly-hedron is that of an Archimedean anti-prism. Tin tetrabromide34 hasdeformed, hexagonal, close packing of bromine atoms with tin atoms intetrahedral holes ; this structure is distinguishable from the cubic tetraiodidewhich has cubic close-packed iodine atoms.Thoriun tetraiodide has anovel layer structure;35 each thorium has eight iodine atoms at the cornersof a deformed square anti-prism ; these polyhedra share edges and triangularfaces, to give layers only weakly bonded together. A novel chain structureis found in the or-form of niobium tetraiodide ;36 octahedrally co-ordinatedniobium atoms are joined into chains by sharing edges.The niobium atomsare 0.26 A from the centres of the octahedra and appear as pairs with a 3.31 ANb-Nb separation, and d(Xb-I) = 2.65-2.90 A. There is also evidenceof strong metal-metal interaction in molybdenum tribromide 37 and tri-chloride : the halide ions are hexagonally close packed with the metal atoms29 R. D. Burbank, Actu Cryst., 1962, 15, 1207.30A. J. Edwards, J. Chem. SOC., 1964, 3714.31 J. H. Holloway, R. D. Peacock, and R. W. H. Small, J. C'hem. SOC., 1964, 644.32 R. Hoppe and W. Dahne, Naturwiss., 1962, 49, 254.33 A. C. Larson, R. B. Roof, Jr., and D. T. Cromer, Actu Cryst., 1964, 17, 555.34 P. Brand and H. Sackmann, Actu Cryst., 1963, 16, 446.35 A. Zstllrin, J. D. Forrester, and D. H. Templeton, Inorg.Chern., 1964, 3, 639.38 L. F. Dahl, D. L. Wampler, Acta Cryst., 1962, 15, 903.37 D. Babel and Mr. Rndorff, Naturwiss., 1364, 51, 85.572 CRYSTALLOGRAPHYin octahedral holes; there is distortion which brings pairs of metal atomstogether; d(Mo-Mo) = 3-30 A in MoBr, and 2-77 A in MoC1,. Rhodiumtrichloride 38 is isomorphous with aluminium chloride, and terbium tri-chloride 39 with PuBr,. Indium tri-iodide 40 approximates to cubic close-packed iodine atoms with indium atoms in adjacent pairs of octa,hedralholes, an arrangement which suggests discrete In$, molecules ; d(1n-I)= 2-84 (bridging) and 2.64 A (terminal). @-Antimony tribromide 41 con-sists of discrete pyramidal SbBr, molecules, with d(Sb-Br) = 2.49 tf, andLBrSbBr = 95.1 '.The structure of lead dichloride42 has been confirmed with improvedparameters, and barium dibromide and barium dichloride have similarstructures with 9-co-ordinated metal atoms.Strontium dibr0mide,~4 incontrast, has been shown to contain 8-co-ordinated strontium, with a verydistorted configuration. The y-form of zinc chloride 45 is isostructural withmercuric chloride.A fluoride 46 of chromium, Cr2F5, contains chromium(n1) at the centreof a regular fluorine octahedron and chromium(n) a t the centre of a distortedoctahedron (the angular distortion is similar Do that observed in CrF,).The octahedra share edges and corners to give an infinite network.The compound, Co( OH)Br, is isostructural 47 with @-Zn( 0H)Cl; eachcobalt atom is at the centre of a distorted octahedron of three bromine andthree oxygen atoms.In a similar fashion the copper hydroxide chloride,Cu(OH)Cl, is formed from layers of formula Cu(0H)Cl; each copper atom issurrounded by three oxygen atoms a t d(Cu-0) = 2-01 and one chlorine a td(Cu-Cl) = 2.30 A in a square-planar arrangement;48 two chlorine atoms at2.71 A complete a distorted octahedral co-ordination; the layers are joinedtogether by weal; O-H--Cl hydrogen bonds. Four oxygen atoms a t thecorners of a square surround the copper in Cu,(OH),Br and the isomorphouschloride and iodide ;49 the octahedron for one crystallographically uniquecopper atom is completed by five bromine atoms at 2-88 (iodine at 3.13)and one oxygen a t 2.41 A. CrOCl 50 is isomorphous with InOCl and FeOCl;and the compounds, InSC1, InSBr, InSeC1, and InSeBrS5l have a structuresimilar to that of cadmium chloride.Complex habogen-containing anions and derivatives.I n CUTiF6,4H20octahedral TiF62- ions and square-planar [Cu(H,O),] groups are joined to3aI-I. Barnighausen and B. K. Handa, J . Less-Common Metals, 1964, 6, 226.39 J. D. Forrester, A. Zalkin, D. H. Templeton, and J. C. Wallmann, Inorg. Chent.,413 5. D. Forrester, A. Zalkin, and D. H. Templeton, Inorg. Chem., 1964, 3, 63.4 l D. W. Cushen and R. Hulme, J . Chem. SOC., 1962, 2218.42 R. I. Sass, E. B. Brackett, and T. E. Brackett, J . Phys. Chem., 1963, 67, 2863.49 E. B. Brackett, T. E. Brackett, and R. L. Sass, J . Phys. Chem., 1963, 67, 2142.44 R. L. Sass, T. Brackett, and E.Brackett, J . Phya. Chem., 1963, 67, 2862.4 5 B. Brehler, 2. Krist., 1961, 115, 373.46 H. Steinfink and J. H. Burns, Acta Cryst., 1964, 17, 823.4 7 A. Ludi, X. Locchi, and Y. Iitaka, Chimia (Switx.), 1961, 15, 532; Helv. Chim.48 Y. Iitaka, S. Locchi, and H. R. Oswald, Helv. Chim. Acta, 1961, 44, 2095.4 9 H. R. Oswald, Y . Iitaka, S. Locchi, and A. Ludi, Helw. Chim. Acta, 1961, 44,5 0 H. E. Forsberg, Acta Chem. Scand., 1962, 16, 777.51 H. Hahn and W. Nickels, 2. anorg. Chem., 1962, 314, 307.1964, 3, 185.Acta, 1962, 45, 479.2103POWELL, PROUT, AND WALLWORK 573form chains by the completion of distorted octahedral co-ordination aroundthe copper by fluorine atoms of the TiF62- octahedra;52 the fluorine bridgeis not linear; interatomic distances and angles are not given.Ammoniumhexafluorogallate 53 is isostructural with caesium hexachloroantimonate,CS3SbC1,. The isolated Sn2F5- anion (5) is found in NaSn,F,, d(Sn-F)= 2.22 (bridging) and 2.07 A (terminal) ;54 the isolated anions are joined toform chains by long Sn-F bonds (2.53 8). The regular trigonal bipyrarnidalSnC1, anion has been observed j 5 in its 3-chloro-1,2,3,4 tetraphenylcyclo-butenium salt, with d(Sn-Cl) = 2.30, 2.38, 2.40 (equatorial), and 2.37,2.39 (apical). Lithium cupric chloride dihydrate 56 has been examinedCI(5) (6)by two groups of investigators, one using neutron diffraction; planar [CU,C~~]~-anions are joined by longer Cu*-Cl links (2-9A) to form chains; d(Cu-Cl)in the anion = 2.3 8; in addition, each copper atom has a water molecule atabout 2-6 A, completing a tetragonally distorted co-ordination octahedron ;in each Cu,C1,2- anion the copper spin vectors are antiparallel and lie alongthe Cu-Cu vector; the lithium atoms also have an octahedral co-ordination,with three chlorine atoms and three water molecules as nearest neighbours.In the halides, CsCdC1, and Cs2CdC1,, octahedral CdCl, groups are present ;57in CsCdC1, they share corners and in Cs,CdCl, they share faces.Cobaltoustetrachloroaluminate, Co(A.lCl,),, contains chains of this empirical formulain which the aluminium is tetrahedrally and the cobalt octahedrally co-~ r d i n a t e d ; ~ ~ the structure may also be described in terms of a hexagonalclose packing of chloride ions, between alternate layers of which the cobaltatoms occupy octahedral holes and the aluminium atoms tetrahedral holes.Following the report of the anion [Re3C1,,] ,-, an ion Re,ClI22-, withone in-plane terminal chloride less than its parent, has been found59 asthe tetraphenylarsonium salt ; and a related complex, nonachlorotris-(diethylphenylphosphine)trirhenium(m) (6), is reported;,* d(Re-Re) = 2.48,d(Re-C1) = 2.30 (out of plane) and 2.39 A (bridging), andLReClRe = 62.4".An alternative structure for the ion of empirical formula ReC1, is reportedin the pyridinium salt (PyH)HReCl,.61 This is a complex, [Re2C1,l4-,consisting of two nearly planar ReCl, groups joined by a Re-Re bond.The53 R. Weiss, J. Fischer, and G. Keib, Compt. rend., 1964, 259, 1125.53 S.Schwarzmann, 2. Krist., 1964, 120, 286.54 R. R. McDonald, A. C. Larson, and D. T. Cromer, Acta Cryst., 1964, 17, 1104.5 5 R. F. Bryan, J . Amer. Chem. SOC., 1964, 86, 733.56 P. H. Vosos, D. R. Fitzwater, and R. E. Rundle, Acta Cryst., 1963, 16, 1037;6 7 S. Siege1 and E. Gebert, Acta Cryst., 1964, 17, 790.68 J. A. Ibers, Acta Cryst., 1962, 15, 967.b Q J. E. Fergusson, B. R. Pengold, and W. T. Robinson, Nuture, 1964, 201, 181G o F. A. Cotton and J. T . Mague, Inorg. Chem., 1964, 3, 1094.61 V. G. Kuznetsov and P. A. Kozmin, Zhur. strukt. Khim., 1963, 4, 55.S. C. Abrahams and H. J. Williams, J . Chem. Phys., 1963, 39, 2923574 CRYSTALLOGRAPHYchlorine atoms lie at the corners of a square prism, i.e., in the eclipsed posi-tions. The Re-Re distance of 2-22 A is exceptionally short; d(Re-C1)= 2.43 A.Bismuth subchloride,62 the lower chloride formed in the BiC1,-Bi system,has been shown to be Bi12Cl14 (BiCll.167).Each crystallographic unit cellcontains four Big5+ ions. This ion has the form of a trigonal prism of sixbismuth atoms with three additional bismuth atoms, one projecting fromeach rectangular face, giving each bismuth atom four neighbours, withd(Bi-€3) = 3.08-3.29 A. In each cell are also eight BiClS2- ions [tetra-gonal pyramids, d(Bi-C1) = 2-61-2437 A] and two Bi,Cl?- anions. TheBi2CJS2- anion may be regarded as formed by a pair of BiC1,2- ions sharinga basal edge; one BiClS2- group is considerably distorted, with d(Bi-Cl)= 2.61-2-78 A.Tetramethylammonium tri-iododiargentate 63 is formed from doublechains of [Ag4I6I2- ions, containing tetrahedra similar to those in CsAg213and CsCu,Cl,.The a-form of cadmium sulphide 64has the zinc blende type of structure; large crystals of it have been grown.In the isostructural sulphide, Rh17S15,65 and selenide, Pd1,Sel5,66 the metalatoms occur in two types of co-ordination, square-planar and octahedral.I n the rhodium compound the octahedral are shorter than the square-planarbonds, but for the palladium compound the opposite is found.Two kinds ofcobalt atom, one with regular octahedral co-ordination and one tetrahedral,are found in CO,S,;~~ each cobalt atom with tetrahedral co-ordination is alsolinked to three similarly co-ordinated cobalt atoms at 2.58, which is thedistance Co-Co found in cobalt metal.Sesquisulphides of lutecium andytterbium 68 provide examples of octahedrally co-ordinated rare-earthcations; they are isotypic with corundum, Al,O,. In contrast, the ses-quisulphide of gallium 69 has a structure based on the wurtzite type withfour cation vacancies per cell ; the structure differs from that previouslysuggested only in the distribution of the vacancies. Short metal-metalcontacts of 2.85 A are found in Mo,S,;~O the sulphur atoms form a distortedclose-packed array with the layer sequence chhchh . . . and metal atoms are0.34 A from the centres of octahedral holes. A new type of US2,'l a tetra-gonal form, has ten uranium atoms per unit cell, eight of which are six-co-ordinated, with d(U-S) = 2.77 8.The other two, distributed over a crystal-lographic four-fold site, are eight-co-ordinated, with d(U-S) = 2.81 A; thistype is not related to the orthorhombic form. The ternary thallium chal-cogenides,72 T1,VS4, T13NbS,, Tl,TaS,, T1,NbSe4, TlVSe,, and T1,TaSe4, maySulphides, selenides, and tellurides.62 A. Hershaft and J. D. Corbett, Inorg. Chem., 1963, 2, 979.6aH. Ahlburg and R. Cakes, J. Phys. Chem., 1962, 68, 185.8 6 S. Geller, Acta Cryst., 1962, 15, 1198.6E S. Geller, Acta Cryst., 1962, 15, 713.6 7 S. Geller, Acta Cryst., 1962, 15, 1195.6* J. Flahaut, L. Domange, and M.-P. Pardo, Compt. rend., 1964, %8, 594.69 J. Goodyear and G. A. Steigman, Acta Cryst., 1963, 16,946.7 0 F. Jellinek, Nature, 1961, 192, 1065.71 R. C. L. M. Slater, 2. Krist., 1964, 120, 278.7 a C.Crevecoeur, Acta Cryst., 1964, 17, 757.H.-J. Meyer, Acta Cryst., 1963, 16, 788POWELL, PROUT, AND WALLWORK 575be described as having a substituted CsCl structure with four chalcogenatoms displaced towa.rds the transition metal around which they form atetrahedron. In T13VS4 each thallium has four sulphur neighbours at 3.1and four at 3.7 A, but each vanadium has only sulphur neighbours at 2-3 A.The ammonium salt, (NH,),WS,,73 is isostructural with ,6-K2SO4 with amean d(W-S) of 2.17 8. Two double copper sulphides are reported: the&st is formed when copper is dissolved in NbS, to give CuPbS, 74 (0.6< x < 0.8), the NbS, structure being deformed to resemble MoS,, andhaving vacancies for the copper atoms; the other, Cu5PeS4, has a modifiedantifluorite structure with six metal atoms statistically distributed overeight tetrahedral ~ites.7~ For a second polymorph it was found necessaryto postulate a statistical distribution of the metal atoms about the alreadystatistically distributed tetrahedral sites.The mixed sulphide, Ba2ZnS3,76has chains of ZnS, tetrahedra parallel to the [OOl] axis and connected bybarium ions; each barium ion has seven sulphur neighbours, and the structureis isotypic with that of K,CuCl,. A close packing of sulphur atoms in thelayer sequence ABCACABCBCABC. . . . . . . . . . is found in In,ZnS4;77 one-half of the indium atoms is in octahedral holes and the other half of them,together with all the zinc atoms, in the tetrahedral holes.In AgSbS,,7smiargyrite, the silver and antimony atoms lie near alternate lead-atomsites in the galena-type structure, but the sulphur atoms are greatly dis-placed; as a result the antimony and sulphur atoms have co-ordinationmembers of three and two, respectively. The co-ordination of antimony issimilar to that in tetrahedrite, Cu12Sb4S13,79 and other antimony-containingminerals. In tetrahedrite there are two types of copper atom, one tetra-hedrally co-ordinated and the other with a trigonal plane co-ordinationsystem. A re-examination of galenobismsthite 80 shows the presence ofcomposite (Bi4S8)cr, chains. Sulphur -sulphur bonds are found in a-Na2S2,a-K2S2, and p-Na,S, ;81 selenium-selenium bonds occur in Na,Se, ; d( S-S)= 2.13 8, and d(Se-Se) = 2-38 8.The S, system occurs in V(S,),,s2 wherethe shortest S-S distances are 2.03 8; there are other sulphur-sulphurcontacts at 3.14 A; in the eight-co-ordinated square anti-prism of sulphuratoms around vanadium d(V-S) = 2.41 A.There are three phases of the Ti-Se system-TiSe,.,,, TiSe,.,,, andTiSe,.2-,.o.s3 The fist has an orthorhombic NiAs-like structure. InTiSel.,, this is changed to the hexagonal NiAs system with 5% of the titaniumsites vacant. There is discontinuity over the region Se1.2-1,3 and a mono-clinic deformation of NiAs is found in the composition range Se1.3.-1.4. Inthe range Sel.4.-2.0 a structure based on close packing of selenium atoms isK. Sasvari, Acta Cryst., 1963, 16, 719.7 4 K. Koerts, Acta Cryst., 1963, 16, 432.7 5 N.Morimoto, Acta Cryst., 1964, 17, 351.i 8 H. G. Schnering and R. Hoppe, 2. anorg. Chem., 1961, 312, 99.77 F. Lappe, A. Niggli, R. Nitsche, and J. G. White, 2. Krist., 1962, 117, 146.'13 C. R. Knowles, Acta Cryst., 1964, 17, 847.7 9 B. J. Wuensch, 2. Krist., 1964, 119, 437.*l H. Foppl, E. Busmann, and F.-K. Frorath, 2. anorg. Cltern., 1962, 314, 12.8 2 R. Allmann, I. Baumann, A. Kutoglu, H. Rosch, and E. Hellner, Naturwiss.,Y. Iitaka and W. Nowacki, Acta Cryst., 1962, 15, 691.1964, 51, 263.F. Grunvold and F. J. Langmyhr, Acta Chern. Scand., 1961, 15, 1949576 CRYSTALLOGRAPHYformed. All the forms of niobium and tantalum diselenides 84 have hexa-gonal layer structures with metal atoms in trigonal prism environments.Palladium selenide Pd,Se 85 is isomorphous with the sulphide, Pd4S.Osmiumtelluride, O S T ~ , , ~ ~ has a pyrites structure. Introduction of 5% of antimonyto give OsTe,.,Sb,., causes a change to the marcasite type. OsSb, has a,lollingite structure .Oxides and oxy-acids. (a) Oxides. Scheelite, CaW04,S7 the prototypeof a large group of mixed oxides, has been re-examined and accurate atomicparameters have been deduced. The ilmenite-type structure has been foundin CdSnO, 88 and in the A1,0,-Cr2O3 89 system. The ordered magneticstructure of ilmenite, COT~O,,~~ has been shown by neutron-diffractionmethods to be of the same type as NiTiO,; within each (111) plane the Co2+spin is ferromagnetically coupled, but alternate layers are antiparallel.A n unusual anti-type of the well-known mixed oxide form, perowskite, isfound in the nitrides Mn,AgN, Mh,GaN, Cr,GaN, and Mn3CuN.91 Thesesquioxide, In203,92 surprisingly is isostructural with Mn,O,, and notFe203 as might have been expected, but the indates, CdIn,O,, SrIn,04,and BaIn,0,,g3 are closely related to CaFe,O,.A neutron-diffractionstudy 94 of U308 has shown an unusual arrangement in which the uraniumhas six near neighbours at 2.07-2.33 8 and an even more distant neighboura t 2.71 8 for one of the two crystallographically distinct uranium atoms,the other being at 2.44 8. Uranyl hydroxide, U02(OH)2,g5 has a structureformed from hydrogen-bonded layers of UO,( OH), octahedra sharing corners.Sodium cobaltomolybdates, NaCo,.,,(Mo04) has an unusual structure 943built up from a framework of MOO, tetrahedra and COO, octahedra; thetetrahedra provide the link between the sheets and columns formed by theoctahedra; in the sheets, octahedra share corners and edges, and in thecolumns they share faces; over all octahedra, only about 75% of the totalcobalt required is present in the lattice; a zig-zag void left by the MOO,tetrahedra links is filled with sodium atoms. In CaTa,OBYg' octahedra ofTaO, share edges and corners.The calcium ions lie in channels in thestructure. KTiNbO, has a layer structure 98 where each sheet consists ofdouble zig-zag strings of octahedra sharing edges, the strings being bondedthrough potassium ions in distorted cube environments.The st'ructure of the quartz-like GeO, has been determined:g9 < GeOGe84 F. Kadijk, R.Huisman, and F. Jellinek, Rec. Trav. chim., 1964, 83, 768.as F. Grmvold and E. Rast, Acta Cryst., 1962, 15, 11.86 W. D. Johnston, J . Inorg. Nuclear Chem., 1961, 22, 13.87 A. Zalkin and D. H. Templeton, J . Chem. Phys., 1964, 40, 501.88 I. Morgenstern-Bsdarau, P. Poix, and A. Miehel, Compt. rend., 1964, 258, 3036.89 H. Saalfield, 2. Krist., 1964, 120, 342.90 R. E. Newnham, J. H. Fang, and R. P. Santoro, Acta Cryst., 1964, 17, 240.91 C. Samson, J.-P. Bouchaud, and R. Fruchart, Compt. rend., 1964, 259, 392.92 M. Betzl, W. Hase, K. Kleinstuck, and J. Tobisch, 2. Krist., 1963, 118, 473.OS F. R. Cruickshank, D. McK. Taylor, and F. P. Glasser, J . Inorg. NwZear Chem.,g 4 B. 0. Loopstra, Acta Cryst., 1964, 17, 651.9 5 R .B. Roof, Jr., D. T. Cromer, and A. C. Larson, Acta Cryst., 1964, 17, 701.96 J. A. Ibers and G. W. Smith, Acta Cryst., 1964, 17, 190.97 L. Jahnberg, Acta Chem. Scand., 1963, 17, 2548.98 A. D. Wadsley, Acta Cryst., 1964, 17, 623.Q9 G. S. Smith and P. B. Isaacs, Acta Cryst., 1964, 17, 842.1964, 937POWELL, PROUT, AND WALLWORK 577= 130.1" (cf. a-quartz 142"); d(Ge-0) = 1.737 and 1.741 8. In the oxy-nitride,lO0 Si2N20, each silicon atom is tetrahedrally surrounded by threenitrogen atoms [d(Si-N) = 1.71 A] and one oxygen atom [d(Si-0) = 1.71 A].The most remarkable new oxy-acid anion is theperxenate ion, the structure of which has been determined in K4Xe06,9H20,101Na4Xe06,8H,0,102 and Na,Xe06,6H,0.10z It is agreed that the Xe064-ion is a regular octahedron, the largest deviation from 90" octahedral anglesbeing about 2".Estimates of the xenon-oxygen bond length lie between1.84 and 1.86 8. For all three structures the metal-ion co-ordinations andthe hydrogen-bond systems are discussed in detail in the papers cited.Closely related to the perxenates are the tellurates. In mercuric tellurate,Hg,Te0,,lo4 the [Te06]6- ion is octahedral, with d(Te-0) = 1.98 8; so isthe [Te(OH),O]- ion in KTeO(OH),,H20,105 but here the deviations from90" angles are as much as 7". Five Te-0 distances of 1-90-1-95A arebelieved to involve the hydroxyl group, and the single Te-0 distance of1.83 A is to the isolated oxygen atom. Quadrivalent tellurium in den-ningite, (MY1,Lu,Zn)Te,O5,lo6 has three oxygen neighbours in pyramidalarrangement, with d(Te-0) = 1-92 8; two TeO, groups share an oxygenbridge, to give Te2OS2- ions, each tellurium having one long Te-0 distanceof 2.36 A.In sodium biselenate lo' two forms (7) and (8) of the anionare found. The three-co-ordinated selenium is pyramidal. The form of( b ) Simple oxy-acids.the tetrathionate ion in sodium tetrathionate log confirms the observationon this ion in the barium salt BaS4O6,2H2O. The chromat'es, TCr0,,lo9where T is a lanthanon, are isostructural with ZrSiO, below 650", but abovethis temperature they have perowskite structures. The structures of HCrO,and DCrO, have been examined by neutron diffraction;l10 the results con-cerning the hydrogen-bond system were consistent with those obtained earlierby nuclear magnetic resonance and infrared techniques.The 0-D-0bond, d(O...O) = 2-55 8, is unsymmetrical, d(0-D) = 0.96 8; t,he situationfor the O-H-0 bond is less certain, but agreement is as good with a syrn-metrical bond as with any other model. The hydrated tetraperoxytungstate,K2W,011,4H20, contains discrete [W,011,2H20]2- ions.lll Each tungstenatom is surrounded by a pentagonal bipyramid of oxygen a.toms; theloo C. Brosset and I. Idrestedt, Nature, 1964, 201, 1211.lol A. Zalkin, J. D. Forrester, D. H. Templeton, S. M. Williamson, and C. W. Koch,lo2 J. A. Ibers, W. C. Hamilton, and D. R. MacKenzie, Inorg. Chem., 1964, 3, 1412.loa A. Zalkin, J. D. Forrester, and D. H. Templeton, Inorg. Chem., 1964, 3, 1417.lo4 M.T. Falqui, Ricerca sci. Rend., 1963, 3, 627.lo5 S. Raman, Inorg. Chem., 1964, 3, 634.lo6 E. M. Walitzi, Naturwiss., 1964, 51, 334.lo' Chou Kung-du, Hu Sin-chou, and Yu. Da-jiun, Sci. Sinica, 1963, 12, 1938.lo8 0. Foss and A. Hordvik, Acta Chem. Xcand., 1964, 18, 662.log G. Buisson, F. Bertaut, and J. Mareschal, Compt. rend., 1964, 259, 411.110 W. C. Hamilton and J. A. Ibers, Acta Cryst., 1963, 16, 1209.ll1 F. W. B. Einstein and B. R. Penfold, Acta Cryat., 1964, 17, 1127.J . Amer. Chem. SOC., 1964, 08, 3569578 CRYSTALLOGRAPHYequatorial planes of two bipyramids are approximately at right angles, andeach equatorial plane contains two laterally co-ordinated peroxide groups anda shared oxygen bridge; one apical position is occupied by a water molecule,and the other by a doubly bonded oxygen atom; d(W-0) = 1.93, d(0-0)= 1-50, d(W-H,O) = 2.30, and d(W-0) = 1.68 8.Ammonium perortho-niobate, (NH,),Nb08,112 is said to contain the isolated NbO,3- ion.Polyoxy-acids. A new germanate, Na,Ge,0,,,113 is the first germanatein which the GeO, octahedral group has been observed; the GeO, octahedraare linked with GeO, tetrahedra to form a three-dimensional network; inthe GeO, group d(Ge-0) is, on average, 1.90 8, markedly longer than thetetrahedral Ge-Q bond of 1.74 8.The crystal structures of the silicate minerals, bresterite,ll4 dechiardite,ll5hodgkinsonite,l16 ~nonticellite,~~~ rhodonite,llS and low and high albites,ll9have been reported. Work has continued on the interpretation of thephysicochemical properties of the chabazite minerals in terms of crystalstructure.120The potassium hydrogen metasilicate, K4(HSiO,),,l2f is found to containa (Si,012)s- ring system, analogous to the phosphate (NH,),P,Ol, butunusual in silicate chemistry.The P,O,,*- ring anion has been reported in the triclinic form of sodiumtetrametaphosphate tetrahydrate 122 and the structure is in general similarto that of the monoclinic form of this salt.It has been suggested that adisordered array of P,Ql,4- rings and [PO,-], chains is present in the an-hydrous form of sodium tetrarnetaphosphate,l23 Similar [PO,-], chainsare found ordered in [Pb( In crystals of the aluminophosphat,e,turquoise, CuAl,( PO,),( OH)2,4H20,125 zig-zag chains of AlO, octahedrashare corners with each other and with PO, tetrahedra; the copper atom isat a tetragonally distorted octahedral site surrounded by oxygen atoms offour AlO, octahedra. Aluminium phosphate, is an isotype ofa-quartz.The metaborates CrBO,, VBO,, and TiB0,,127 all have the calcite struc-ture.In anhydrous zinc metaborate 128 all the boron atoms a.re tetrahedral,the BO, tetrahedra being linked to each other to give a three-dimensionalnet; the zinc atom also lies at the centre of a tetrahedron of oxygen atoms,three of which are attached to boron atoms while one is free. Lithium112 J. E. Guerchais and R. Rohmer, Compt. rend., 1964, 259, 1135.1 1 3 pu’. Ingri and G. Lundgren, Acta Chem. Scand., 1963, 17, 617.l l * A . J. Perrotta and J. V. Smith, Acta Cryst., 1964, 17, 857.G.Gottardi and W. M. Meier, 2. Krist., 1963, 119, 53.ll6 P. J. Rentzeperis, 2. Krist., 1963, 119, 117.11’ H. Onksn, Naturwiss., 1964, 51, 334.lls D. R. Peacor and N. Nilzeki, 2. Krist., 1963, 119, 98.119 P. P. Williams and H. D. Megaw, Acta Cryst., 1964, 17, 882.120 J. V. Smith, J . Chem. Soc., 1964, 3759.1 2 1 W. Hilmer, hTatumuiss., 1963, 50, 662; Acta Cryst., 1964, 17, 1063.laa H. 31. Ondik, Acta Cmjst., 1964, 17, 1139.123 K. Dornberger-Schiff, Acta Cryst., 1964, 17, 482.lZ4 K.-H. Jost, Naturwiss., 1963, 50, 688.lZ5 H. Cid-Dresdner, Naturwiss., 1964, 51, 380.lZ6 B. Sharan and B. N. Dutta, ,4cta Cryst., 1964, 17, 82.la’ H. Schmid, Acta Cryst., 1964, 17, 1080.lZ8 P. Smith, S. Garcia-Blanco, and L. Rivoir, 2. Krist., 1964, 139, 375POWELL, PROUT, AND WALLWORIC 579metaborate 129 has a structure built up of endless chains of trigonal planarBO, groups, lithium atoms holding the chains together. The sodium borate,NaB( OH)*,2H20, consists of discrete tetrahedral [B( OH),]- ions and octa-hedrally co-ordinated sodium ions ;130 hydrogen bonds link the oxygen atomsinto sheets and the sheets into a network.Refinements of the structuresof the orthorhombic form of boric acid 131 and of hambergite, Be2B03.0H,132have been reported.Two independentexaminations have been made of the ferroelectric lithium hydraziniumsulphate ;I33 lithium ions and sulphate ions form a three-dimensional networkin which there are channels; the hydrazinium ions lie in these channels andare linked in infinite chains by hydrogen bonding ; the ferroelectric proper tiesappear to be associated with movement of hydrogen atoms within the33chains.Lithium oxalate 134 has been subjected to very careful scrutiny:the lithium ion has an irregular tetrahedral co-ordination by oxygen atoms;the oxalate ion is planar, with d(C-C) = 1.561 8, which is more than theseparation expected for single bond order; d(C-0) = 1-264 and 1-252 A;all these distances are corrected for libration of the oxalate ion. In sodiumhydroxide tetrahydrate each metal ion has six oxygen neighbours, of whichfive involve acceptor hydrogen bonds and one a donor hydrogen bond. InKF,4H20,136 edge- and corner-sharing octahedra [F(H,O),]- and [K(H20)6]+are found; d(K-0) = 2.79 8, d(F-H-0) = 2-71 and 2-78 A; the 0.-H-0bonds linking the octahedra have lengths 2432 and 2.858.InBa( OH),,8H20 137 eight water molecules complete a distorted square anti-prism about the barium ion [d(Ba-0) = 2.69-2.77 A].A neutron-diffraction study of MgS04,4H,0 138 has confirmed the struc-ture determined by X-ray methods; the hydrogen bonds from water mole-cules to sulphate groups are considerably bent. There has also been are-appraisal of the hydrogen bonding in magnesium ammonium sulphatehexahydrate:139 this shows that the metal atom is surrounded by a regularoctahedron of water molecules each of which is hydrogen-bonded to twosulphate ions; one of the N-H bonds is involved in a bifurcated hydrogenbond with two sulphate-oxygen atoms.Manganese dichloride tetrs-hydrate 140 contains octahedrally co-ordinated manganese, each manganeseatom having four water molecules at 2.21-2-22 A and two chloride ionsseverally at 2.476 and 2.600 if. Ferrous sulphate heptahydrate, BeSO4,7H,O,contains six water molecules bound to the metal ion, and the seventhHydrated metal salts and salts of simple oxy-acids.lz9 W. H. Zachariasen, Acta Cryst., 1964, 1'9, 749.13* S. Block and A. Perloff, Acta Cryst., 1963, 16, 1233.lS1 C. R. Peters and M. E. Milberg, Acta Cryst., 1964, 1'7, 229.132 W. H. Zachariasen, H. A. Plettinger, and M. Marezio, Acta Cryst., 1983, 16,133 J. H. van den Hende and H. Boutin, Acta Cryst., 1964, 17, 660; I. D. Brown,134 B. Beagley and R. W. H. Small, Acta Cryst., 1964, 17, 783.135 G.Beurskens and G. A. Jeffrey, J. Chem. Phys., 1964, 41, 924.138 G. Beurskens and G. A. Jeffrey, J . Chem. Phys., 1964, 41, 917.13' H. Manohar and S. Ramaseshan, 2. Krist., 1961, 119, 357.133 W. H . Baur, Acta Cryst., 1964, 17, 863.1 3 9 T. N. Margulis, Diss. Abs., 1963, 24, 995.140 A. Zalkin, J. E. Forrester, and D. H. Templeton, Inorg. Chem., 1964, 3, 529.1144.ibid., p. 654580 CRYSTALLOGRAPHYhydrogen-bonded to one of the other six and not to the sulphate ion; thewater molecule bound to the metal ion and hydrogen-bonded to the seventhwater molecule has a Fe-0 separation (2.198) longer than the other fiveFe-0 distances (2.12 4 . 1 4 1The sulphate tetrahedra in the isotypic anhydrous cadmium and mer-cury sulphates are also surrounded by distorted octahedra of oxygen atoms.142In mercuric sulphate monohydrate, however, each mercury ion has sixoxygen neighbours-five sulphate-oxygen atoms and one water molecule-at the corners of a very distorted octahedron;143 the Hg-0 distances varybetween 2.17 and 2.51 8. Cerium in cerium magnesium nitrate hydrate 144has twelve oxygen neighbours, from six chelating nitrate ions, at the cornersof an irregular icosahedron. Each magnesium has six water molecules atthe corners of an octahedron.EuSO, is isomorphous with SrSO,, andEuCO, with KNo3.145The Stereochemistry of Covalent Compounds of the Typical and B Sub-group Elements of Groups III, V, and VI.-Boron compounds. Isomerismhas been established in the boron hydride series. In normal and iso-B18Hzz,two B,, units as found in B1oHl4 share B(s~-B(lo~ edge;1*6 in normal B&&they are joined so that the molecule has a two-fold symmetry axis.InB2,H1,, two BloH14 cages join at the open faces, with the loss of bridgingand terminal hydrogen on the four boron atoms which join the ~ages.1~7The B,, skeleton is also present in 1-ethyldecaborane and several othercompounds.148 In Bl,H12[S(CMe3),]2,14s the sulphur atoms are attached tothe terminal boron atoms; B,H,,(MeCN) 150 has essentially the B,, skeleton,with one boron missing and the MeCN attached through the nitrogen tothe boron atom opposite the vacancy in the skeleton. In octachloro-1,2-dicarbadodecaborane, Bl,H2C18C,H,,151 a near-regular icosahedral BloC2framework was found [d(C-C) = 1.68 A], with chlorine atoms on all theboron atoms except those nearest the carbon atoms; both the molecular-orbital and the resonance approach lead to the conclusion that the chlorineatoms are the most positively charged.The stable Bl,H1,2- ion 152 (sym-metry Dad) has eight boron atoms at the corners of a square anti-prism,the remaining two being each above one of the square faces of this poly-hedron; the B-B distances are 1.86 in the basal planes and 1-82 A along theother sides of the square anti-prism. The two apical boron atoms are atI 4 l W. H. Baur, Acta Cryst., 1964, 17, 1167.142 P. A. Kokkoros and P. J. Rentzeperis, 2. Krist., 1963, 119, 234.143 L. K. Templeton, D. H. Templeton, and A. Zalkin, Acta Cryst., 1964, 17, 933.144 A.Zalkin, J. D. Forrester, and D. H. Templeton, J . Chem. Phys., 1963, 39,lP6 I. Mayer, E. Levy, and A. Glasner, Acta Cryst., 1964, 17, 1071.146 P. G. Simpson and W. N. Lipscomb, J . Chem. Phys., 1963,39,26; P. G. Simpson,K. Folting, R. D. Dobrott, and W. N. Lipscomb, ibid., p. 2339; P. G. Simpson, K. Folt-ing, and W. N. Lipscomb, J . Amer. Chem. SOG., 1963, 85, 1879.14' R. D. Dobrott, L. B. Friedman, and W. N. Lipscomb, J . Chem. Phys., 1964,40, 866.148 A. Perloff, Acta Cryst., 1964, 17, 332.149 D. E. Sands and A. Zalkin, Acta Cryst., 1962, 15, 410.laoF. E. Wang, P. G. Simpson, and W. N. Lipscomb, J . Chem. Phys., 1961, 35,151 J. A. Potenza and W. N. Lipscomb, J . Amer. Chem. SOG., 1964, 86, 1874.la2R. D. Dobrott and W. N. Lipscomb, J. Chm.Phys., 1962, 37, 1779.2881.1335POWELL, PROUT, AND WALLWORK 5811.73 A from their nearest neighbours. Et*NH,,B,H,,*NHEt is the fkstcompound found to have a B, fragment of the boron icosahedron;'53 theEt-NH, group is attached to boron by a single bond, but the Et-NH groupforms a bridge between two boron atoms, an arrangement previously ob-served only in B,H5*NEt,. Iodopentaborane, B,H,I (9), has a tetragonalpyramid of boron atoms with the iodine attached to the atom at the apex;154the distances between the apical boron atom and an atom in the base is1-71 A, but between two adjacent boron atoms both in the base the distanceis 1-84 A; the B-I distance 2.20 is little different from that in boron tri-iodide.ls5I1B-H-BM e Me(9) ( ' 0)HIIf localised bonds are used the best structure for the carboraneB,H,C,Me,, based on X-ray-diffraction evidence, is (10) ;156 the boron-carbon bond length is 1-52 and &(C=C) = 1.432 8.The carborane, B5H,C,,has been shown by microwave spectra techniques to be pentagonal-bipyra-midal with terminal boron atoms and '' in-plane '' non-adjacent carbonatorns.l57 Dichlorodimethylamioborane dimer [BCl,N( CH3),], has a four-membered B,N, planar ring with peripheral chlorine atoms and methylgroups;W8 the rather long single bonds [d(B-C1) = 14335and 1.826, andd(C-N) = 1.505 A] and the acute angles (NBN 86.9") suggest the possibilityof three-centre bonds. Boron trifluoride dihydrate 159 contains the F,B-OH,tetrahedral molecule and a, water molecule, or more probably the [F,B-OH]-ion and a hydronium ion H30+; the boron tetrahedron is only slightly dis-torted [d(B-F) = 1.36, 1.34, 1.40 8; d(B-0) = 1.565 A], but there are someshort hydrogen bonds and long van der Waals' contacts in the crystal.Tridecaboron diphosphide l60 is formed from B12 icosahedra with linearP-B-P units between the icosahedra.B,, icosahedra are also found inaluminium boride, AlB,,.Phosphorus, arsenic, and antimony. The expected trigonal-pyramidalforms have been found for various compounds in which these elements arein the tervalent state. In phosphorus tricyanide, P(CN),,lG1 angles CPChave an average value of 93" with d(P-C) = 1.78 A and LPCN = 172".153 R. Lewin, P. G. Simpson, and W. N. Lipscomb, J .Chem. Phys., 1963, 39, 1532.154 L. H. Hall, J . Amer. Chem. SOC., 1964, 86, 4729.155 M. A. Ring, J. D. H. Donnay, and W. S. Koski, Inorg. Chem., 1962, 1, 109.lK6 W. E. Streib, F. P. Boer, and W. N. Lipscomb, J . Amer. Chem. Xoc., 1963,15' R. A. Beaudet and R. L. Poynter, J . Amer. Chem. SOC., 1964, 86, 1258.15* H. Hess, 2. Krist., 1963, 118, 361.15* Won-Bong Bang and G. B. Carpenter, Acta Cryst., 1964, 17, 742; Won-Bong160 L. H. Spinar and C. C. Wang, Acta Cryst., 1962, 15, 1048.161 K. Emerson and D. Britton, Acta Cryst., 1964, 17, 1134.85, 2331.Bang, Diss. Abs., 1964, 24, 3552582 CRYSTALLOGRAPHYAll the intermolecular P40.N contacts are shorter than the sums of the normalvan der Waals' radii. Triphenylphosphorus l 6 2 is also pyramidal, withd(P-4) = 1-82 8, but owing to unequal rotations of the phenyl groupsabout the P-C bonds the molecule as a whole is without symmetry.Tri-pxylylarsine,163 arsenic t r i b r ~ m i d e , ~ ~ ~ and antimony tri-iodide 165 [d(Sb-I)= 2.72 8, LISbI = 99.1'1 are essentially similar.The trigonal-bipyramidal pentaphenylphosphorus 165a [d( P-C) axial =1-99, equatorial = 1 a85 A] and pentaphenylarsenic contrast sharply withthe tetragonal-pyramidal arrangement of pentaphenylantirnony.165b In thelast mentioned d(Sb-C) lies between 2.05 and 2-35 A and there is no evidenceto suggest that the axial bond is larger or shorter than the rest.Bisdiphenylarsenic oxide, ( Ph2As),O,lGs contains the expected pyramidalco-ordination about the arsenic atoms; the angle AsOAs of 137" is ratherlarge and the As-0 distances of 1-67 8 are somewhat shorter than expected;p n 4 n bonding between the arsenic and oxygen is suggested.The structure of '' methyl metadithiophosphonate," 167 (MePS,),, hasbeen refined in detail, and that of cacodyl disulphide, (Me,AsS), (ll), deter-mined.168 The tervalent arsenic atom is pyramidally co-ordinated withS y A ~ - S /'s( ' 2) ( 1 !Iangles at the arsenic atom of 96-99'; the quinquevalent arsenic atom hamstetrahedral environment with angles of 101-1 16 O ; the angle AsSAs is96.5', and the shortest arsenic-arsenic separation is 3.24 8, i.e., shorter thanthe sum of the van der Waals' radii.Smithite, AgAsS2, contains theAs& group (12) ;Iss each arsenic is pyramidal and d(As-4) is 2-21-2.36 8.Arsenic telluride, a semiconductor, is formed of zig-zag chains inwhich arsenic is bonded to tellurium octahedrally, [d(As-Te) = 2.76-2.93 A]or trigonally [d(As-Te) = 2.68-2.77 A]; the structure is closely related tothat of @-Ga,O,.In germanium arsenide, GeAs2,171 each germanium atomis tetrahedrally bonded to arsenic, and each arsenic has three long andthree short germanium contacts in the form of a distorted octahedron.Electron-diffraction has been used 172tlo investigate the stereochemistry of SF, which has the form of a distortedSulphur, selenium, and tellurium.l G 2 J. J. Daly, J . Chem. SOC., 1964, 3799.lG3 J. Trotter, Acfa Cryst., 1963, 16, 1187.lG4 A. K. Singh and S. Swaminathan, Current Sci., 1964, 33, 429.lG6 A.Almenningen and T. Bjorvatten, Acta Chem. Scand., 1963, 17, 2573.P. J. Wheatley, J . Chem. SOC., 1964, 2206.l e 6 b P . J. Wheatley, J. Chem. SOC., 1964, 3718.lG6 W. R. Cullcn and J. Trotter, Canad. J . Chem., 1963, 41, 2983.lG7 J. J. Dsly, J. Chem. SOC., 1964, 4065.168 N. Cameron and J. Trotter, J . Chem. SOC., 1964, 497.E. Hellner and H. Burzlaff, Naturwiss., 1964, 51, 35.G. J. Csrron, Acta Cryst., 1963, 16, 335.171 J. H. Bryden, Acta Cryst., 1962, 15, 167.172K. Kimura and S. H . Bauer, J . Chem. Phys., 1963, 39, 3172POWELL, PROUT, AND WALLWORK 583trigonal-bipyramidal molecule with one equatorial atom missing, and ofOSF, in which the vacant equatorial site is occupied by an oxygen atomwith some change in the distortion of the bipyramid as shown schematicallyCI(13) (14) (15) (16)in (13, 14).Electron diffraction has also shown that the angle SiSSi of97.4" in (SiH,),S l T 3 is considerably smaller than the angle SiOSi of 144"in (SiH3),O;l7, d(Si-S) = 2.136, and d(Si-0) = 1.63 8. An interestingsulphur chain has been observed in C13C*S,*CC1,;175 d(S-S) = 2.03 8; anda remarkable selenium chain in the anion (SeCN), 176 (15) in K(SeCN),,QH,O;here d(Se-Se) = 2.7 and 2.64 8 and LSeSeSe = 177"; the SeCN systemhas been assumed to be linear and the whole anion appears to be coplanar.Four-co-ordinated selenium, trigonal-bipyramidal with one equatorial atommissing, has been observed in 1,1,4,4-tetrachlor0-1,4-diselenan 177 (16) ;it has d(Se-C) = 1-86 and d(Se-C1) = 2.24 8; the angle ClSeCl is approx-imately 180 '.Di-iododi-4-chlorobiphenylyltellurium 178 also contains asimilar four-co-ordinated tellurium derivative ; however, d( Te-I) is ratherlong and d(I--I) somewhat short.Co-ordination compounds. Much of the work in this field has been onco-ordination complexes of elements of the first transition series.Diammonium oxotetratrisisothiocyanatovanadate pentahydrate 179 con-tains the tetragonal-pyramidal [(SCN),V0J2- ion (17), with d(V-0) = 1-62and d(V-N) = 2.04 8; a distorted octahedron is completed by zb watermolecule, with d(V-0) = 2.22 8. Diperoxotriamminechromium(1v) 18* hasa distorted pentagonal-bipyramidal form (18), with d(Cr-NH,) = 2.08-2-15 A; the oxygen-oxygen distance in the peroxo-group is 1-43 8, the same0 / s /='.c ,S NH,17$ A.Almenningen, K. Hedberg, and R. s i p , Acta Chm. Scand., 1963, 17, 2264.174 A. Almenningen, 0. Bastiansen, V. Ewing, K. Eedberg, and M. Traettenberg,175 H. J. Berthold, 2. Krist., 1961, 116, 290.176 0. Foss and S. Hauge, Acta Chem. Scand., 1963, 17, 1807.177 A. Amendola, E. S. Gould, and B. Post, Inorg. Chm., 1964, 3, 1199.178 G. Y. Chao and J. D. McCullough, Acta Cryst., 1962, 15, 887.17u A. C. Hazell, J . Chem. Soc., 1963, 5745.180 R. Stomberg, Arkiu Kemi, 1964, 22, 49.Acta Chem. Scand., 1963, 17, 2455684 ClRYSTALLOGRAPHYas is found in the dodecahedra1 peroxochromate.lsl Stromberg lS2 nowagrees that CrO( 02)C5H5N has the distorted pentagonal-pyramidal form.The oxomolybdenum(v) xanthate (19) complex lS3 is binuclear with a linearoxo-bridge, the Mo-S distances varying between 2.46 and 2.715 A andd(Mo-0) from 1.644 to 1.87 A; the authors give a detailed discussion ofthe electronic structure.The trioxodiethylenetriaminemolybdenum(vI)group lS4 has three mutually cis-oxygen atoms, with d(Mo-0) = 1.735 A,as in formula (20); the octahedron is very distorted with LOMOO of106" and LNMoN of 75"; the chelate rings have the expected puckeredform.The low-spin trisacetylacetonatomanganese(m) has the expected octa-hedral structure, but distorted with 0-Mn-0 angles of 97";185 the M-0distance is rather short, 1460-14393 8.The solvate of manganese(I1) dichlorophosphate, Mn(P02C12),,2EtOAc,has a most unusual chain structure (21) of infinite strings of MnO, octahedrajoined by 0,PC12 molecules;186 the ester groups are in cis-positions; thedistances of manganese to phosphato-oxygen and keto-oxygen are, respec-tively, on average, 2.13 and 2.20 8.Dichlorodihydrazinemanganese(n) lg7is an isotype of the corresponding zinc compound. Here chains are formedfrom hydrazine-bridged MnCl,N, octahedra but with the chlorine atoms intrans-positions. The stereochemistry of ethylenediaminetetra-acetato( HY)-complexes of manganese(@, as Mn,(HY),,lOH,O;lbs and of iron(m), asRb[Fe(OH,)Y],H,O lS9 and LiFe(OH,)Y,2H20,190 have been examined;the existence of seven-co-ordinated [Mn(H20)Y]2- and [Fe(H,O)YI- ionshas been established. The former of these may be related to an octahedronwith two nitrogen atoms occupying one octahedral site opposite the oxygenatom [d(Mn-0) varies between 2.212 and 2.261 A and d(Mn-N) is very long(2-40 and 2-35 A)].The [FeH,OYl- ions differ in that the co-ordinationpolyhedron is much nearer to a pentagonal bipyramid; d(Fe-0) is muchlE1 R. Stomberg, Acta Chem. Scand., 1963, 17, 1563.183 R. Stomberg, Arkiu Kemi, 1964, 22, 29.183 A. B. Blake, F. A. Cotton, and J. S. Wood, J. Amer. Chem. SOC., 1964, $6, 3024.lS4 F. A. Cotton and R. C. Elder, Inorg. Chem., 1964, 3, 397.lE6 J. Danielsen and S. E. Rasmussen, Acta Chem. Scand., 1963, 17, 1971.18' A. Ferrari, A. Braibanti, G. Bigliardi, and F. Dallavalle, 2. Krist., 1963, 119, 284.lE8 S. Richards, B. Pedersen, J. V. Silverton, and J. L. Hoard, Inorg. Chena., 1964,lDo M. J. Wamor, T.A. Hamor, and J. L. Hoard, Inorg. Chem., 1964, 3, 34.B. Morosin and 5. R. Brathovde, Acta Cryst., 1964, 17, 705.3, 27.M. D. Lind and J. L. Hoard, Xnorg. Chem., 1964, 3, 34POWELL, PROUT, AND WALLWORK 585shorter (1.94-2.13A) and d(E'e-N) a little shorter (2.30 and 2.35& thanthe corresponding distances in the manganese compound. The anions in themanganese salt are joined together by very short hydrogen bonds Ed( O-H.-O)= 2-47 81 to give chains of [Mn(OH,)YH]"-; the stoicheiometry of the crystalis achieved by the presence of further six-co-ordinated manganese ionswhich are linked to four water molecules and two carboxyl-oxygen atoms.The iron atom bonds in sodium nitroprusside, Na,[Fe(CN) ,NO],H,O, areoctahedrally disposed;lgl the Fe-N-0 system is linear and d(Fe-N) is veryshort (1.63 if).Anhydrous acetylacetonatocobalt(n) is a tetramer with four octahedrallyco-ordinated cobalt atoms in a chain;192 there are three distinct types ofacetylacetone groups, one chelating with both its oxygen atoms bonded toa terminal cobalt atom, a second with one oxygen bonded to a terminalcobalt atom and one bridging oxygen bonded to two cobalt atoms, and athird with both oxygen atoms bridging and bonded to two cobalt atoms.Dinitratobis(trimethy1phosphine oxide)cobalt(rr) 193 has the cobalt atomoctahedrally co-ordinated with chelating nitrate groups [see (22)] ; the ex-pected octahedral cation is found in trans-dichlorobisethylenediammine-cobalt(m) nitrate [Co en,C1,]N03,1g4 where d(Co-N) 1.99-2-00 and d(Co-Cl)= 2.26 if; the nitrate ions occupy two sites in the same plane in a disorderedMe,P0I"\0 0\ / ' / O X 0o-NXN-o - 0 -CO - 0- PMe 3/ \ 9 P 0 0Narray with equal occupation numbers in the positions indicated diagrammati-cally in formula (23).Azidopentamminecobalt Ig5 azide has the expectedoctahedral co-ordination, a slight difference being found between the ionicand the co-ordinated azide groups; the ionic form is almost linear (LN"= 179.3") and nearly symmetrical [d(N-N) = 1.158 and 1.172 if)] ; the otherdeparts a little from the linear form (L"N = 177.5") and is not sym-metrical [d(N-N)= 1.145 and 1.208 4 1 . The purpureo-salt, [Co(NH,),Cl]Cl,,has a structure similar to those of the ruthenium and rhodium salts, withd(Co-N) = 1.91-1.97 ,4.lg6 Powell and Wells' structure of Cs,CoCl, hasbeen confirmed in general, but a detailed refinement 197 has shown that thedistortions of the [COC~,]~- tetrahedron are in the opposite sense to thoselglP.T. Manoharan and W. C. Hamilton, Inorg. Chem., 1963, 2, 1043.Ig2F. A. Cotton and R. C. Elder, J. Amer. Chem. SOC., 1964, 86, 2294.lS3 F. A. Cotton and R. H. Solderberg, J . Amer. Chem. SOC., 1963, 85, 2402.lS4 S. Ooi and H. Kuroya, Bull. Chem. SOC. Japan, 1963, 36, 1083.lS5 G. J. Palenik, Acta Cryst., 1964, 17, 360.lS6 Y. Shigeta, Y . Komiyamct, and H. Kuroya, Bull. Chern. SOC. Japan, 1963, 36,lg7 B. N. Figgis, M. Gerloch, and R. Mason, Acta Cryst., 1964, 17, 506.1159586 CRYSTALLOGRAPHYsuggested by them. Nickel(0) in tetrakis-( l-difluorophosphinopiperidine)-nickel has the expected tetrahedral form with d(Ni-P) = 2.2 Thepossibility of steric interference in bis(di-2-pyridyliminato)palladium(II) 199(24) producing a tetrahedral form has been examined; in fact, inter-ference is avoided by the bending of the chelate rings into a boat form.The nickel and palladium bis-o-phenylenebismethylarsine complexes,Ni[C,H,(AsMe2),]12 and Pt[C6HP(AsMe2),]Cl2, show no steric anomalies ;ZOOthe PtAs, and NiAs, groups are square-planar and the halogen atoms com-plete distorted octahedra; d(Pt-C1) = 4-16 A, an ionic distance, but d(Ni-I)is much shorter than an ionic contact.The nickel-iodine interaction isso strong that the arsenic tetrahedron is distorted; however, the compoundis diamagnetic.Di-(N-isopropylsalicyla81diminato)nickel(rr) 201 has tetra-hedral nickel bonds, but in very distorted form, with d(Ni-N) = 1.950 andd(Ni-0) = 1.895 8. /I-Alaninenickel dihydrate 202 is octahedral and littledistorted; the alanine is bidentate by co-ordination through one nitrogenand one oxygen atom. In dichlorotetrakisthioureanickel [ (NH2)2CS]4NiC12,203octahedral bonds also occur, but very distorted, with d(Ni-C1) = 2-40 and2-52 8. The molecular structures of the Lifschitz metal(@ complexes,2o4the blue and the yellow form of bis-meso-stilbenediaminemetal(11) dichloro-acetate, have been examined: the blue form contains only octahedral nickel,an octahedron being made up from the square-planar bis-nzeso-stilbenedi-anlinenickel with two molecules of water; the yellow form contains the simplesquare-planar complex and the octahedral dihydrate in equal numbers.Nickel xanthate 205 and bis-N-ethyl- 206 and bis-N-butyl-salicylaldiminato-palladium 207 are normal square-planar complexes.The structures of thetetraphenylporphine complexes of nickel, copper, palladium, zinc, and irondiffer among themselves;208 the first three metals in the list form normal19* S . Greenberg, A. Amerdola, and R. Schmutzier, Natumuiss., 1963, 50, 593.lg9 H. C. Freeman, J. F. Geldard, F. Lions, and M. R. Snow, Proc. Chem. SOC.,2oo N. C. Stephenson and G. A. Jeffrey, Proc. Chem. Soc., 1963,173; N. C. Stephenson,201 M. R. Fox, P. L. Orioli, E. C. Lingafelter, and L. Sacconi, Acta Cryst., 1964,202 P.Jose, L. M. Pant, and A. B. Biswas, Acta Cryst., 1964, 17, 24.203 A. Lopez-Castro and M. R. Truter, J. Chern. Soc., 1963, 1309.20* W. C. E. Higginson, S. C. Nyburg, and J. S. Wood, Inorg. Chem., 1964, 3, 463;205 M. Fritnzini, 2. Krist., 1963, 118, 393.206 E. Frasson, C. Panattoni, and L. Sacconi, Acta Cryst., 1964, 17, 85.207 E. Frasson, C. Panattoni, and L. Sacconi, Acta Cryst., 1964, 17, 477.208 E. B. Fleischer, C. K. Miller, and L. E. Webb, J. Amer. Chern. SOC., 1964, 86,1964, 258.Acta Cryst., 1964, 17, 592.17, 1159.S. C. Nylsurg and J. X. Wood, Inorg. Chem., 1964, 3, 468.2342POWELL, PROUT, Ah'D WALLWORK 587square-planar complexes, with d(Ni-N) = 1.957, d(Cu-N) = 1.981, andd(Pd-N) = 2.009 A; the zinc complex is a dihydrate and the water mole-cules complete a distorted octahedron, with d(Zn-N) = 2.042 and d(Zn-OH,)= 2447 A; the iron complex is also a dihydrate, but the iron atom isvirtually five-co-ordinate, with d(Fe-N) = 2.03 and d(Fe-OH,) = 2.95 and2.179 A.Copper(1) diethyldithiocarbamate is a tetramer [Et,NCS,Cu], ;aos thefour copper atoms are at the corners of an almost regular tetrahedron[~(CU-Cu) = 2.658 and 2-757 A] ; the diethyldithiocarbamate moleculesare bound through sulphur to the four faces of the tetrahedron, one of thetwo sulphur atoms being linked to two copper atoms and the second to thethird copper atom of a tetrahedral face; a detailed discussion of this structureis described by the author as an application of chemical topology.Thecuprous ion-benzene complex in C6H6,CU~Cl4 210 contains copper bound tothree chlorine atoms at 2-55, 2-37, and 2.40 8, severally, and to a benzenering (25); the copper interacts with a specific double bond of the benzenemolecule; it is at distances 2.15 and 2.30 A from the carbon atoms joined bythis bond, and at a distance of 2.13 A from the centre of the bond, in whichd(C=C) = 1.20 A; the other C-C bond lengths (141, 1.25, 1-37, 1.29, and1.40 d) show a clear alternation of double and single bonds in the ring.Eachaluminium atom is bound to four chlorine atoms at the corners of a tetra-hedron. One chlorine is unshared; the others form bridges between alumin-ium and copper.In tristhiourea copper(1) chloride, the bonds from copper are tetrahedral,with angles nearer normal than those previously reported.211Electron-diffraction measurements made on copper(=) nitrate as a gas 212show the molecule %o be planar and the nitrate groups bidentate, withd(Cu-0) = 2-00 5 0.02 8, LOCuO = 70°, LON0 = 120" & 2".Thesquare-planar copper amidines (26) and (27), as prepared from the racemicztmidine, have all t,he molecules of one enantiomeric form attached in pairsto one set of copper atoms and all the molecules of the other enantiomersimilarly to another set of copper atoms.3 The compounds Cu,Cl,(MeCN),,Cu,Cl,(MeCN),, and Cu,Cl,,(C,H,*OH), form crystals whose basic units2oB R. Hesse, Arkiv Kemi, 1963, 20, 481.210 R. W. Turner and E. L. Amma, J . Amer. Chem. SOC., 1963, 85, 4046.211 Y . Oknya and C. B.Knobler, Actcz Cryst., 1964, 17, 928.%12 R. E. LaVilla and S. H. Brtuer, J . Amer. Chern. SOC., 1963, 85, 3597588 CRYSTALLOQRAPHYare (28), (as), and (30), respectively;213 these linear bridged complexes arepacked together so that the chlorine atoms of neighbouring complexes com-plete a distorted octahedron about the copper; d(Cu-C1) is about 2.30 8 forthe four bridging chlorine atoms and d(Cu-Cl) for the others, which completethe octahedron, is 2.6-3-2 8. Bisethylenediaminecopper( a) nitrate 214MeCN, cu/_ CI, Cil‘ ,Cl MeCN, ,CI, “:cI\cuOc‘P r * ~ ‘ ” ~ C I ~ ‘ c l ~ c u Y I / ‘CI .CICI’ CI’ NCMe cIycu\CI’ CI’ ‘NCMe(28) 29)CI, ,CI, ,CI. , CI, ’CI; ”, 0 Pr(30)has two truns-co-ordinating monodentate nitrate groups [d( Cu-0) = 2.591,and the corresponding thiocyanate 215 has two trans-thiocyanate groups[d(Cu-S) = 3.27 A]; in both, the copper atom has a dist,orted octahedralarrangement of bonds.I n bis-5-chlorosalicylaldoximatocopper(11),~~~d(Cu-N) = 1.96 and d(Cu-0) = 1.91 8; for bis-salicylaldoximinatocopper-(11) 217 d(Cu-N) = 1.94 and d(Cu-0) = 1.91 8; in both, copper atoms havean octahedral environment, the distorted octahedra being completed byoxygen atoms of neighbouring molecules. In di-( N-phenylsalicyla1dimato)-copper(I1) the ligands are not co-planar;218 the phenyl group is a t right anglesto the rest of the molecule and the copper has square-planar co-ordination.A third determination of the structure of anhydrous copper oxinate (quinolin-8-01 complex),219 designated the B-form, shows dimer units similar to thosein dimethylg 1 yoximat o copper.Further evidence of an association between conjugated systems andcomplexed copper atoms is provided by bis-salicylaldehydatocopper.220The structure of one of the crystal modifications shows the molecules ar-ranged so as to bring benzene rings from neighbouring ligands directly overthe fifth and sixth co-ordination positions of the metal atom and distant3-22 8 from it.A second modification is reported 221 to have close contacts(3.15 8) with oxygen atoms of the chelate rings, and the possibility of donor-acceptor interactions between different sections of the molecules is said toaccount for the crystal forms. Such long-distance associations are nowseen to be a feature of a number of copper complexes.222The little work there has been on complexes of non-transition metalshas produced interesting results.The zinc complex, bis(dipivaloy1meth-anido)zinc( 11) ,223 contains tetrahedral zinc and the chelate rings are213 R. D. Willett and R. E. Rundle, J . Chern. Pltys., 1964, 40, 838.214 Y. Komiyama and E. C. Lingafelter, Actu Cryst., 1964, 17, 1145.215 B. W. Brown and E. C. Lingafelter, Actu Cryst., 1964, 17, 254.217 M. A. Jarski and E. C . Lingafelter, Acta Cryst., 1964, 17, 1109.218 L. Wei, R. M. Stogsdill, and E. C . Lingafelter, Actu Cryst., 1964, 17, 1058.21g G. J. Palenik, Actu Cryst., 1964, 17, 687.220 A. J. McKinnon, T. N. Waters, and D. Hall, J . Chem. SOC., 1964, 3290.221 T. P. Cheeseman, D. Hall, and T.N. Waters, Nature, 1965, 205, 49-1.222 D. Hall, A. D. Rae, and T. N. Waters, Proc. Chem. SOC., 1962, 143.223 F. A. Cotton and J. X. Wood, Inorg. Chem., 1964, 3, 245.P. L. Orioli, E. C. Lingafelter, and B. W. Brown, Actu Cryst., 1964, 17, 1113POWELL, PROUT, AND MALLWORK 589symmetrical. The similar anhydrous cobalt complex is isomorphous, and adistorted tetrahedral arrangement of the cobalt bonds may account for theanomalous visible spectrum. Hydrozincite, Zn,( OH),(CO,), 224 containstetrahedrally and octahedrally co-ordinated zinc atoms in the ratio 2 : 3 ;the zinc octahedra form C,-type sheets with rectangular holes 6-3 x 5.4 8,the zinc tetrahedra being above and below t,hese holes; two oxygen atomsof the carbonate ions form bonds to the octahedra, and one to the tetrahedra[d(Zn-0) = 2.10 (octahedral) and 1.95 A (tetrahedral)].Potassium tetra-nitritomercurate(rr) nitrate 225 is said to contain four nitrite ions groupedaround the mercury atom with eight oxygen atoms [d(Hg-0) = 2.4 A].The crystals of 2HgC12,Et,S are built up of [Cl-Hg-SEt,]+ ions (LClHgS= 158"), chloride ions, and HgCl, mo1ecules,226 linked together by bridgingchlorine to a two-dimensional network of distorted HgSC1, and HgO,octahedra with two short and four long bonds; d(Hg-S) = 2.41; d(Hg-C1)is short (2-30-2.35 A). Bismethylthiomercury, Hg(SNe),,,,' is a co-ordin-ation polymer with mercaptide bridges. The basic linear S-Hg-S unit[d(Hg-S) = 2.36 81 has three other sulphur neighbours, at 3.26 A from themercury atom, completing an irregular tetragonal pyramid.Approximatelyoctahedral tin(rv)228 occurs in the complex (31) which contains a stronghydrogen bond between the hydroxyl and the methoxyl group, withd(O-H*-.O) = 2.6 A.Uranium tetra-acetate 229 is said to form (U[CH,*C00],) chains withbridging acetate groups, the uranium having eight-co-ordination in theform of a square anti-prism of oxygen atoms. Dioxo-bis-S-hydroxyquinol-inato-8-hydroxyquinolineuranium(1v),~~~ with one molecule of chloroformof crystallisation, contains a linear UO, group. The uranium atom is linkedto two chelating 8-hydroxyquinoline molecules and co-ordinated with athird molecule through oxygen only; d(U-0) is 2.25-2.32 A. d(U-N) is2.51-2-58 for two-co-ordinated nitrogen atoms ; the unco-ordinatednitrogen of the third molecule is 4.1 A distant from the uranium atom.Theseven bonds have the pentagonal- bip yramidal disposition.Two complexes have been reported that contain benzene and are probablyclathrate compounds. The first is a bis- (L)-ephedrinecopper-benzenecompound ;231 the square-planar copper complexes are hydrogen-bonded224 S. Ghose, Acta Cryyst., 1964, 17, 1051.225 D. Hall and R. V. Holland, Proc. Chem. SOC., 1963, 204.226 C.-I. BriCnden, Arlciv Kemi, 1964, 22, 83.227 D. C. Bradley and N. R. Kunchar, J. Chern. Phya., 1964, 40, 2258.228 G. Sterr and R. Mattes, 2. anorg. Chem., 1963, 322, 319.229 I. Jelenic, D. Grdenic, and A. Bezjak. Acta Cryst., 1964, 17, 758.230 D. Hall, A. D. Rae, and T. N.Waters, Proc. Chem. SOC., 1964, 21.231 Y. Amano, K. Osaki, and T. Watanabe, Bull. Chem. SOC. Japan, 1964, 37, 1363590 CRYSTALLOGRAPHYtogether in trimers; the benzene molecules fit in holes in the lattice betweenthe trimers. The second is the compound COH~,(SCN),,C,H,;~~~ the cobaltatom is surrounded by six nitrogen atoms in a nearly regular octahedralform, with d(Co-N) = 2-08-2-17 A; although the Hg:S ratio is 3: 1, eachmercury atom is bound to four sulphur atoms, two of which are shared withsome other mercury atom; the distance from mercury to these bridgingsulphur atoms (2.72-2.86 A) is significantly greater than that to the othertwo sulphur atoms (2-42-2.46 A); the distances from mercury to carbonsof the benzene molecule are 3.6A or more.Examination of the morecomplex metal carbonyls has continued.The most remarkable is Rh,(CO),,(32).233 This is the first carbonyl to be found containing six metal atoms.Each rhodium atom has two electrons more than xenon, the next inert gas.Each rhodium atom has eight neighbouring atoms or groups at the cornersof a tetragonal anti-prism. Four of these are other rhodium atoms at 2.78 A,two are terminal carbonyl groups, and the remaining two are bridgingcarbonyl groups, these being the first examples bonded to three metal atoms.Metal carbonyls and organometallic compounds.""\ i"In (32), the non-bridging CO groups of the lowest rhodium atom and the completesurroundings of the rhodium atom at the top are shown. Other CO groups are omittedto avoid confusion in the diagram.The whole structure is such that all rhodium atomsare equivalent. There is a bridging CO group above the octahedron face formed byatoms (l), (2) and (3) and another above that formed by atoms (3), (4) and (5). EveryThe ruthenium carbonyl, Ru,(CO) 12,233 is isomorphous with the osmiumanalogue, Os,(CO) 12, reported previously. Hydridopentacarbonylman-ganese, (CO),MnH,234 has a manganese atom located above the basal planeof a tetragonal pyramid of carbonyl-carbon atoms, the hydrogen atomprobably completing a distorted octahedral arrangement around the metal.Further re-examination of iron pentacarbonyl 235 indicates that the co-ordination polyhedron is a regular trigonal bipyramid ; no deviation fromthe regular form exceeds the experimental error.The selenocarbonyl,Se,Fe,(CO), (33),1 contains a new type of seven-co-ordinated metal atom;one of the iron atoms lies at the apes of a square pyramid whose base con-tains the other two iron atoms and the two selenium atoms; d[Fe-Fe (apical)]= 2.66 A; d(Fe-Se) = 2-34-2-37 8; the apical iron atom and therhodium atom has two non-bridging CO groups.232 R. Grmbaek and J. D. Dunitz, Helu. Chirn. Acta, 1964, 47, 1889.233 E. R. Corey, Diss. Abs., 1963, 24, 1384.234 S. J. LaPlaca, J. A. Ibers, and W. C. Hamilton, J . Amer. Ckern. Soc., 1961,235 J. Donolme and A. Caron, Acta Cryst., 1964, 17, 663.86, 2288POWELL, PROUT, AND WALLWORK 591selenium atoms lie in a mirror plane of the molecule. Dicobaltoctacarbonyl 236 has the structure of Fe,(CO), less one bridging carbonylgroup; d(Co-C, bridging) = 1.92, d(Co-C, terminal) = 1.80 8.The com-pound, CO,(CO),(C~HBU~)~C,H~,~ decomposes to give o-di-t-butylbenzene ;in the form indicated (34) it has a two-fold symmetry axis. This is describedas a " fly-over " rather than a '' bridged " compound.Further fluorocarbon-metal compounds have been described, includingoctafluorotricarbonylcyclohexn- 1,3-dieneir0n,~~' which has the form (35)with d(Fe-C) = 1.993 and d(Fe-C) = 2.06 8, three carbonyl groups at1.801 completing the pseudo-octahedron. The compound (36) 237a has abridging acetylene group, with d(Co-C) = 1.83-1.95 A.(34) (35)F0(36)In tetrakis(trifluoromethy1)cyclopentadienone-n-cyclopentadienylcobalt(37) the metal forms a ferrocene type of linkage to the cyclopentadiene anda c- and n-bond system with the fluoro-ketone;238 the carbonyl-carbon atomis repelled away from the metal atom, with d(C0-C) = 1.978-2*1138;for the ketone-carbon atom d(Co-C) = 2.4168.The bonding in theseand related compounds is discussed in detail. Biferrocenyl (38)239 andferrocenyl ruthenocenyl ketone ( 39)240 have the expected structures ; inthe former the rings are very nearly in the staggered position, and in theCF3( 3 7)0 Fle 0( 3 9)s3* G. G. Sumner, H. P. mug, and L. E. Alexander, Acta Cryst., 1964, 17, 732.237 M. R. Churchill and R. Mason, Proc. Chem. Soc., 1964, 226.237@ N. A. Bailey, M. R. Churchill, R. Hunt, R. Mason, and G. Wilkinson, Proc. Chem.238 M. Gerloch and R.Mason, R o c . Roy. Soc., 1964, A , 279, 170.239 A. C. MacDonald and J. Trotter, Acta Cryst., 1964, 17, 872.Z4O G. J. Small and J. Trotter, Canad. J. Chem., 1964, 42, 1746.Xoc., 1964, 401592 CRYSTALLOGRAPHYlatter midway between eclipsed and staggered. The dibenzenechromiumdiscussion continues. In the latest paper 241 it is deduced that Cotton'sdata imply no deviation from D6, symmetry, supporting Cotton's own con-clusion. Gas-phase electron-diffraction measurements on cyclopentadienyl-indium 242 indicate an open-faced half sandwich; d(1n-C) = 2.62 8, whichis 0*4A less than the sum of ionic radii. Two further methylplatinumderivatives have been reported,243 of structures (40) and (41), but detailsof the molecular dimensions are not yet given.The molecular structure (42)of the synthetic molecular-oxygen- carrier, O,IrCl( CO) (PPh,), , has beenMeI(42) PPh,reported;2u the two oxygen atoms are equidistant from the metal, as pre-dicted in Griffith's model for oxyhaemoglobin; the 0-0 distance, 1.30 8, ismidway between that in 0, and 02-; the chlorine and the carbonyl groupoccupy similar sites in a disordered array.There have been considerable advances in the crystallography of thealkali-metal organometallic compounds. Methyl-lithium is a tetramer,245the lithium atoms forming a regular tetrahedron, with d(Li-Li) = 2.56 Aand the methyl groups in the centre of each face; the bonding has been dis-cussed by a molecular-orbital approach. In ethyl-lithium there is a basic-ally similar tetramer, but the distortions of the tetrahedron, [d(Li-Li) = 2.42and 2-63 81 suggest two strongly associated dimers.246 In lithium tetra-ethylal~minate,~~' chains of alternate lithium and aluminium atoms arebridged by methylene groups of ethyl radicals; the structure, it is claimed,can probably be largely accounted for in terms of Li+ ions and AlEt4- ions;d(Li-C) = 2.02, d(A1-C) = 2-32, and d(A1-Li) = 2-30 8.Chains of pyra-midal trimethyltin groups and fluorine atoms are found in Me3SnF;248 thereis some uncertainty in the structure but a simple ionic lattice seems im-probable. Tetramethylstibonium tetrakistrimethylsiloxyaluminate 249 con-sists of tetrahedral anions and cations, with &(Si-0) = 1-568 andLAlOSi = 147".Compounch containing metal-metal bonds.Crystal-structure analysis haspreviously shown or confirmed the existence of metal-metal bonds in a2 4 1 J. A. Ibers, J. Chem. Phys., 1964, 40, 3129.248 8. Shibata, L. 8. Bartell, and R. M. Gavin, Jr., J . Chem. Phys., 1964, 41, 717.24s J. E. Lydon, M. R. Truter, and R. C. Watling, Proc. Chem. Soc., 1964, 193.244 J. A. Ibers and S. J. LaPlaca, Science, 1964, 145, 920.245 E. Weiss and E. A. C. Lucken, J. Organometallic Chem., 1964, 2, 197.246 H. Dietrich, Acta Cryst., 1963, 18, 681.247 R. L. Gerteis, R. E. Dickenson, and T. L. Brown, I n o r g . Chem., 1964, 3, 872.s48 Clark, O'Brien, and Trotter, Proc. Chem, SOC., 1963, 85.249 9. J. Wheatley, J. Chem. SOC., 1963, 3200POWELL, PROU'f, AND WALLWORK 593number of compounds, but until recently these bonds have been betweentwo or more atoms of the same element.It is now apparent that manycompounds can be made in which different metal atoms are bonded to eachother. Several crystal structures provide direct proof that this is so andsome metal-metal interatomic distances have been obtained. In triphenyl-tin tetracarbonyltriphenylphosphemanganese, Ph,SnMn(CO),PPh,, thethree atoms Sn, Mn, and P are collinear. The distance Sn-Nn was reportedas 2.55 but a revised value is 2.627 8 . 2 5 0 In the closely related bispenta-carbonylmanganese diphenyltin, Ph,Sn[Mn(CO)5J2,251 there is a sequence ofatoms Mn-Sn-Mn with bond angle at the tin atom of 117' and two agreeing(though crystallographically independent) Sn-Mn distances of 2.70 A ; theother two bonds from tin complete a distorted tetrahedral arrangement,LCSnC = 110".The Au-Mn bond has been confirmed for Ph,PAuMn(CO),and Ph,PAuMn(CO),P( OPh) 3.252 The SnCl , group is linked through tinto the iridium atom in biscyclo-octa-1 ,5-dieneiridium trichlorotii~~52ORGANIC STRUCTURESCarboxylic Acids.-As part of a study of the effect of replacing CH, byCF, in compounds containing the H,GC-0 group the crystal structure ofammonium triffuoroacetate has been determir~ed.~~a The original hyper-conjugation theory predicts a shortening of the C-C bond, but lengtheningis also possible by a change in hybridisation. In practice, no significanteffect is observed because &(C-C) is 1-542 -+ 0.009 8, to be compared with1.55 & 0.02 A in acetic acid.The two C--0 bonds do not differ significantlyin length and each oxygen atom accepts two hydrogen bonds from ammoniumions.At high concentrations of D,O, an unstable form of dideuterioxalic aciddideuteriohydrate crystallises which is not isomorphous with oxalic aciddihydrate, although it has a similar hydrogen-bond network in its crystalstructure;254 the long hydrogen bonds have similar lengths in the two forms,but the short hydrogen bonds are extended from 2.49 in H2C04,2H,0 to2-588 in the deuteriated form, showing the expected isotope effect. Thefull accounts 255 have now appeared of the accurate structure determinationsof lithium oxalate and ammonium oxamate, which show abnormally longC-C bonds (1.561 &- 0.004 and 1.564 0.002 8, respectively); in both casesthe anions are planar, suggesting that intramolecular repulsions are unlikelyto be the cause of this lengthening, which is more probably due to parti-cipation of the oxygen lone-pair electrons in molecular orbitals embracingthe whole ion.Rather long central bonds (1.55 8) are also found 256 forboth ions and molecules in the structure of potassium tetraoxalate,2 5 0 R. F. Bryan, Proc. Chem. SOC., 1964, 232.251B. T. Kilbourn and H. M. Powell, Chem. and Ind., 1964, 1578.252 H. M. Powell, K. Mannan, B. T. Kilbourn, and P. Porta, Proc. 8th Internat.253 D. W. J. Cruickshank, D. W. Jones, and G. Walker, J. Chem. SOC., 1964, 1303.2 5 4 F. Fukushima, H. Iwasaki, and Y. Saito, Acta Cryst., 1964, 17, 1472.255 B.Beagley and R. W. H. Small, Acta Cryst., 1964, 17, 783; Proc. Roy. SOC.,256 D. J. Haas, Acta Cryst., 1964, 17, 1511.Conference on Co-ordination Chemistry, Vienna, 1964.1963, A, 275, 469594 CRYSTALLOGRAPHYK(HC20,)(H2C20,),2H,0 ; in this case the oxalic acid molecules are planarbut there is a 6" twist between the two ends of each ion; the hydrogenbonds formed by t,he C-OH groups as donors are all short (2.50, 2.50, and2.54 A).The crystal structure of sodium 2-0x0-octanoate 257 resembles that ofsodium a-oxobutyrate but, by contrast, the molecules of the 0x0-octanoateseem to be in the keto-form; however, the crystals exhibit one-dimensionaldisorder 258 and this, together with an unexpectedly long d(C=O) of 1.32 8,indicates that this distinction between the two molecules is open to doubt.In the crystal structure of suberic acid,2S9 HO,cfCH,],*CO,H, the centro-symmetric molecules have their planar terminal C*C02H groups linked inthe usual way across centres of symmetry by pairs of hydrogen bonds.Dimet'hyl 2,5-dihydroxycyclohexa- 1,4-diene-1,4-dicarboxylate (43) is a newform of cyclic condensation product of methyl succinate; it exists in twocrystal fornis,360 which differ only in having parallel or antiparallel packingof chains of molecules; in both, the cyclohexadiene ring is planar.In furan-3,4-dicarboxylic acid (44) 261 the furan ring is planar, and theplane of symmetry in the structure is perpendicular to the ring and passesthrough the centre of the intramolecular hydrogen bond of length 2-555 A;the molecules are also linked across centres of symmetry by single hydro-gen bonds of length 2.639 8; in each type of hydrogen bond the protonsmust be placed either centrally or symmetrically about the centre, statisti-cally or in double potential wells; the thermal parameters make statisticalaveraging unlikely.Each carboxyl group is rotated by 3.8" and slightlytilted out of the plane of the ring. The C-0 distances to the intra- andinter-molecularly linked oxygen atoms are 1.267 and 1.234 8, respectively.In 3-thenoic acid262 the carboxyl group is twisted about 44" out of theplane; it seems that heterocyclic acids are distorted in this way more easilythan aromatic acids; the molecules are hydrogen-bonded to form centro-symmetric dimers with a 0.21 A separation between the planes of the twolinked carboxyl groups; the bond angle at the sulphur atom is 98" (cf.92"in 2-thenoic acid), and the average d(S-C) of 1.70 A indicates consider-able double-bond character at these points. In indol-3-ylacetic acid 263the dihedral angle between the planes of the acid group and of the indole2 5 7 S. S. Tavale, L. 31. Pant, and A. B. Biswas, Acta Cryst., 1964, 17, 215.258 L. M. Pant, Acta Cryst., 1964, 17, 219.269 J. Hausty and M. Hospital, Acta Cryst., 1964, 17, 1387.260 P. Ganis, C. Pedonc, and P. A. Ternussi, Atti Accad. naz. Lincei, Rend. Classe261 D. E. Williams and R. E. Rundle, J . Amer. Ghem. SOC., 1964, 86, 1660.262 P. Hudson and J. H. Robertson, Acta Cryst., 1964, 1'7, 1497.26s I.L. Karle, K. Britts, and P. Gum, Acta Cryst., 1964, 17, 496.Sci. Jis. mat. nut., 1963, 35, 68, 175POWELL, PROUT, AND WALLWORK 595group is 63", and the two hydrogen-bonded carboxyl groups in the centro-symmetric dimers are very nearly coplanar. It is interesting that the indole-NH groups are not involved in hydrogen bonding.Acyclic Compounds.-n-Pentme appears264 to be too small to have thenormal orthorhombic parallel packing in the crystal lattice characteristic ofhigher paraffins. The chain axes are parallel neither to the c-axis nor toeach other. The average &(C-C) found in the structure determination at-145" is 1.525 & 0.010 A and the average LCCC is 112" & 0-50". Thecrystal structure of O-methylhydroxylamine hydrochloride has beendetermined from three-dimensional data, but the reported R value of0.276 is remarkably high; so, although the d(C-0) of 1.46 A, d(0-N) of1.42 8, and ,/-CON of 109" agree fairly well with electron-diffraction values,they should be accepted with reservation; each hydrogen atom of the NH,+group is involved in hydrogen-bond formation to a different C1- ion.Crystalsof trirnethylamine oxide,266 Me3N0, have the hydrogen atoms of the methylgroups in a staggered conformation and the pecking of the molecules isdominated by dipole-dipole forces, though there are no short N-s.0 contacts.It is interesting to compare the d(N-0) of 1.404 & 0.005 A in this structure,where the dative bond N+O results i s a formal negative charge on theoxygen atom, with the d(N-0) of 1.438 -J-- 0.011 A in Me3N+-OH,Cl-.Afurther refinement z87 of previous three-dimensional data 268 for urea givesdimensions correc+,ed for the r.m.s. libration of 13" about C-0 bond as119.0' & 0.6" and LNCO = 120-5" rf 0.3". The N-H-w.0 hydrogen-bondlengths are now 2.985 0.007 and 3.009 0.008 8. An alternativehydrogen-bond scheme has been proposed z69 for taurine, NH2*CH,*CH2*S03H ;this fits the experimental results equally well and avoids the previous un-likely conclusion that the molecule did not have the zwitterion structure.The cation in tetramethylenediammonium chloride has its carbon andnitrogen atoms in the form of a coplanar zig-zag chain,27* this trans-con-figuration contrasting with the gauche configuration found previously forthe adipate. Preliminary results are reported 271 for the structure ofspermine phosphate hexahydrate :+H3N.[CH,],*NH,+.~CH,],~NH,+~[CH2],*NH,+2HPO,~-,6H,Owhich has been determined to provide information on the binding of thephosphate and water units in view of the affinity which this amine showsfor nucleic acids; the arrangement of sgermine ions in " herring-bone "pattern layers, hydrogen- bonded to interleaving phosphate + water layers,shows some similarity to the arrangement of the phosphate groups in DNA.In the crystal structure of dicinnamyl d i s ~ l p h i d e , ~ ~ ~ (Ph*CH:CH*CH,*S),,follows: d(C-0) = 1.276 rf 0.008, d(C-N) = 1.356 & 0.007 A, LNCN =2a4N.Xorman and H. Mathisen, Acta Chem.Scand., 1964, 18, 353.265 A. Lsurent and C. Rerat, Acta Cryst., 1964, 17, 277.266 A. Caron, G. J. Pitlenik, E. Goldish, and J. Donohue, Acta Cryst., 1964, 17, 102.267 A. Caron and J. Donohue, Acta Cryst., 1964, 17, 544.268 P. Vaughan and J. Donohue, Acta Cryst., 1952, 5, 530.26s J. Donohue, Acta Cryst., 1964, 17, 761.z7* T. Ashida and S. Hirokawa, Bull. Chenz. SOC. Japan, 1963, 38, 1086.271 Y. Iitaka and Y. Huse, Bull. Chem. SOC. Japan, 1964, 37, 437.2 7 2 G. W. Smith and P. E. Whyman, Nature, 1964, 202, 999596 CRYSTALLOGRAPHYthe molecule adopts a curled configuration which is thought to be stabilisedby interaction between each double bond and a sulphur atom; it is a pitythat this unusual structure was investigated in one projection only.Allthe carbon and nitrogen atoms of the centrosymmetric molecule of (' hexa-acrylonitrile," 273 [(NC*CH2*CH2)2C(CN)*CH:]2, lie in three planes, one foreach pair of cyanoethyl groups which have the tram-staggered configurationand one for the rest of the molecule which has a trans-arrangement aboutthe central double bond; the rather short &(CzS) of 1.123 8 is thought tobe due, partly to the use of spherical form factors for the atoms in spite ofthe concentration of electrons in the C a bond, and partly to the lackofcorrection for molecular libration; the antiparallel packing of CN groups inthe crystal suggests dipoledipole interaction and the possibility of CH,-Nhydrogen bonding is discussed. A preliminary description of two carbanionstructures, NH,+C-(CN), and C,H,N+-C-(CN)2, has been given;27* in bothcases the bonds to the trigonal carbon atom deviate significantly (by about3") from planar, in spite of the possibility of resonance stabilisation of planarconfigurations.Aromatic and Other Homocyclic Molecules.4yclopropenyl is expectedto be a stable aromatic system, according to the (4n + 2) rule, but onlyderivatives which provide further stabilisation have so far been isolated.One of these is sym-triphenylcyclopropenium perchlorate, the structure ofwhich is the subject of a preliminary rep0rt.~7~ The cyclopropenyl ringand the three carbon atoms attached to it are approximately coplanar butthe phenyl rings are twisted about 21" out of the plane to relieve repulsionsbetween the ortho-hydrogen atoms.The average cyclopropenyl andexocyclic C-C bond lengths are 1.40 and 1.45 A, respectively.Neutron-diffraction studies 276 of solid benzene at -55" and -135"provide bond lengths requiring only small librational corrections [meand(C-C) = 1.398 8; mean d(C-H) = 1.077 at -55" and 1.090 A at -135'1and indicate small changes in molecular orientation with temperature toallow more economical packing. The same effect is found in a comparisonof low-temperature and room-temperature structure determinations ofanthracene;,77 from new data, and by further refinement of earlier data, itis found that the molecule has mmm symmetry, within experimental error,though only a centre of symmetry is required crystallographically ; compari-son of the bond lengths with those predicted theoretically shows that thelimitations in the theoretical calculations may be disguised by the choice ofbond-order/bond-length curve so that any method may be able to predict273 M.J. Kornbleu and R. E. Hughes, Acta Cryst., 1964, 17, 1033.274 C. Bugg, R. Desiderato, and R. L. Sass, J. Anw. Chm. SOC., 1964, 86, 3157.M. Sundaralingam and L. H. Jensen, J. Amer. Chem. SOC., 1963, 85, 3302.276 G. E. Bacon, N. A. Curry, and S. A. Wilson, Proc. Roy. SOC.. 1964, A, 279, 98.R. Mason, Acta Cryst., 1964, 17, 547POWELL, PROUT, AND WALLWORH 597bond lengths to better than 0.02 8. Perylene (45) is one of the simplestpolynuclear aromatic hydrocarbon molecules to have some formally singlebonds (the peri-bonds) in all the non-excited bond structures; a three-dimensional structure analysis 278 shows these t o have &(C-C) = 1.471 &0.006 A and all the bond lengths agree with values predicted by valence-bond and molecular-orbital calculations.The molecule is slightly foldedabout its long axis, probably owing to intermolecular steric effects.A new examination of the structure of phenol279 on the basis of thespace group 2'2, and by means of three-dimensional data results in onlyminor modifications from the earlier determination on the basis of P212,2,.Overcrowding is expected in 1,2,4,5-tetrabromobenzene but the molecularconformation is the same in both the 8- and the y-phase,280 stable below and' above 46 O , respectively, with neither asymmetry nor deviation from planarityof any significance; in both structures the molecules are stacked in columns,but staggered so as to avoid direct overlap of atoms, and the phases H e rin the types of intermolecular contacts-mainly between stacks in thep-phase and within each stack in the y-phase.Crystals of pentabromo-and pentachloro-fluorobenzene are interesting in that they show increasingdegrees of disorder;281 two of the halogen positions in the pentabromo-compound are statistically occupied by bromine and fluorine, so that eachis effectively (+Br + +F)¶ whereas there is a statistical distribution amongstall the halogen positions in the pentachloro-compound amounting to(5/6C1+ 1/6F) in each position. Nuclear magnetic resonance (n.m.r.)evidence shows that the pentachloro-compound also has a partially disorderedphase below 195"~.2,6-Dichloronaphthalene has a normal structure 282with expected molecular dimensions.The effect of steric hindrance on molecular conformation has beenexamined for a number of overcrowded molecules. In 5-bromo-6-chloro-acenaphthene (46) the structure is disordered,283 so that the two halogenpositions are each occupied statistically by (+C1 + *Br), but it is still clearthat these two positions are pushed apart, both within the plane of thenucleus, and by moving in opposite directions out of this plane. Similardistortions of the halogen positions occur in 5,6-dichloro-ll,12-diphenyl-naphthacene,2S4 and t,he phenyl substituents are also twisted about 70" out278 A.Camerman and J. Trotter, Proc. Roy. Soc., 1964, A , 279, 129.280 G. Gafner and F. H. Herbstein, Acta Cryst., 1964, 17, 982.281 T. L. Khotsyanova, V. I. Robaa, and G. K. Semin, Zhur. strukt. Khim., 1964,282 T. L. Khotsymova and Yu. T. Struchkov, Zhur. strukt. Khim., 1964, 5, 404.28s R. L. Avoyan and Yu. T. Struchkov, Zhur. strukt. Khirn., 1964, 5, 407.284 R. L. Avoyan, A. I. Kitaigorodskii, and Yu. T. Struchkov, Zhur. strukt. Khim.,C. Scheringer, Z. Krist., 1963, 119, 273.5, 644.1964, 5, 420598 CRYSTALLOGRAPHYof the plane of the naphthacene nucleus. In 1,8-dinitronaphthaIene 285 thenitro-groups are twisted about 45" round the C-N bond, and the nitrogenatoms are also pushed apart and in opposite directions out of the meanplane of the naphthalene nucleus which is itself distorted from a regularplanar form.The withdrawal of the n electrons from the ring by the two substituentsin p-nitrophenyl azide causes a quinonoid deformation of the ring;286 theazide chain is nearly linear and a t an angle of 118" to the main molecularaxis, though only 5" away from being coplanar with the ring. There isstrict planarity of the whole molecule, except €or the methyl group, inmethyl o-nitrobenzenesulphenate (47),287 together with the short (244 A)non-bonded S--0 distance it indicates both strong resonance stabilisationand partial S-.O bonding, probably involving the sulphur p - and d-orbitals ;the single bond length (1.648 & 0412 8) between t,he bivalent sulphurand oxygen atoms is somewhat shorter than expected.Investigation ofo-nitroltenzaldehyde by X-ray 288 and neutron diffraction 289 shows noevidence for an internal C-H*-O hydrogen bond; in fact, both substituentsare rotated about 30" out of the plane of the ring and they are tilted slightlyin opposite directions away from the plane, so as to avoid each other; theC-N bond length does not appear to be affected by the consequent reductionin conjugation. The intermolecular C-He-0 interactions are discussed inthe last section. By contrast, internal O-H*-O hydrogen bonding insalicylamide 290 reduces the twist of the amide group from the plane of thebenzene ring to about 3".A comparison of the structure of N-metliyl-p-chlorobenzaldoxime (pre-pared in the anti-configuration by the use of dimethyl sulphate) with thoseof syn- and anti-p-chlorobenzaldoxime 2Q1 shows a remarkable shortening ofthe N-0 distance to 1.284 & 0.006 A in the N-methyl compound from,e.g., 1.408 If: 0.007 A in the syn-form of the non-alkylated aldoxime.Thereis an accompanying increase in the C=N bond length and the oxime group istwisted slightly out of the plane of the ring. Nitrosophenols can exist alsoas quinone-oxime tautomers. The oxime form has been establishedpreviously for the stable, orange =-form of 4-n-propoxy- 1,2-benzoquinonel-oxime and it has now been found to predominate in an intramolecularlyhydrogen-bonded syn-configuration in the green /3-f0rm,~9~ though there maybe some disordering of the hydrogen-atom positions to give some of thenitrosophenol tautomer.The propoxy-group has the guuche conformationwith the methyl group out of the plane of the rest of the molecule. A some-what analogous tautomerium can exist in molecules where there is thepossibility of bonding between adjacent nitroso- or related groups, but thisdoes not occur in cis-1,2-acenaphthenediol dinitrate (48) because the two2s5 Z. A. Akopyan and Yu. T. Struchkov, Zhur. atrukt. Khim., 1964, 5, 496.288 A. Mugnoli and C. Mariani, Cazzetta, 1964, 94, 665.W. C. Hamilton and S. J. LaPlaoa, J. Amer. Ghem. SOC., 1964, 86, 2289.zssP. Coppens and G. M. J. Schmidt, Acta Cryst., 1964, 17, 222.289 P. Coppens, Acta Cryst., 1964, 17, 573.290 T. Sasada, T. Sasada, T. Takano, and M. Kakudo, Bull. Chem. SOC. Japan,291 K.Folting, W. xi. Lipscomb, and B. Jorslev, Acta Cryst., 1964, 17, 1263.292 C. Romers, Acta Cryst., 1964, 17, 1287.1964, 37, 940POWELL, PROUT, AND WALLWORK 599nitrato-groups make angles of 62 O and 71 O, severally, with the plane of thecarbon atoms;293 the long C(l)-C(Z) bond (1.60 A) in the peri-ring conformswith previous results for similar compounds and is ascribed to 0--0 repulsion.Ring closure by formation of an 1-0 bond is found in o-iodosobenzoic acid,so that it exists as l-hydroxy-1 ,2-benziodoxol-3-0ne;29~ the whole moleculeis planar but the new 1-0 bond is longer than expected, possibly owing tosteric strain or to greater ionic character.N-0 P 9 O-N(48)The combined(4 9 ) (50)effects of intramolecular hydrogen bonding and resonancein producing a planar molecule are seen by comparing the structures ofdi-m-chlorobenzoylmethane (49) 295 and p-bromobenzoic anhydride (50).296In the latter, the two carboxyl groups are twisted about 28" each in oppositedirections and, in addition, the benzene rings are twisted in the oppositesense about 8" out of the planes of their respective carboxyl groups.Inthe crystal structure of a-naphthol297 the molecules are linked in chains byOH-OH hydrogen bonds of length 2.79 A; previous reports of shorterhydrogen bonds in this structure were based on an incorrect molecularorientation. The crystal structures of violanthrone (51) and isoviolanthrone,the isomer in which the left- and the right-hand half of the molecule arerelated by a centre instead of a plane of symmetry, are remarkably similar 298(5 I ) (52)and are likened to stacks of ploughshares, each ploughshare being representedby a pair of mutually inclined, planar molecules; viewed down the normalsto the planes, the molecules appear superposed in a graphite-like manner;the formally single bonds are shorter than expected, indicating appreciablecontributions to the resonance structure from excited canonical forms.Three structures are reported of derivatives of cyclobutenedione.Thebond distances in the phenyl derivative 299 (52; R = H, R' = Ph) suggest293 T. C. W. Mak and J. Trotter, Acta Cryst., 1964, 17, 367.2 s 4 E. Shefter and W. Wolf, Nature, 1964, 203, 512.295 G. R. Engebretson and R. E. Rundle, J . Amer.Chern. SOC., 1964, 86, 574.Zs6 C. S. McCammon and J. Trotter, Actu Cryst., 1964, 17, 1333.2 9 7 B. Robinson and A. Hargeaves, Acta Cryst., 1964, 17, 944.298 W. Bolton and H. P. Stadler, Acta Cryst., 1964, 17, 1015; W. Bolton, ibid.,29s Chi-Hsiang Wong, R. E. Marsh, and V. Schomaker, Acta Cryst., 1964, 17, 131.p. 1020600 CRYSTALLOGRAPHYa considerable degree of conjugation between the two rings, which explainsthe surprising stability of the compound; the C=O groups a and b havedimensions 1.235 &- 0.01 and 1-21 & 0.01 8, respectively, indicating someresonance with structures involving C-O- for a. However, in cyclohexyl-cyclobutene-1,2-dione (52; R = H, R' = cyclohexyl), which has a reducedconjugation path and the two carbon atoms remote from the double bondin the cyclohexyl group out of the plane of the rest of the molecule, thedimensions of the C=O groups are 1.17 and 1.22 A for a and b, respectively,with standard deviations of about 0.015 A, indicating more double-bondcharacter in a.300 This suggests that further related compounds should bestudied before definite conclusions are drawn about the resonance states inmolecules of this type.In dipotassium 3,4-dioxocyclobutene- 1,2-diolate(52; R = R' = 0-),301 resonance causes all the C-C bonds to be equivalent,and all the C-0 bonds to be equivalent, with mean lengths 1.457 -J= 0*008 and1.259 & 0.007 8, respectively, giving an anion which is a new aromaticspecies of D4h symmetry; the interpretation of the molecular stacking interms of possible self-complex formation is discussed in the last section.Diammonium croconate contains the closely related anion of D&symmetry.302 Here, the mean d(C-C) and d(C-0) are 1.457 and 1.265 8,respectively, and the best molecular-orbital parameters for the ion havebeen calculated.The anion in ammonium nitranilate (53) is not so com-pletely conjugated 303 because, although the carboxyl groups are all virtuallyequivalent with pairs of d(C-0) of 1.18 and 1.22 8, the ring has one pair oflong bonds [d(C-C) = 1-55 81 joining the C-0 groups, and two pairs ofshmter bonds, [d(C-C) = 1.42 and 1-44 81; the ion is centrosymmetric andplanar, apart from the nitro-groups which are both slightly tilted out of theplane and slightly twisted about the C-N bonds.The structure determination 304 of what was thought to be C,Ph,2+SnC1,2-has shown it to be 3-chloro-l,2,3,4-tetraphenylcyclobutenium pentachloro-stannstte, C,Ph,Cl+SnCl,-; discussion of the bond lengths in the carboniumion must await further refinement, but its shape implies delocalisation of thepositive charge mainly over the phenyl rings in positions 2 and 4; an unusualfeature is that the phenyl rings and the 3-chlorine atom are almost coplanar ;the anion is a regular trigonal bipyramid.The molecule of cubane, C8HS,is found to have the full symmetry of a within experimental error,300 I. L. Karle, K. Britts, and S . Brenner, Acta Cryst., 1964, 17, 1506.301 W. M. Macintyre and M. S . Werkema, J . Chem. Phys., 1964, 40, 3563.302 N.C. Baenzinger and J. J. Hegenbarth, J. Amer. Chem. SOC., 1964, 86, 3250.SO3 G. B. Jensen and E. K. Anderson, Acta Cryst., 1964, 17, 243.304 R. F. Bryan, J . Amer. Chem. SOC., 1964, 86, 733.305 E. B. Fleischer, J . A m r . Chenz. SOC., 1964, 86, 3889POWELL, PROUT, AND WALLWORK 601wit,h a mean d(C-C) of 1.551 & 0-003 A. However, what was thought tobe octaphenylcubane has been found by two independent investigations tobe octaphenylcyclo-octatetraene.306 The tub-shaped cyclo-octatetraenering is composed of four nearly planar ethylene-like residues with little orno conjugation between them or with the attached phenyl rings. Thepossibility of partial fixation of double bonds in a benzene ring has beeninvestigated in the structure of trindane (54), but no significant alterationof the aromatic bond lengths was found 307 and all the single bond lengthswere normal; the molecule is planar apart from the outermost CH, groupswhich are about 0.175 A out of the plane, probably owing to repulsionsbetween hydrogen atoms.The non-centrosymmetric space group P2,2,2, was unexpected for both2 - bromo- and 2,6 -dibromo -3,3,5 ,5- tetramethylcyclohexanone.30 For thefirst compound this must mean separate crystallisation of the two enantio-morphs from originally optically inactive material; for the second, the twoasymmetric carbon atoms are internally compensated to produce a moleculewith a plane of symmetry.The strain due to repulsion between the axialmethyl groups is taken up mainly at C-4 and C-1 in both cases, producinginternal angles of 120" and 110", respectively, at these two positions, i.e., thereverse of the usual cyclohexanone ring values.Two independent structuredeterminations of cyclohexane-1,4-dione, one at -140" 309 and one at roomgive concordant results in which the '( twisted boat," withtwo planar acetonyl groups at 38" to each other, provides a quantitativeexplanation for the observed dipole moment in solution; the mean d(C-C)values of 1.536 and 1.515 8 do not differ significantly from accepted sp3-sp3and sp2-sp3 C-C bond lengths, and the mean d(C=O) is 1.210 8. A structureanalysis of myoinositol (cyclohexanehexol) 311 confirms the chair conforma-tion, with one hydroxyl group axial, a,s found previously for the dihydratre,312but indicates small distortions from the perfect chair form which are the samein both the independent molecules in each asymmetric unit.One of theproducts obtainable from o-tolyloxyacetic acid is a cyclic ester (55) ofH Me( 5 5 ) (56) (57)glycollic acid and 4,5,6-trichloro-2-methylcyclohex-2-enone. Structureanalysis 313 has verified its constitution and has shown that, apart from C-6,306 G. S. Pawley, W. N. Lipscomb, and H. H. Freedman, J. Amer. Chem. SOC.,1964, 86, 4725; H. P. Throndsen, P. J. Wheatley, and H. Zeiss, Proc. Chem. SOC., 1964,357.307 E. R. Boyko and P. A. Vaughan, Acta Cryst., 1964, 17, 152.308 L. G. G. Goaman and D. F. Grant, Acta Cryst., 1964, 17, 1604.309 A. Mossel and C. Romers, Acta Cryst., 1964, 17, 1217.310 P.Groth and 0. HasseI, Acta Chem. Scand., 1964, 18, 923.311 I. N. Rabinowitz and J. Kraut, Acta Cryst., 1964, 17, 159.312 T. R. Lomer, A. Miller, and C. A. Beevers, Ann. Reports, 1963, 60, 604.313 C. 0. Haagensen and J. Danielson, Acta Chem. Scund., 1964, 18, 581602 CRYSTALLOGRAPHYthe cyclohexene ring is planar and nearly at right angles to the five-memberedring; the 4-chlorine atom is axial but the other two are equatorial.A preliminary report 314 gives the conformation of the bicyclo[3,3,1]-nonane system in the alcohol (56; R = p-Br*C,H,*SO,*O); both rings adoptthe chair conformation, but both are flattened to relieve the C-3-C-7 repulsion.The carbon skeleton (57) in the structure of cyclodecylamine hydrochlor-,ide, 1$H,O, has almost 2/m (C2h) symmetry315 and is significantly differer,tfrom the " crown " model assumed earlier; the amino-group is in a positionof type 111.The same carbon skeleton is found in trans-1,6-dibromocyclo-de~anc,~le where the bromine atoms are pseudo-equatorial in positions oftype 11; a relatively large distortion of the valency angle, averaging aboutSo, is typical of the cyclodecane ring. A preliminary reportal7 of thestructure of symmetrical 5,6,11,12,17,18-hexadehydo[l8]annulene (58) con-firms its expected 3/m (C3rl) symmetry, and the bond-length variations( 5 8 ) (59)suggest less aromatic character than in tetradehydro[l4]annulene, in accordwith n.m.r. results. Two structures are reported which involve an aziridinering fused to a large saturated ring.In cis-8,8'-dimethyl-S-azoniabicyclo-[5,l,O]octane iodide (69) the cycloheptane ring has a distorted chair con-formation;31s the molecule would have a plane of symmetry if it were notfor small distortions, probably due to packing effects. In trms-13,13-dimethyl-13-azoniabicyclo[ 10,l ,O]tridecane iodide the cyclododecane ring iscomposed of four nearly planar units forming an oblong;319 carbon atoms incorresponding positions along opposite parallel sides of the oblong are dis-placed up and down, severally, €rom the mean plane of the cyclododecanering, but the structure is disordered, producing a statistical mirror plane ;a t the points of fusion of the large and the small ring a compromise betweentheir angular requirements is reached, with an internal angle of 127" in thecyclododecane ring.The cryst a1 structure of dimet hylphen ylsulphonium perc hlorat e ,Me,PhS fC10,-, has been determined,320 mainly for the information providedon the stereochemistry of three-covalent sulphur(u).As expected, the threebonds to the sulphur atom are pyramidal, suggesting sps-hydridisation,with C-S-C angles of 102", 103", and 105" (each &lo); these are reduced814 W. A. C. Brown, G. Eglinton, J. Martin, W. Parker, and G. A. Sim, Proc. Cliem.315 M. H. Mladeck and W. Nowacki, Helv. Chim. Acta, 1964, 47, 1280.316 J. D. Dunitz and H. P. Weber, Helv. Chim. Acta, 1964, 47, 951.s17 N. A. Bailey and R.. Mason, Proc. Chem. SOC., 1964, 356.318L. M. Trefonas and R. Towns, J . Heterocyclic Chem., 1964, 1, 19.319 L.M. Trefonas and J. Couvillion, J. Asner. Chena. SOC., 1963, 85, 3184.32'JA. Lopez-Castro and &I. R. Truter, Acta Cryst., 1964, 17, 465.SOC., 1964, 57POWELL, PROUT, AND WALLWORK 603from the tetrahedral value, probably by lone-pair repulsion ; it is surprisingthat the d(S-Ph) of 1-82 & 0.02 A is the same length as the two S-Me bonds.Heterocyclic Compounds.-The molecule of tetrahydrofuran-3,3,4,4-tetrolhas one methylene group above and one below the plane defined by 0, C-3,and C-4, so that there is a 44" twist in the ring;321 this relieves the repulsionbetween adjacent hydroxyl groups; each molecule is linked to its neighboursin the structure by eight hydrogen bonds. The thiazolidine ring is signi-ficantly non-planar in the structure of sodium salt of 5-phenylthiazolidine-dione (60), C-5 deviating by about 0.13 A from the best plane through therest of the ring;322 there is appreciable resonance between C=O and C-0-.The molecular structures of trans-2,3-dichloro- and trans-2,3-dibromo-l,4-dioxan are very similar;323 in each the ring has the chair form; and bothMeV(60) ( 6 1) ( 6 2)the carbon-halogen bmds are axial, though slight twisting of the ring causesthe angles between these two bonds to be reduced to about 163".A three-dimensional refinement of the structure of trioxan 324 shows that the mole-cule has a regular chair configuration with d(C-0) = 1.430 -+ 0.004 8,LOCO = 107.8" & 0.1" and LCOC = 108.0" & 0.2". Polymerisation ofthe cyclohexanealdehyde has been found to give 2,4,6-tricyclohexyl-trioxan,325 in which each of the rings has the chair form.The cis-1 4 , 5 4-dilactone (61) of 4,5-dihydroxyocta-2,6-diene- 1,s-dicarboxylic acid, whichcan be synthesised directly from acetylene and carbon dioxide, is planar 326and, although the bond lengths are not accurate, comparison with the trans-isomer suggests that there is conjugation within each ring but not betweenthe rings. The same is true of the merocyanine (62), except that the ethylgroup is well out of the main molecular plane.327The six-membered ring in 3,3 - diet hyl- 6,6- diphen yl- 3- azoniabicyclo-[3,l,O]hexane bromide (63) monohydrate has tt chair f0rrn,~~8 with anglesof 65-0" and 34.5" between the mean plane of the four central carbon atomsand the three-membered ring and the C-N-C plane of the five-memberedring, respectively. The relative positions of the oxygen atom and the NHgroup in perkinamine hydrochloride (64) have been confirmed ;329 the hetero-cyclic ring is approximately planar and at an angle of 117 O to the plane formed321 A.D. Mighell and R. A. Jacobson, Acta Cryst., 1964, 17, 1554.322 B. W. Matthews, Acta Cryst., 1964, 17, 1413.323 C. Altona and C. Romers, Rec. Trav. chim., 1963,82, 1080; C. Altona, C. Knobler,324 V. Busetti, M. Mammi, and G. Carazzolo, 2. Krist., 1963, 119, 310.325 G. Diana and P. Ganis, Atti Accad. naz. Lincei. Rend. Classe Sci. $8. ?nut. nut.,326 A. Colombo and G. Allegre, Atti Accad. naz. Lincei, Rend. Classe Xci.$9. mat.3 2 7 G. Germain, C. Paternotte, P. Piret, and XI. van Meerssche, J. Chim. phys.,328 F. R. Ahmed and E. J. Gabe, Acta Cryst., 1964, 17, 602.329 B. R&at and C. RBrat, Acta Cryst., 1964, 17, 1119.and C. Romers, ibid., p. 1089.1963, 35, 80.nut., 1964, 36, 187.1964, 61, 1059.604 CRYSTALLOGRAPHYby four of the five atoms of the carbon ring; the 5-methylene group is tiltedfhrough 51 O towards the heterocyclic ring. The only way of drawing formalbond diagrams for the nucleus in the dianion, 2,5-dimethyl- 1,3a,4,6a-tetra-azapentalene-3,6-dicarboxylate without introducing anomalous valencies isPhto introduce partial ionic structures; the one shown (65) seems to be themain contributor to the resonance state in the structure of the rubidiumsalt ;330 both triazole rings in this new meso-ionic aromatic system areplanar.The existence of this new system is confirmed in a preliminarystudy of 3,6-dibromo-2,5-dimethyl- 1,3a,4,6a-tetra-a~apentalene.~~~The thioamide group in trimethylenethiourea (66) is planar but the six-membered ring approximates to a chair form and has a plane of symmetryin which the C=S group also lies;332 t,he molecules are linked into chains byeach S accepting two N-H-S hydrogen bonds of lengths 3.30 8; these andthe S=C bond form a pyramidal arrangement with LC=S*-N = 102" andLN-S-N = 128". A plzotodimer of l-methyl-2-pyridone is found to have( 6 6 ) (67) (68)structure (67) which seems to be more strained than usual for this type ofsystem;333 the C-C bonds linliiiig the two pyridone rings are stretched to1.60 but there are still some intramolecula,r C.-C contacts as close asabout 2-70 A.A dimeric cyclohexanone peroxide is shown to be dispiro-[5,2,5,2]-7,8,15,16-tetraoxohexadecane (68) in which each of the rings hasa chair Recent studies of tetraphenylporphine 335 and some of it,smetal derivatives 336 emphasise the fact that the porphine system is flexible,being sometimes planar and sometimes buckled, probably depending on theeffects of molecular packing; there is little evidence for conjugation wit,h thephenyl rings, which are twisted at large angles to the porphine nucleus, and330 M. Brufani, W. Fedeli, G. Giacomello, and A. Vaciago, Gazzetta, 1963, 93, 1556.331 M. Brufani, W. Fedeli, and G.Giacomello, Gazzetta, 1963, 93, 1571.s 3 a H. W. Dias and M. R. Truter, Acta Cryst., 1964, 17, 937.333 M. Laing, Proc. Chem. SOC., 1964, 343.334P. Groth, Acta Chem. Scand., 1964, 18, 1301.335 S. Silvers and A. Tulinsky, J. Arner. Chem. SOC., 1964, 86, 927.ss5 E. B. Fleischer, C. K. Miller, and L. E. Webb, J . Amer. Chem. SOC., 1964, 86,2342POWELL, PROUT, AND WALLWORK 605the double bonds opposite the nitrogen atoms in the pyrrole rings do notseem to be part of the resonance system, though the pyrrole rings are flat.There are a number of reports of pyrimidine and purine structures againthis year and, since they are nearly all based on three-dimensional data, theconclusions about the tauiorn2ric forms adopted can mostly be acceptedwith confidence.Cytosine (69) exists in the amino-form and has a hydrogenatom on N-1 and none on N-3.337 Isocytosine, related to cytosine by inter-change of the C=O and C-NH, groups is remarkable in that it exists as two( 6 9 ) (70) ( 7 ' ) (72) (7 3) 1tautomers crystallising togetlher in a P : 1 ratio 338 and linked by three hydrogenbonds in a manner analogous to the pairing of the bases in DNA-the secondtautomer is derived from the first by moving the l-hydrogen atom to the3-position ; their co-existence implies equal stability and emphasises theneed to consider the distribution of protons and the pH in proposing st'ructuresfor nucleic acids and their derivatives. A study concerning the position ofprotonation in acid conditions is that of l-methyluracil hydrobromide ;339the proton is attached to the 4-oxygen atom and the shortening, from single-bond lengths, of the bonds joining C-4, C-5, C-6, and N-1 is evidence ofresonance mainly between structure (70) and that iiivolvingI 1MeN *CH=CH*C-OH+ ;the cations are held in layers by zig-zag O-H-a-Br- and N-H-.Br- bondsand the packing is unusual in having the bromide ions of one layer sand-wiched between pyrimidine rings in the layers above and below. Theanion (71) in rubidium 5-fluoro-orotate is not planar ;a40 steric hindrancebetween the 4-, 5-, and 6-substituents causes the carboxylate group to betwisted 7" out of the plane formed by most of the atoms of the ring; thefluorine atom is also slightly out of the plane, and the 2-carbonyl group isalso tilted out of the plane; unfortunately, poor data limited the accuracyof this structure, and even the conclusions about the hydrogen-bonding seemopen to doubt.The structure of ammonium barbiturate 341 shows that theacid (72; X = H,) forms the anion by losing a proton from X; the ionapproximates to a planar configuration with 2mm symmetry, and a compactthree-dimensional network of hydrogen bonds links the whole structuretogether. Violuric acid (72; 3 = N-OH) monohydrate has been studied,mainly in the perdeuterated form, by both X - r a ~ ~ ~ z and neutron diffraction ;343337 D. L. Barker and R. E. Marsh, Acta Crpt., 1964, 17, 1551.338 J. F. McConnell, B. D. Sharma, and R. E. Marsh, Nuture, 1964, 203, 399.339 H. M. Sobell and K.-I.Tomita, Actu Cryst., 1964, 17, 122.340 W. M. Macintyre and 31. Ziralrzadeh, Acta Cryst., 1964, 17, 1305.341 B. M. Craven, Acta Cryst., 1964, 17, 282.342 B. M. Craven and Y. Mascarenhas, Acta Cryst., 1964, 17, 407.343 B. M. Craven and W. J. Takei, -4cta Cryst., 1964, 17, 415606 CRYSTALLOGRAPHYthe main point of interest is the hydrogen-bond scheme which involves abifurcated bond between a water molecule and two oxygen atoms of theacid molecule; the distances from the shared deuterium atom to the twooxygen atoms are 2.07 and 2.10 A; the bond lengths involving deuterium ared(0-D) = 0-97 and 1.06 A; LDOD = 106" in D,O; some interesting inter-molecular interactions in this structure are discussed in the last section(beIow). Two crystallographically independent molecules of dilituric acid(72; X = NO*OH), in the monoclinic form of the trihydrate, both have thea~i-nitro-triketo-form,~~~ in contrast with the monohydroxy-diketo-tautomerfound previously for the anhydrous acid; the molecules are slightly distortedfrom planarity towards a boat form, and they are hydrogen-bonded intolayers together with water molecules which are further linked by un-expectedly short hydrogen bonds; some of these hydrogen bonds are thoughtto be bifurcated and a neutron-diffraction study is planned.Further inter-actions between the layers are discussed later, as are those in the compactstructure of alloxan (72; X = 0) where the molecule has a planar tetraoxo-f0rm.~~5 An accurate low-temperature study 346 of the electron density incyanuric acid (72; C=X replaced by NH) provides evidence for a shift ofsome electron density from t'he atoms into the bonds; additional maximanear one of the oxygen atoms may be due to its lone-pair electrons.Asynthesis from 4,5-diaminopyrimidine and acetylacetone, which was expectedto form a fused ring compound, resulted in 4-(4-aminopyrimidin-5-ylimino)-pent-2-en-2-01;~~' the 0-C-N side chain is planar, making a dihedral angleof 68" with the planar ring, but it is not certain whether it is in the enol orthe keto-form.As a further study of the protonation sites of pyrimidines and purinesthe structure of 9-methylguanine hydrobromide has been determined ;34* inthis case the proton is attached directly to the ring at N-7; the cation isplanar and has the keto-form (73), with resonance mainly between NH,*C=N-and NH,+=C*N--; the cations are not hydrogen-bonded directly but in-directly, by N-H...Br- ; possible C-H...O bonding is discussed below.Anapproximate determination 349 of the structure of g-methyladenine givessubstantially the same dimensions as were found earlier for a complex with1 -methylthymine : ribbons of hydrogen-bonded molecules are formed by theamino-group linking to N-1 of the one molecule and N-7 of another. Theproduct formed during an attempt to synthesis 6,6-di-(2-chloroethyl)-adenine has been shown by structure analysis of the methiodide to be 9-2'-chloroethyl-7,8-dihydro-9H-imidaz0[2,1 - i ] p ~ r i n e . ~ ~ ~Natural Products and Related Compounds.-A preliminary report 351 of arevision of the crystal structure of L-ascorbic acid confirms the generallyaccepted formula, with a nearly planar, five-membered ring, though the344 B. M.Craven, S . Martinez-Camera, and G. A. Jeffrey, Acta Cryst., 1964, 17,345 W. Bolton, Acta Cryst., 1964, 17, 147.346 G. C. Verschoor, Nature, 1964, 202, 1206.347 N. F. Yannoni and J. Silverman, Nature, 1964, 202, 484.348 H. M. Sobell and K.-I. Tomita, Acta Cryst., 1964, 17, 126.349 R. F. Stewart and L. H. Jensen, J . Chem. Phys., 1964, 40, 2071.350 W. M. Macintyre and R. F. Zahrobsky, 2. Krist., 1963, 119, 226.351 J. Hvoslef, Acta Chem. Xcand., 1964, 18, 841.891POWELL, PROUT, AND WALLWORK 607molecular arrangement is modified. The structure of N-acetylglucosamine mais of interest because of the inhibiting effect of this substance on lysozyme;the pyranose ring has the usual flattened chair form, and the amide groupis almost planar.In ribose p-bromophenylhydrazone 353 the sugar is foundto have the open chair form with a staggered arrangement round all theC-C bonds; the carbon chain is planar, except for the terminal C-5, and thezig-zag C-N-N=C-C chain is also roughly in a plane a t an angle of about116" to the other plane; an unusual feature is the intramolecular hydrogenbond of length 2.66 A between the 2- and the 5-hydroxyl group.It has been confirmed by structure analysis of the rubidium salt that asulpholipid, widely distributed in plants and photosynthetic micro-organismsand the only sulphonic acid derivative so far known in Nature, is a fattyacid ester of 6- deoxy-6 - sulpho- a-D -glucop yranos y l- ( 1 +l ' ) -DThe arginine molecule in L-arginine dihydrate is in a zwitterion form withthe transferred proton on the guanidyl group;355 the molecule can bedescribed in terms of two planes with a dihedral angle of 74" between them,one through the acid group and 0.28 A away from the amino-group, and theother through the extended side chain containing the guanidyl group.Thestructure of histidine hydrochloride monohydrate has been refined further 356in order to compare it with recent structures of complexes containing histi-dine; the bond lengths are found to be similar to those in the complexes inspite of differences in the conformation ; a feature common to all the structuresis the staggered arrangement of the hydrogen bonds formed by the NH3+group relative to the three atoms joined to the adjacent carbon atom.In order to gain structural information about dinucleotides and poly-nucleot,ides the structure of /3-adenosine-2'-~-uridine-5'-phosphoric acid hasbeen determined;357 this is a dinucleotide, but with only one phosphategroup, and it differs from naturally occurring adenosylribose also in thepoint of attachment of the phosphate group ; t,he adenine ring, which receivesa proton a t N-1 from the phosphate group, is planar, and the amino-group istwisted by 25" from this plane by hydrogen-bonding; the uracil ring is inthe keto-form, and the two ribose rings have their usual conformation; thetwo ester P-0-C planes have a dihedral angle of 123", and the torsion anglesabout the adenosine and uridine " glycosidic " C-N bonds are -55" and -5",respectively.Structural work on deoxyribonucleic acid has been reviewed 358with emphasis on recent X-ray-diffraction studies of DNA in solution.DNA which contains uracil in place of the more usual thymine has a similaroverall configuration,359 and it is therefore deduced that the difference insecondary structure between DNA and RNA (which usually contains uracil)must be due to the extra 2'-hydroxyl group of the latter.352 L. N. Johnson and D. C. Phillips, Nature, 1964, 202, 588.353 K. Bjamer, S. Furberg, and C. S. Petersen, Acta Chem. Scand., 1964, 18,3 5 p Y.Okaya, Acta Cryst., 1964, 17, 1276.355 I. L. Karle and J. Karle, Acta Cryst., 1964, 17, 835.356 J. Donohue and A. Caron, Acta Cryst., 1964, 17, 1178.357 E. Shefter, M. Barlow, R. Sparks, and K. Trueblood, J. Arner. Chem. SOC.,35a V. Luzzati, Progr. Nucleic Acid Res., 1963, 1, 347.359 R. Langridge and J . Marmur, Xcience, 1964, 143, 1450.587.1964, 86, 1872608 CRYSTALLOGRAPHYThe crystal-structure dotermination of securine hydrobromide di-hydrate 360 confirms the chemical structure and the absolute configurationof the alkaloid, and shows that the piperidine ring has the boat form. Con-firmation of the chemical structure and absolute configuration is alsoobtained for galanthamine methiodide ;381 the proposed intramolecularhydrogen bond from the hydroxyl group to the ether-oxygen atom haslength 2.95 8.The carbon and nitrogen atom skeleton of heteratisine (74),in its hydrobromide monohydrate, is found to be similar t.0 that of lycoctonineand related alkaloids ;362 the six-membered ring carrying the methoxyl groupf i . . - O M e(74)has a distorted boat form and the methoxyl group itself has the same con-figuration as the corresponding hydroxyl group in delcosine. The molecularst,ructure and absolute configuration found 363 for cleavamine (75) in itsmethiodide is in accord with chemical evidence; the indole nucleus, and thetwo carbon atoms attached to it, are planar ; the two ethylenic carbon atoms,and the three nearest carbon atoms in the same ring also lie in a plane.Structure analysis 364 of the hydrobromide of a lactone bromo-derivative ofthe alkaloid tetrodotoxin has shown it to be the anhydro-derivative (76), andpreliminary work 365 on tetrodotoxin itself disproves the suggestion that itmight occur as two units joined by an ether oxygen.A preliminary report 366of the structure of vobasine methiodide shows it to have the configurationMe, ..MeH HO .H I-Br- T p g H .... CHlsOH o7mMe+ H ~ NH O --- HHO - oH'*0 (76) (77)(77) with the indole and the keto-group approximately in one plane, andthe other carbon atoms of the eight-membered ring in a second plane almostperpendicular to the first; the piperidine ring has the chair form and is fusedtram to the indole nucleus and roughly parallel to it; the methyl-carbonatom of the ester group is only about 4 8 above the pyrrole ring, so itsrotation will be hindered.The chemical formula of jamine is found toI.360 S. Imado, M. Shiro, and Z . Horii, Chem. and Ind., 1964, 1691.3151 D. Rogers, Proc. Chem. Xoc., 1964, 357.363 M. Przybylska, Cunad. J . Chem., 1963, 41, 2911.363 N. Camerman and J. Trotter, Acta Cryst., 1964, 17, 384.364 Y . Torniie, A. Furusaki, K. Kasami, N. Yasuoka, K. Miyake, M. Haisa, andNitta, Tetrahedron Letters, 1963, 2101.365 R. B. Woodward and J. Z. Gougoutas, J . Amer. Chem. SOC., 1964, 86, 5030.366 H. Jaggi and U. Renner, Chinaia (Switz.), 1964, 18, 173POWELL, PROUT, AND WALLWORK 609be (78);367 there are six saturated six-membered rings, five of which havethe chair and one the boat form.Himbosine, a typical member of a groupof bases which are highly oxygenated hexacyclic esters, has been shown,by X-ray analysis of its hydrobromide,368 to have a structure in agreementwit’h that deduced by recent chemical studies.Although previous chemical work has related the antifungal metabolite,C1,HZ4O4, to trichothecin, it has now been shown to be a derivative of tricho-dermol (79) by a structure determinat,ion of the p-bromobenzoate.369 The(7 8) (79)molecular structure and absolute configuration of or-bromoisotutin (80) hasbeen shown 370 to have the unusual feature of a cyclopentane ring with two-epoxy-rings attached, one in a spiro-ring and the other fused ot#l with respectto the first.The six-membered ring in the monoterpene, iridomyrmecin (81), isrestrained in a boat conformation by the planar lactone group and it has afive-membered ring endo to it;371 the points of fusion and the two adjacentcarbon atoms in the cyclopentane ring form a plane, but the fifth carbonatom is 0-6 8 out of the plane in such a way as to continue the curvature ofthe boat; the relative configurations of the asymmetric atoms are in accordwith chemical deductions.Two independent crystal-structure determina-tions 372 of the silver nitrate adduct of humulene show that this sesquiterpenehas the all-trans-structure (82); each of the two silver ions per molecule iscomplexed with only one C=C bond with an average d(Ag--C) of 2.39 A, in( 8 1 ) ( 8 2 ) (83)contrast with the corresponding adduct of cyclo-octatetraene, where eachAg+ interacts with two non-adjacent double bonds with average d(Ag.43)of 2.49 and 2.81 8; the unusually large difference between the two sets of367 I. L.Karle and J. Icarle, Tetrahedron Letters, 1963, 2065; Acta Cryst., 1964,17, 1356.388 F. M. Lovell, Proc. Chem. SOC., 1964, 58.369 S. Abrahamsson and B. Nilsson, Proc. Chem. SOC., 1964, 188.370 B. M. Craven, Acta Cryat., 1964, 17, 396.371 J. F. McConnel, A. McL. Mathieson, and B. P. Sehoenborn, Acta Cryst., 1964,372 G. A, Sim, Chem. and Ind., 1964, 976; J. A. Hartsuck and I. C. Paul, ibid.,17, 472.p. 977610 CRYSTALLOGRAPHYcell dimensions given for this structure suggests that one or both should beredetermined. The molecular structure of helanin (83), found from an X-rayanalysis of its br~mo-derivative,~~~ confirms that postulated on chemicalgrounds.Enmein is found to have the configuration (84), from a study ofacetylbromoacetyldihydroenmein, 374 with a cisfusion between ring A andthe five-membered ring. Both the m-iodobenzoate and the 4-iodo-3-nitro-benzoate were studied 375 as means of determining the structure and absoluteHOconfiguration of simarolide (85), which, by its structural relationship to thebitter principles of the quassin group and triterpenoidstof the limonin group,provides further evidence for the proposed biogenesis of the quassin groupfrom euphol-derived triterpenoids. Swietenine (86 ; R = tigloyl) is anothertriterpenoid biogenetically related to the limonin group ; the structure wasdetermined 376 for the derivative (86; R = p-iodobenzoyl), and the positionof the double bond attached to ring c was established by the coplanarityof this region of the molecule.The structure of the 2-oxazoline derivative(86)of phytolaccagenin has been solved377 without use of the heavy-atommethod; a model based on chemical information was tested by trial rotationsand translations against the Patterson synthesis and by structure factorcalculation; the resulting structure (87) has the unusual features of a highdegree of oxidation and a methoxycarbonyl group which appears to be ofnatural origin. The molecular structure of the bitter lactone, glaucarubin(88), determined as the p-bromobenzoate differs somewhat from that373 M.T. Emerson, C. N. Caughlan, and W. Hem, Tetrahedron Letters, 1964, 621.374 Y . Iitak and M. Natsume, Tetrahedron Letters, 1964, 1257,3 7 5 W. A. C. Brown and G. A. Sim, Proc. Chem. SOC., 1964, 293.376 A. T. McPhail and G. A. Sim, Tetrahedron Letters, 1964, 2599.G. H. Stout, B. M. Malofsky, andV. R. Stout, J . Amer. Chem. SOC., 1964, 86,957POWELL, PROUT, AND WALLWORK 61 1previously proposed on chemical grounds, especially in the region of thehemiacetal bridge.378The structure of b-carotene 379 and those of its 7,7‘-dihydro- 380 and15,15’-dehydro-derivatives 381 resemble each other in having planar, orapproximately planar, all-trans carbon chain’s which are slightly curved intheir own planes because of steric hindrance between the methyl groupswhich are attached to the same side of the chain.The B-ionone ring iss-cis in its orientation about the single bond joining it to the chain, exceptOH OH_..OH0Br(88) ( 8 9 )in the 7,7’-dihydro-compound where the two adjacent single bonds allowthe ring to be inclined at a large angle to the plane of the chain. Theprogression from alternate single and double bonds to bonds of mixed natureas the centre of the chain is approached, which has been observed in relatedcompounds and predicted theoretically, is found again in t’he two derivatives.The lack of evidence for this in @-carotene itself may be due to the appreciablestandard deviations of the bond lengths (m 0.03 A) in this structure.In 4-bromo-oestradiol (89), rings B and c have the chair form and ring Dhas two planar parts, with a dihedral angle of 137” between them; and thehydroxyl and the methyl group are attached to ring D equatorislly andaxially, respectively.382 Androsterone has a similar carbon skeleton exceptthat ring A, which is there saturated, also has the chair form ;383 the 18-methylgroup is axial with respect to ring D and the 19-methyl group is axial withrespect to rings A and B.Ergosterol can be converted into a novel benzenoidsteroid whose structure is found 384 to be 22,23-dibromo- 12-methyl- 18-norergosta-8,11,13-trien-3~-yl acetate (90) ; the novel feature is the benzenoidAcO375 G. Kartha, D. J. Haas, H. M. Schaffer, and K. K. Kaistha, Nature, 1964, 202,379 C . Sterling, Actu Cryst., 1964, 17, 1224.380 C.Sterling, Actu Cryst., 1964, 17, 500.381 W. G. Sly, Actu Cryst., 1964, 17, 511.382 D. A. Norton, G. Kartha, and Chia Tang Lu, Actu Cryst., 1964, 17, 77.383 D. A. Norton and J. 3%. Ohrt, Nature, 1964, 203, 754.384 T. N. Margulis, C. F. Hammer, and R. Stevenson, J . Chem. SOC., 1964, 4396.389; G. Kartha and D. J. Haas, J . Amer. Chem. SOC., 1964, 86, 3630612 CRYSTALLOGRAPHYring C, which is planar; rings A and B have chair and half-chair conformations,respectively; the side chain is interesting in being an essentially planarcarbon skeleton with the bromo- and methyl groups in completely staggeredconformations.Contrary to expectation, the plant pigment harunganin (91) is not anoxygen-heterocyclic compound ;385 the molecular skeleton is derivable fromthe natural product emodin, but it has the unusual gem-di-isopentenylsubstitution. Besides the rather short intramolecular hydrogen bonds,d(OH-*-OH) = 2.58 A and d(OH-0) = 2.47 8, the molecules are linked byintermolecular hydrogen bonds; one of the terminal methyl groups in thesingle isopentenyl group is disordered, occupying statistically two positionsabout 1 A apart.Molecular Complexes and Molecular Interactions.-Although hydrogen-bonding of the conventional type has been referred to in the previoussect'ions for specific structures, there are some aspects which deserve specialmention here. A further example of the short hydrogen bonds in acidsalts has been studied in the crystal structure of di-p-chlorophenyl hydrogenp h o ~ p h a t ~ e ; ~ ~ ~ successive molecules along the b direction are linked byO-.H.-O bonds of length 2.40 & 0.02 8 between PO(0H) groups; crystallo-graphic two-fold axes pass through the centres of these hydrogen bonds andit is probable that they are actually, rather than statistically, symmetrical.The strong tendency for carboxylic hydrogen-bonded dimer groups to adopta planar configuration has been explained in terms of a specific interactionbetween each proton and a lone pair of electrons in the plane of the sp2-hybridised oxygen at0rn.~87 The small distortions from planarity in somecryst a1 st'ructures are due to other packing inff uences.Further examples have been reported which confirm the importance inalkaloid structures of hydrogen bonds t o halogen ions, including I-.Asignificant feature of the packing arrangement in cleavamine methiodide 363is the NH-I- hydrogen bond, of length 3.4 A, involving the indole group.Revised hydrogen- bond schemes have been proposed for echitamine halides 3*8and ( + )-dimethanolaconinone hydroidide trihydrate ;389 also for codeine andmorphine salts,390 involving hydrogen bond distances such as d( OH*-I-) =3.57 and 3.58 A, d(NH.**I-) = 3.79 8, and avoiding less likely features ofthe earlier proposals such as CH-0 and OH-C hydrogen bonds and lackof ionisation in halogen acid molecules.It is interesting that the structures of two cyclobutenedione deriva-t<ives 2999 300 exhibit similar intermolecular CH*-*O interactions which maybe hydrogen bonds.In both cases the strongest interaction involves a CHgroup of the four-membered ring (52; R = H) and the C=O group conjugatedwith a ring substituent (52; a conjugated with R' = Ph or cyclohexenyl).These interactions give distances d(CH*.*O) = 3.32 and 3-23 8, respectively.Interactions between CH groups and the oxygen atoms of C=O groups are also386 R. A. Alden, G. H. Stout, J. Kraut, and D. F. High, Acta Cryst., 1964, 17, 109.386 M. Calleri and J. C. Speakman, Acta Cryst., 1964, 17, 1097.387 J. H. Robertson, Acta Cryst., 1964, 17, 316.3i3* B. D. Sharma, R. E. Marsh, and J. Donohue, 2. Krist., 1963, 119, 252.389 J. Donohue, Actu Cryst., 1964, 17, 771.390 J. Donohue, B. D. Sharma, and R. E. Marsh, Acta Cryst., 1964, 17, 249POWELL, PROUT, AND WALLWORK 613found in the structures of 1 -methyluracil hydrobr~mide,~~~ with d(CH.*.O) =3-05 and 3-12 8, and 9-methylguanine hydrobr~mide,~~~ with d(CH*.*O) =2-95 A.CH.*.O interactions are also reported in the structures of 2-methj-l-4,5,6-trichlorocyclohex-2-enone 313 and irid~myrmecin.~~l Some of theCH2-*N distances in " hexacrylonitrile " 273 are rather short (3-44 and3.36 A) and it is suggested that these may represent hydrogen bonds. Doubthas been expressed 289 whether these types of interaction should be classedas hydrogen-bonding, partly because in o-nitrobenzaldehyde, where an intra-molecular CH-*.ONO bond could be readily formed, the substituent groupsseem to avoid each other, and partly because so few CH protons seem to beinvolved in intramolecular interactions of this type even in structures wheresuch hydrogen-bonding has been suggested. In contrast with this view, thesolid complex formation at low temperatures between diethyl ether andbrornodichloromethane has been shown 391 by structure analysis at - 130"to be due to CH*-O interaction, with d(CH.-O) = 3.1 A, interpreted as ahydrogen bond.Complex formation by hydrogen-bonding of the more conventional typeis found in the crystal structures of the alcohol semi hydrate^.^^^ Theoxygen atom of each water molecule is surrounded, nearly tetrahedrally,by the oxygen atoms of four alcohol molecules, to two of which it donateshydrogen bonds and from two of which it receives hydrogen bonds, givinginfinite chains of the type -.water (alcohol), water (alcohol), water... .Inclsthrate hydrate structures, a small molecule is usually enclosed in a cageof hydrogen-bonded water molecules forming a polyhedron with 12, 14, 15,or 16 sides. A larger and more general form of cage is found in the mono-clinic form of the clathrate hydrate of tri-n-butylsulphonium fluoride,(n-C,H,) 3SP,23H,0.393 The structure consists of layers of face-sharingH,oO,, pentagonal dodecahedra, and hydrogen-bonding of these layers,through further water molecules, forms cages which are large enough tocontain t'he pyramidal butylsulphonium ions in pairs, back-to-back, withd(S+.-S+) = 3-49 A. The fluoride ions probably occupy some water sitesrandomly, and further disorder is found in the carbon chains.The structureof the complex, HI3,2BzNH,, has been determined 394 because it is consideredt o be a model for the more complicated starch-iodine complex. Thebenzamide molecules are dimerised by hydrogen-bonding and the dirners arestacked in such a way as to leave long channels in which the nearly linearI,- ions are aligned. There is strong attraction between successive I,- ions,with d(I-I) = 3-80 A, [cf. d(1-I) = 2.90 and 2.96 A], and it is suggestedthat this pseudopolymerisation is responsible for the blue colour. Thereare two such polyiodidc chains in each channel, probably cross-linked byhydrogen bonds formed by the HI, protons. An unusual type of channelinclusion compound is reported 395 in which the host lattice of trans-anti-trans-anti-trans-perhydrotriphenylene molecules can include linear non-polymeric molecules, such as hydrocarbons and their halogen and other391 P.Andcrsen and T. Thurmann-Moe, Acta Chern. Scalzd., 1964, 18, 433.392 K. Pachler and N. Stackelberg, 2. Krist., 1963, 119, 15.393 P. T. Beurskens and G. A. Jeffrey, J. Chern. Phys., 1964, 40, 906, 2800.3 9 4 J. M. Reddy, K. Knos, and &I. B. Robin, J . Chem. Phys., 1964, 40, 1082.3 9 5 M. Farina, G. Allegra, and G. Natttl, J. Amer. Chem. SOC., 1964, $8, 516614 CRYSTALLOGRAPHYderivatives, linear macromolecules, such as polyethylene, polybuta-cis- 1,4-diene, and polyoxyethylene glycol, as well as various flat molecules, andeven approximately spherical molecules such as carbon tetrachloride.Three molecular complexes of the z-n charge transfer type have beenreported involving s-trinitrobenzene as the acceptor. That with anthraceneas donor 396 shows an elaboration of the usual plane-to-plane stacking ofalternate donor and acceptor molecules in that each component exists intwo different orientations within the repeat distance along each stack. Themolecules are planar apart from the slightly twisted nitro-groups, and theaverage perpendicular separation between adjacent molecules in the stackis about 3.28 A at room temperature and about 3.23 A at -100". Thedirection of maximum thermal contraction for this structure is not parallelto the stacking direction because there are small reorientations of themolecules on cooling. The complexes with skatole and indole 397 show, inaddition to the usual interplanar interaction, evidence of specific interactionbetween the nitrogen atom of the donor and a non-substituted carbon atomof the trinitrobenzene molecule, though this molecule undergoes a stronglibrational motion in its o m plane. The average perpendicular separationbetween molecular planes within each stack is about 3-30 A in each of thesetwo structures a t -140", but again the nitro-groups are slightly twistedout of the planes of the benzene rings. The indole complex is disorderedby having the donor molecule in two orientations, in which its two rings areapproximately interchanged. Closely related to such complexes are thehighly conducting, radical-ion salts formed by the powerful acceptor,tetracyanoquinodirnet,hane (TCNQ). The first of these whose crystalstructure has been reported,398 is Cs,[(NC),C:C,H4:C(CN),1,. The TCNQmolecules are arranged in centrosymmetric groups of three with the normalsto their planes slightly inclined to the monoclinic b-axis and these groups arestacked along the b-axis, which is also the direction of maximum electricalconductivity. The perpendicular separations between successive TCNQmolecules are 3-21 0.01 A within each group and 3.44 & 0.01 A betweengroups in the same stack. The cmium ions are in adjacent stacks, alsoparallel to the b-axis. The plane-to-plane stacking of the anions in thestructure 301 of potassium squarate monohydrate with a mean separationof 3.30 A suggests that this may be an example of a charge-transfer self-complex; the rotation of successive anions round the stacking axis throughabout 45" relative to each other is in agreement with molecular-orbitalpredictions for the maximum overlap of appropriate n-orbitals ; however,unlike the TCNQ radical-ion salts, this crystal shows no large electricalconductivity.Recent structural results suggest that specific polar interactions betweencarbonyl groups may be of two types. In some cases 2929 309, 342, 344 theC=O groups in adjacent molecular layers overlap in an antiparallel mannergiving d(C.-O) = 3.1 1-3.15 in directions approximately perpendicularto the C=O axis. The second type, which was first noticed in the structure3Q6 D. S. Brown, S. C. Wallwork, and (in part) A. Wilson, Acta Cryst., 1964, 17, 168.3Q7 A. W. Hanson, Acta Cryst., 1964, 17, 559.3Q8 P. Arthur, Acta Cryst., 1964, 1'7, 1176POWELL, PROUT, AND WALLWORK 615of chloranil, involves a nearly linear C=O-.C arrangement. It is furtherexemplified in the structure of alloxan 345 where d(C=O-.-C) = 2-79 8. Inthis case t'here is a new feature in that the same carbon atom is involved intwo such interactions on opposite sides of the molecule. These are indica-tions that this type of interaction may occur when there are several carbonylgroups in the same planar molecule which also has insufficient hydrogen-bonding protons to satisfy all the electronegative atoms attached to thering in adjacent molecules. A comparison between theoretical calculationsand structural data399 for a number of substances in which this type ofinteraction occurs shows that it is not the carbonyl groups of highest polaritywhich are involved, but rather those which have a high mobile bond ordertogether with a highly positive carbon atom but a relatively weakly negativeoxygen atom.Other specific interactions which are reported as having structuralsignificance involve iodine atoms in association with either selenium oroxygen atoms. In the 2 : 1 addition compound between iodoform and 1,4-di~elenane,~oO two iodine atoms of each iodoform molecule take part ino-type charge-transfer interactions with selenium atoms belonging to twoneighbouring diselenane molecules, and each selenium atom is linked in thisway to two iodoform molecules, one in a roughly equatorial direction andone axial. The I-.Se distances of 3.47 and 3-51 L% are about 0.65 L% lessthan the expected van der Waals separation. The 1 : 1 molecular complexbetween iodine and tetrahydroselenophen, C4H ,Se, also has each seleniumatom linked to two iodine but in this case one link, with d(Se-I) =2.76 8, is only slightly longer than a covalent bond while the other, withd(Se..-I) = 3.64 A is a relatively weak interaction. The I-+3e...I angle is167" and the stronger Se-I link is at an angle of 100.5" to the plane ofthe selenium atom and its two adjacent carbon atoms. The structureof 1 -hydroxy-l,2-benziodoxol-3-one involves a short I-.O contact of 2-90 &0.05 A, resembling the interactions found in various iodate structures;this is thought to be related to the tendency for iodine to act as a weakLewis acid.399 B. Pullman, Acta Cryst., 1964, 17, 1074.'OO T. Bjoruatten, Actu Chem. Scand., 1963, 17, 2292.4 0 1 H. Hope and J . D. McCullolgh, Actu Cryst., 1964, 17, 712

ISSN:0365-6217    

DOI:10.1039/AR9646100567

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

ERRATAVOL. 68, 1963.Page 9, line 7'. For specifially read specifically.Page 31, Eine 8.Page 39, line 9. For 1402 read 140".Page 400. Formulae (6), (7), and (8) should contain a double bondFor yRNHI + ycl- read yRN&,+ ycl-.as shown:Page 41 1. Formula (68) should beM

ISSN:0365-6217    

DOI:10.1039/AR9646100616

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

I N D E X O F AUTHORS’ NAMESAaronoff, B. R., 282.Abel, E. W-., 129, 130, 179.Abel, K., 532.Abell, P. I., 316.Aboderin, A. A., 247.Abraham, N. A., 302, 528.Abraham, R. J., 219, 456.Abrahams, S. C., 189, 569,Abrahamsson, S., 360, 560,Abramovitch, R. A., 370,Abramsson, S., 310.Abramyan, A. A., 543.Acevedo, R., 416.Achaya, K. T., 319.Acher, R., 507.Acheson, R. M., 376, 383,Achmatowicz, O., 410.Ackerman, M., 78.Ackermann, G., 528.Ackermann, R. J., 78.Ackman, R. G., 299.Acrivos, J. U., 202.Scton, E. M., 437, 438.Acton, N., 297.A4dachi, K., 363.Adam, F. C., 32.Adam, G., 408.Adam, IT., 258.Adams, D. G., 270.Adams, D. M., 166, 179.Adams, F., 558.Adams, G. A., 429, 444.Adams, J., 504.Adams, J. Q., 29.Adams, K. A. K., 409.Adams, M.R., 545.Adams, P. R., 276.Adams, R., 121.Adams, R. N., 97.Addink, N. W. H., 559.Addison, C. C., 132, 148,150, 156, 170.Addy, J. K., 246.Adeniran, 35. A., 280.Aditya, S., 74.Adityachaudhury, N., 367.Adler, A. D., 290.Adler, M., 447.Adler, S. F., 103.Adrian, F. J., 41, 199.Aebli, H., 419.Affsprung, H. E., 529.Agahigian, M., 139.Ager, J. W., jun., 121.Ageta, H., 366.573.609.384.386.Aggamal, R. C., 134.Agnihotri, R. K., 302.Agova, M., 207.Ahlberg, D. L., 533.Ahlburg, H., 574.Ahluwalia, J. C., 74.Ahmad, H., 528, 552.Ahmad, M., 217, 349.Ahmad, Y., 388.Ahmed, F. R., 603.Ahn, M.-K., 286.Aikazan, A. M., 111.Aimi, N., 356.Akabori, S., 100, 103, 497.Akagi, M., 430, 437.Akamatsu, A., 103.Akhtar, M., 421, 422.Akhtar, M.I., 263.Akimov, V. K., 529, 534.Akopyan, Z. A., 598.Aksel’rud, N. V., 148.Aksenova, I. V., 128.Aksnes, D., 250.Aksnes, G., 250.Alabran, D. M., 420.Aladzheva, I. M., 314.Alauddin, M., 420.Albers, R. J., 331.Albert, A., 390.Alberti, G., 532.Albonico, S. M., 400.Alchudzhan, A. A., 111.Alden, R. A., 612.Aldridge, D. C., 322.Aldous, J. G., 552.Aldus, L. J., 549.Alekseeva, T. A., 75.Al&ma,gna, A., 219.Alexa, J., 532.Alexander, L. E., 179, 591.Alexander, R. P., 121, 122.Alexandrova, P. V., 528.Alexandrov, A., 528.Alexandrova, D. P., 98.Alfes, F., 492.Alfes, H., 436.Alhojiirvi, J., 319.Ali, S. I., 102, 561.Ali, W. R., 297.Allavena, M., 22.Allbutt, M., 154.Allcock, H. R., 139.Allegra, G., 613.Allegre, G., 603.Allen, B.T., 31.Allen, E. A., 157.Allen, G., 139, 183.Allen, J. D., 270, 480.Allen, J. F., 157.617Allen, J. R., 162.Allen, L. C., 47.Allen, M. J., 96, 474.Allen, R. G., 263.Allen, R. J., 484.Allen, R. R., 299.Allen, T. L., 205.Allenstein, E., 142, 540.Allfrey, V. G., 455, 519.Allinger, J., 214.Allinger, N. L., 214, 220,Allmann, R., 575.Allmeningen, A., 117.Allulli, S., 532.Almenningen, A,, 130, 209,582, 583.Altenau, A. G., 533.Altona, C., 603.Altwicker, E. R., 119.Alworth, W. L., 396.Amano, Y., 589.Amberger, E., 118, 128,Ambler, R. P., 507.Ambrose, J. R., 65.Amendola, A., 583.Amerdola, A., 586.Ames, B. N., 476.Ames, D. E., 387.Amir, S.M., 492.Amma, E. L., 187, 587.Amorosa, M., 422.Anacker, E. W., 158.Anaclerio, A. M., 468.Anantakrishnan, C. P., 541.Anantakrishnan, S. V., 218.Anastasi, A,, 507.Anbar, M., 135, 280.Anchel, M., 359.Anderegg, G., 73, 74.Anders, M., 453.Anders, M. W., 466.Anders, 0. U., 543, 559.Anders, U., 155.Andersen, B., 209.Andersen, I. G. K., 260.Andersen, P., 613.Andersen, P. S., 384.Andersen, R. A,, 473.Andersen, T. N., 85.Anderson, A. G., 275.Anderson, A. G., jun., 392.Anderson, B., 494, 495.Anderson, C. B., 430.Andersm, C. D., 450.Anderson, C. M., 478.Anderson, D. G., 274.Anderson, D. H., 479.385, 411.13261 8 I:Anderson, D. M. W., 545.Anderson, E. K., 600.Anderson, E. P., 476.Anderson, E. W., 215, 349.Anderson, H.H., 133.Anderson, J., 505.Anderson, J. C., 379, 459,Anderson, J. D., 97.Anderson, J. R., 100.Anderson, M., 393.Anderson, N. R., 549.Anderson, R. A., 442.Anderson, R. B., 109.Anderson, R. S., 316.Anderson, W., 85.Ando, H., 439.Ando, M., 407.Ando, T., 482.Andreades, S., 270.Andres, W. W., 428.Andreu, P., 255, 256.Andrews, D. W. W., 552.Andrews, L. J., 273.Andreyeva, A. P., 492.Andrianov, K. A., 128, 130.Andrievskaya, E. A., 434.Aneja, R., 409.Anet, F. A. L., 217, 327.338, 347, 349, 351, 352,408.507.Anet, R., 327, 347.Anfinsen, C. B., 512.Angelici, R. J., 179, 186.Anger, F., 528.Anger, V., 528.Angus, H. J. F., 430, 433.Anirudhan, C. A., 391.Anisimov, K. N., 191.Annan, W. D., 441.Anner, G., 421.Ansell, M.F., 259.Anselme, J.-P., 380.Anslow, G. W., 554.Anson, F. C., 88.Antener, I., 481, 486.Anthrop, D. F., 78.Antonakis, K., 437.Antonini, E., 443.Antonucci, J. N., 333.Antropov, L. I., 81.Anzai, K., 450.Apin, A. Ya., 66.Appel, B. R., 242.Appel, R., 145.Appelman, E. H., 115, 116.Applebaum, M. N., 340.Applegart,h, D. A., 531.Applequist, D. E., 229, 326,Arai, T., 357.Arata, Y., 211.Arbuckle, J., 570.Archer, D. A., 255.Arcus, C. L., 282.Ardon, M., 177.349.DEX OF AUTHORS' NAMESAref'eva, T. V., 81.Arens, J. F., 314, 317,Argabright, P. A., 273, 308,Ariens, E. J., 460.Arigoni, D., 362, 422, 423,Arisoa, B. H., 414, 450.Arita, T., 552.Ariyaratne, J. K. P., 184.Ariyoshi, H., 321.Arlinghaus, R., 456.Arlt, w., 245, 249.h n a n , T., 479.Armendarez, P.X., 156.Armitage, D. A., 130.Armstrong, J. G., 406.Armstrong, M. D., 480.Arndt, C., 315.Arnek, R., 72.Arnet, E. M., 328.Arnett, E. M., 240.Arnold, H.-S., 130.Arnold, R. T., 254.Arnott, R. J., 157.Amstein, H. R. V., 455.Aroney, M. J., 208, 216,Aronson, S. M., 488.Aroskar, E. V., 333.Arsene, A., 392.Arshadi, M. R., 77.Arthur, J. C., 432.Arthur, P., 200, 614.Artyukh, Yu. N., 110.Arwidi, B., 533.Arzoumanian, H., 437, 438.Asahi, Y., 213.Asatoor, A. M., 485, 486.Asbun, W. L., 367, 426.Ashby, E. C., 123, 126, 290,Ashby, R. A., 105.Ashcroft, A. C., 360.Ashcroft, S. J., 70.Ashida, T., 595.Ashley, J. W., 92.Asinger, F., 259.Asmus, E., 534.Asmus, K.-D., 338.Aso, K., 440.Aspelin, G.B., 267.Asprey, L. B., 150, 168.Assarsson, A., 430, 431.Astakhov, I. I., 98.Aten, A. H. W., jun., 147.Atherton, N. M., 16, 30, 33,Athineos, E., 499.Atkins, G. L., 489, 490.Atkins, P. W., 39, 40.Atkinson, C. M., 220.Atkinson, L. R. E., 380.Atoji, M., 569.Attwood, B., 147.543.329.426.217, 220.324.198.Atwell, W. H., 373.Audier, H., 368, 412.Aue, D. H., 290.Auerbach, V. H., 481, 482.Aufdermarsh, C. A., 311,Augl, J. Bl., 186.Augustin, M., 300.Ault, A., 324, 351.Aumann, D. C., 559.Aumiiller, W., 323.Aurrichio, S., 478.Austin, L. G., 97.Austin, P. W., 440.Austin, S., 144.Averbukh, S. B., 93.Aveston, J., 158.Avin, M. L., 77.Avinur, P., 551.Avoyan, R.L., 597.Avram, M., 231.Axelrod, J., 462, 463, 474.Ayaz, A. A., 528, 535, 552.Ayer, W. A., 408.Ayers, P. W., 261.Aylett, B. J., 129.Aylward, F., 269.Aynsley, E. E., 146.Ayres, F. D., 164.Ayres, G. H., 552.Ayrey, G., 254.Ayscough, P. B., 34.Ayvazian, J. H., 489.Ayyanger, N. R., 258, 300.Aznavourian, W., 533.Baba, S., 419.Babel, D., 571.Bac, N. V., 302.Bach, G., 424.Bach, J. L., 341.Bachman, G. B., 309.Bachmann, G., 299.Baciocchi, E., 274.Bacon, G. E., 596.Bacon, R. G. R., 280, 333.Bactus, E., 453.Baczynskyj, C., 294.Badami, R. C., 319.Baddeley, G. V., 426.Baddiel, C. B., 143.Baddiley, J., 440, 497.Baddley, W. H., 177.Badenhuizen, N., 439.Badger, G. M., 218, 339,376, 387, 395, 531.Badoz-Lambling, J., 81.Baenziger, N.C., 183, 600.Baer, H. H., 430.Bar, H. P., 451.Bagby, M. O., 319.Bagg, J., 99.Bagli, J. F., 423.Bagnall, K. W., 149, 150,Bagotskaya, I. A., 84, 93.325.155, 160INDEX OF AUTHORS’ NAMBagotskii, V. S., 89, 95.Baibuz, V. F., 69.Bailar, J. C., jun,, 117.Bailey, D. M., 234, 258.Bailey, G. F., 284.Bailey, G. M., 266.Bailey, N. A,, 339, 591, 602.Bailey, P. S., 335.Bailey, R. W., 439.Bailey, W. J., 300.Bsin, J. A., 488.Baird, R. L., 247.Baitsch, H., 478.Baizer, M. M., 97.Baker, B. R., 435, 450.Baker, B. G., 100.Baker, C. S. C., 313.Baker, E. B., 238, 241.Baker, F. B., 154.Baker, K., 152.Baker, R., 230, 241, 243,Baker, R. H., 107, 553.Baker, T. N., 257.Baker, W. A., 160.Bakhmet’eva, G.S., 106.Balaban, A. T., 390, 392.Balakhnin, V. P., 45.Balandin, A. A., 101, 110,Balashova, N. A., 87, 88.Balasubramanian, K., 21 1.Balch, A. L., 218.Baldridge, R. C., 481, 482.Baldwin, J. E., 265.Baldwin, R., 482.Bale, W. F., 499, 511.Baliga, B. T., 288.Ball, D. H., 433.Ballantine, J. A., 377.Ballester, M., 336.Ballou, C. E., 441.Balls, A. K., 516.Ballschmiter, K.-H., 543.Balthis, J. H., 120.Bambenek, M. A., 218.Ban, Y., 403.Banarjea, D., 534.Banazek, H., 410.Bancroft, J. L., 21.Bancroft, K. C. C., 275.Randi, W. R., 561.Banerjee, B. C., 443.Banerjee, D. K., 555.Banerjee, R. S., 168.Baney, R. H., 129.Banford, L., 123.Bang, W. B., 125, 241, 327.Bangert, K., 229.Ban-I, K., 491.Banister, A. J., 123.Banitt, E.H., 324.Bankobskii, Yu. A., 158.Banks, C. V., 538.Banks, E., 570.Banks, R. E., 384.245, 275.111, 299.Banks, W., 429.Bannister, E., 156.Bannister, W. D., 185.Banta, M. C., 87.Banthorpe, D. V., 252, 281.Barabas, E., 392.Barakat, M. Z., 535.Barancheeva, N. G., 66.Barand, J., 319.Barash, L., 43, 266.Barbara, C., 314.Barber, G. A., 429.Barber, M., 321, 391.Barber, P., 432.Barbier, C., 219.Barbier, M., 320.Barbieri, R., 133, 532.Barclay, G. A., 152, 167.Bard, A., 88.Bard, A. J., 90, 534.Bard, L., 482.Bar-Eli, K., 35.Bargetzi, J. P., 507.Barinov, N. S., 299.Bark, L. S., 531, 563.Barker, C. K., 69.Barker, D. L., 605.Barker, G. C., 92, 97.Barker, I. R. L., 289, 290,Barker, R., 434.Barkhasch, V.A., 336.Barkulis, S. S., 498.Barlin, G. B., 383.Barlow, C. A., 83, 84.Barlow, J. S., 319.Barlow, M., 607.Barltrop, J. A., 265, 343.Barnartt, S., 94.Barnes, D., 245.Barnes, D. G., 331.Barnes, J. C., 176.Barnhurst, J. D., 301.Barnighausen, H., 572.Barnsley, E. A., 471.Baron, A. L., 430.Baron, D. N., 486.Barr, J., 146.Barraclough, C. G., 152.Barradas, R. G., 86, 87.Barratt, T. M., 478.Barretson, C., 132.Barrett, G. C., 388.Barron, Y., 111.Barry, G. T., 434.Barry, R. D., 370.Barsukov, L. I., 320.Bartell, L. S., 127, 592.Barth, H., 94, 296.Barthel, J., 74.Bartkiewicz, S. A., 546.Bartlett, M., 166.Bartlett, M. F., 403, 404.Bartlett, P. D., 231, 234,Bartlett, R. K., 124.431.237, 264.1s 619Bartman, J., 478.Barton, B.L., 30, 36.Barton, D. H. R., 304, 369,400, 419, 421, 425.Barton, J. M., 276.Barton, J. W., 335.Barton, L., 118.Barton, M. A., 459, 507.Bartz, A. M., 552.Bartz, K. W., 553.Barua, A. B., 305.Barua, R. K., 305.Basco, N., 52, 53, 54.Basinska, H., 536.Basinski, A., 108.Baskin, Y., 148.Basolo, F., 163, 177, 178,Bass, C. D., 77.Basselier, J.-J., 373.Bastiansen, O., 117, 130Bastien, I. J., 238.Bastings, L., 539.Basu, G., 164.Basu, N. K., 419.Basu, S., 168.Batelka, J. J., 248, 346.Bates, F., 431.Bates, R. B., 357.Bates, R. G., 81.Bath, S. S. 335.Batrakov, S. G., 321.Batsakis, J. G., 481.Batta, I., 102.Batterham, T. J., 391.Battersby, A. R., 397, 399,Battin, D. E., 263.Battiste, M.A., 347.Battles, W. R., 547.Batts, B. D., 275.Baudler, M., 140.Baudin, G., 535.Bauer, D., 155.Bauer, H., 381, 382.Bauer, H. H., 81.Bauer, H. J., 53.Bauer, K., 117.Bauer, L., 219, 281, 384.Bauer, S., 463.Bauer, S. H., 8, 68, 170,Bauer, V. J., 411.Bauman, C. P., 377.Bauman, J. E., 175.Bauman, J. E., jun., 74.Baumann, I., 575.Baur, W. H., 579, 580.Bautista, R. G., 61, 62.Bavin, P. M. G., 371.Bayer, H. O., 300, 373.Bayfus, D. A., 116.Beagley, B., 579, 593.Beak, P., 270, 390.Beals, D. L., 96.180, 181.583.400, 403.582,587620 INDEX OF AUTHORS’ NAMESBeamer, P. B., 481.Beamish, F. E., 528, 532.Beard, C., 411, 412.Beard, J. H., 249.Bearn, A. G., 501.Beaton, J. M., 421.Beattie, I. R., 123, 128, 130,Beaudet, R. A., 122, 205,Reaufds, J.-P., 102.Becher, D., 411, 412.Beck, W., 179, 180.Becke-Goellring, M., 138,Becker, A., 549.Becker, F., 74.Beckmann, W., 155.Bedford, A.F., 62.Bedford, G. R., 220, 382,Bedon, H. D., 151.Beer, R. J. S., 245. 392.Beers, &I. J., 311.Beevers, C. A., 601.Beezer, A. E., 62, 67.Behme, M. T., 293.Behmel, K., 129.Behr, 0. M., 314.Behrens, B., 179.Behrens, H., 155.Behringer, H., 133.Beinhofer, F., 130.Beirne, P. D., 252.Beisler, J. A., 228.Belcher, C. B., 550.Belcher, R., 550, 551.Beletskaya, I. P., 271.Belford, R. L., 164.Belikova, N. A., 62, 108.Beljajew, A. I., 81.Bell, C. E., 287.Bell, C. L., 219.Bell, G. M., 85.Bell, H. M., 222, 239.Bell, N. A., 117.Bell, R.A., 234.Bell, R. P., 275, 288, 297.Bell, S., 12.Bell, S. C., 394.Bella, D. D., 466.Bella, S. T., 523.Bellaart, A. C., 303.Bellamy, A. J., 356.Bellavita, V., 364.Bellelli, L., 443.Belman, S., 472.Beltram&, P., 229, 256.Belov, B. I., 328.Belov, N. V., 567.Bender, M. L., 296, 516.Benderskii, V. A., 41.Bendich, A., 389.Ben-Dor, L., 528, 552.Benedikt, G., 122.Benesovsky, R., 570.134, 146.581.144.390.Benitez, A., 450.Benjamin, B. M., 225.Benjamin, L., 75.Benkeser, I. N., 310.Benkeser, R. A., 276, 302,Benkovic, S. J., 292.Benner, G. S., 164.Bennett, J. E., 40, 117.Bennett, M. A., 183.Bennett, M. J., 186.Bennett, R. P., 276, 331.Bennett, W. R., 59.Benchiton, L., 495.Bonseker, R. A,, 333.Benson, A.M., 507.Benson, R. E., 32, 172, 342.Benson, S. W., 68, 256,Bentley, F. F., 208, 210.Bentley, H. R., 450.Bentley, K. W., 401.Bentley, R., 430.Benton, E. E., 50.Bentz, F., 433.Benz, E., 505.Benz, K. W., 60.Benzinger, T., 61.Beress, L., 296.Berezina, K. G., 555.Berg, H., 97.Bergelson, L. D., 305, 320,321, 531.Berger, H., 481.Berger, L., 488.Bergerhoff, G., 167.Bergh, A., 161.Berglund, H., 484.Bergman, J. G., 171.Bergren, W. R., 477.Bergsma, J., 569.Bergson, G., 273, 383.Berka, A., 540, 564.Berlandi, F. J., 535.Berlin, Yu. A., 345.Berliner, E., 246, 273, 297.Bernal, I., 30, 37, 171.Bernardi, L., 259, 507.Bernauer, K., 400.Berner, E., 297.Bernhard, K., 474.Bernhard, S. A., 293.Bernhauer, K., 370.Bernheim, R.A., 43.Bernstein, S., 417, 420.Beroza, M., 533.Berqvist, M. S., 356.Berry, C. T., 548.Berry, K. H., 386.Berry, K. O., 153.Berry, M. P., 321.Berry, R. S., 336.Berson, J. A., 225, 226, 266,Berson, S. A., 511.Bertaccini, G., 507.341.266.267, 284.Bertaut, F., 577.Bertele, E., 308, 375.Berthold, H. J., 143, 583.Berti, G., 249, 366.Bertin, E. P., 546.Bertocchio, R., 299.Bertolacini, R. J., 103.Bertolini, M., 496.Bertsch, H., 299, 306.Besford, L. S., 220.Bespalova, I. I., 309.Bessmann, S. P., 482.Besson, J., 535.Bestmann, H. J., 255, 305,Bethea, T. W., 420.Betina, V., 531.Bettschart, A., 466.Betzl, M., 576.Beugelmans, R., 212, 412.Beurskens, G., 579.Beurskens, P. T., 613.Bevan, C.W. L., 280,Bewick, A., 92.Beychok, S., 443.Beyer, H., 118.Beynon, P. J., 431.Bezjak, A., 589.Bezman, I. I., 139.Bhacca, N. S., 214, 359,362, 364, 368, 411, 412.Bhatt, M. V., 275.Bhattacharya, S. C., 528.Bhattacharyya, A. I<., 444.Bhavanandan, V. P., 442,Bhavsar, M. D., 392.Bick, I. R. C., 400.Biddiscombe, D. P., 63.Biemann, K., 396, 406, 430,Biernoth, G., 366.Biczais, A., 383.Biggins, J., 453.Bigliardi, G., 15S, 584.Bigorgne, M., 180.Bijsterbosch, B. H., 87.Bilevitch, K. A., 127.Bilham, J., 116.Billeter, M. A., 453.Billig, E., 171, 172.Billingham, E. J., 542.Bills, J. L., 65.BiIoen, P., 200.Bilovic, B., 268.Bilovic, D., 379.Binette, J. P., 494.Bingel, W. A., 26.Binger, P., 300.Bingham, C.D., 560.Ringham, J. T., 69.Bingle, J. P., 510.Bids, Pu., 397.Binnig, F., 339.Binsch, C., 206.316.365.496.559Birch, A. J., 322, 330, 369,374, 379, 386, 391, 416.Birch, G. G., 429.Birchall, T., 216.Bird, C. W., 373.Birintseva, T. P., 87.Birkofer, L., 433, 449.Biron, P., 524.Bisarya, S. C., 359.Biscup, M., 338, 394.Biserte, G., 492.Bishop, C. A., 280.Bishop, C. T., 444.Bishop, D. If., 135.Bishop, E., 539, 543.Bishop, R. J., 385.Bisnette, M. B., 182, 183,185, 187, 189.Bissing, D. E., 290.Bissinger, W. E., 324.Biswas, A. B., 586, 594.Bitz, M. C., 321.Bixby, E. M., 483.Bjamer, K., 607.Bjerrum, J., 167.Bjork, R. G., 541.Bjorvatten, T., 582, 615.Blaauw, H. J. A., 189.Black, P. J., 378, 330.Blackburn, G.M., 457.Blackburn, N. R., 470.Blackburn, R., 544.Blacklow, R. S., 487.Blackman, D., 295.Bladon, P., 423.Blaedel, W. J., 534,538,534, 561, 562, 563.Blair, A., 477.Blake, A. B., 73,584.Blake, A. R., 128.Blake, D. E., 460.Blakeley, St.J. H., 542.Blakley, E. R., 552.Blanchard, E. P., 346.Blandamer, M. J., 33, 40.Blanke, E., 423.Blanquet, P., 549.Blaschke, H., 381.Blasse, G., 192.Bliztchly, J. M., 275.Blatter, H. M., 411.Rlau, E. J., 135.Blau, S. E., 273.Blau, W., 331.Blauer, J. A., 75, 76, 77.Bleisch, S., 323.Blinder, S. M., $8.B l i ~ , E., 173.Bliznakov, G., 89.Bloch, H. S., 111.Bloch, K., 519.Block, H., 75.Block, J., 102, 111.Block, R. J., 484.Block. S., 579.Blofeld, R. E., 124.INDEX OF AUTHORS’ NATBlom, L., 543, 563.Blomberg, C., 310, 325.Blomgren, E., 84, 86.Blomgren, E.A., 86.Bloomfield, J. J., 311, 338.Blouin, F. A., 432.Bluhm, H.-J., 378.Blum, P. L., 535.Blumbergs, P., 436, 437,Blumenthnl, G., 168.Blunt, J. W., 413, 418.Bly, C. G., 499.Bly, R. M., 555.Blyumenfel’d, L. A., 41.Bobbitt, J. M., 357.Bobinski, J., 122.Bobinski, T., 121.Bobonich, €1. M., 160.Bocanovski, E., 564.Boccara, N., 311.Bochkov, A. F., 439.Gochkova, A., 59.Bockris, J. OW., 83, 84, 85,86, 87, 88, 94, 95, 96.Bock-Werthmann, W., 557.Bodanszky, M., 521, 522.Boddy, P. J., 87.Bodendorf, K., 309.Bodur, H., 479.Bockmann, A., 434.Boddeker, K. W., 118.Boef, G. D., 541.Eohm, R., 139, 300.Boekelheide, I T ., 31, 229,Bold, W., 89.Biill, W. A., 324, 338, 347,Boern, H.-P., 128.Boer, F. P., 119, 581.BGrjeson, H., 439.Boeters, H. D., 128.Bogdanov, G. N., 330.Bogdanov, V. P., 492.Bogdanova, A. V., 305.Bogdanovski, G. A, 96.Boggs, S. E., 209, 218.Bognar, J., 5G2.Bohak, Z., 495, 513.Bohlmann, F., 286, 313,315, 317, 416.Boijo, B. T., 100.Eoikese, R., 216.Bc&sonas, R. A., 521.Boll, A., 394.Bolle, R., 455.Bolling, D., 48-1.Bollinger, J. M., 325.Bollyky-, L., 323.Bolme, D. W., 112.Bolton, C. H., 492.Bolton, J. R., 29, 30, 35, 36,45, 198, 199, 200.Bolton, R., 246.Bolton, W., 599, 606.450.410.394.E S 621Bolzan, J. A., 92.Bommer, P., 396, 406.Bonacci, M. L., 443.Bonati, F., 182, 191.Bonaventura, M.M., 214.Bond, A., 31.Bond, G. C., 99, 102, 106.Bond, R. P. M., 296.Boned, 31. L., 63.Bodiglioli, R., 188.Bonham, J., 270.Bonnell, J. E., 125.Eonner, J., 453.Bonner, W. A., 379.Bonnett, R., 318, 375, 3i6.Bonthrone, W., 382.Boonian, G. L., 92.Boorstein, S. A., 45, 200.Boos, D. L., 96.Boos, H., 375.Booth, G., 170.Booth, H., 213, 214, 220,Booth, J., 473.Bor, G., 182, 191.Borch, R., 307, 314.Borden, M., 482.Bordwell, F. G., 245, 273,Boreskov, G. K., 103.Borgardt, F. G., 322.Borisov, A. E., 142.Bork, K.-H., 414.Borland, J. L., 485.Bormann, D., 136, 311.Born, M. J., 559.Bornmann, P., 146.Bornowski, H., 315.Borovkov, V. S., 93.Borowitz, I. J., 391.Borst, P., 453.Borgta, D. A., 560.Bose, A. K., 406, 412.Bose, J.L., 429.Bose, R. J., 439.Bose, S., 443, 444.Bosisio, G., 507.Boss, B., 127.Bosshard, H., 423.Bostrom, H., 486.Bostwick, L., 450.Bokhner-By, A. A., 206,Bothorel, P., 206.Bott, R. W., 101, 2’73,Bottari, F., 249, 366.Bottin, J., 368, 412.Bottomley, M. J., 127.Bouchard, R. J., 164.Bouchaud, J.-P., 576.Bouchilloux, S., 493.Eoudart, M., 103.Boudreaux, E. A., 167.Bouillant, XI., 391.Boulton, A. J., 382.235.380.435.276622 INDEX OF AUTHORS’ NAMESBounden, J. E., 559.Bounsall, E. J., 178.Bourgeois, Y., 108.Bourn, A. J. R., 338, 352.Bourne, E. J., 430, 441.Bournique, R. A., 535.Bourns, A. N., 216, 252,Bourrillon, R., 494.Bousquet, W. F., 460, 467.Boutin, H., 570.Bouveng, H. O., 442, 444.Bovet, D., 466.Bovet-Nitti, F., 466.Bovey, F.A., 215, 349.Bowden, K., 297.Bowen, E. J., 328.Bowen, H. J. M., 558.Bowen, R. J., 96.Bowers, A., 416.Bowers, K. W., 31.Bowers, V. A., 41, 199.Bowie, J. H., 389.Bowie, R. A., 334.Bowles, B. J., 92.Bowles, W. A., 449.Boyack, J. R., 532.Boyce, R. P., 447.Boyd, D. B., 240.Boyd, R. H., 62, 258.Boykin, D. W., 379.Boyko, E. R., 601.Boyland, E., 462, 470, 472,Boyle, J. E., 103.Bozzato, G., 423.Brabets, R. I., 143.Brace, N. O., 215, 255,261.Brachet, J., 453.Brackett, T., 572.Bradbury, A., 44.Bradley, D. C., 152, 169,Bradley, J. N., 324.Bradney, M. A. M., 274.Bradshaw, J. S., 336.Brady, G. W., 161.Brady, L. E., 371.Brady, R. O., 487.Briinden, C.-I., 589.Brandle, K., 146.Brahms, J., 458.Braibanti, A., 158, 584..Brainina, E.M., 153.Brammer, K. W., 448.Brand, J. C. D., 18, 24.Brand, P., 571.Brandenburg, D., 508.Brandenburger, N., 66.Brandsma, L., 314, 317.Brandstatter, O., 130.Brannen, W. T., 246.Brannock, K. C., 341.Braschler, V., 249.Brassem, P., 31.Brasted, R. S., 173.254.473, 474.589.Brathovde, J. R., 189, 584.Bratoi, S., 22.Brattain, W. H., 87.Bratu, C., 390.Brauchli, P., 400.Braude, E. A., 325, 425.Brauer, G., 135, 153, 154.Brault, A. T., 181.Brauman, J. I., 203.Braun, T., 557, 563.Bray, G. A., 469.Brechbuhler, T., 481.B-Son Bredenberg, J., 362,Breed, L. W., 130.Bregman, J., 265, 567.Bregman, 3. M., 263.Brehler, B., 572.Breindel, A., 140.Breifbeil, F.W., 371.Breiter, M., 87, 88, 89, 94,Breiter, M. W., 88.Bremer, H., 508, 509.Brendel, K., 435.Brennan, H. M., 103.Brenner, N., 560.Brenner, S., 455, 600.Brent, C. R., 297.Bresinsky, E., 315.Bresler, S. E., 453.Bresler, V. M., 455.Bresler, W. E., 553.Breslow, D. S., 324.Breslow, R., 44, 252.Breslow, S., 521.Bresnick, E., 469.Breuer, E., 301, 371.Breuer, S. W., 397.Brewster, J. H., 300.Brey, W. S., jun., 126, 215,Breyer, B., 81.Briden, D. W., 543, 559.Briegleb, G., 204.Brieskorn, C. H., 362.Brieux, J. A., 278.Briggs, J. N., 479.Briggs, L. H., 363.Brigham, 35. P., 481.Bright Wilson, E., jun.,Brimacornbe, J. S., 436,Brinkhoff, O., 508, 509.Brinkman, G. A., 147.Brinkman, U. A. T., 535.Brinkmann, R.-D., 123.Brisdon, B.J., 157.Britton, D., 134, 581.Britts, K., 594, 600.Broaddus, C. D., 273.Broche, A., 297.Brockenhoff, H., 319.Brocklehurst, W. E., 523.Brockman, I. H., 58.364.96.219.205.437, 492.Brodasky, T. F., 531.Brodie, B. B., 460, 462.Brodie, H. J., 419.Brodowsky, H., 82.Rrogden, W. B., jun., 359.Broida, H. P., 49.Brois, S. T., 123.Brongersma, H. H., 241.Brookes, P., 447.Brooks, S., 441.Broom, A. D., 447.Brosset, C., 570, 577.Brossmer, R., 449.Brotherton, R. J., 126.Brown, A., 570.Brown, B. W., 588.Brown, C. A., 101, 206.Brown, D., 149, 150, 155,Brown, D. H., 138, 162,Brown, D. J., 387, 456.Brown, D. M., 446, 457.Brown, D. S., 614.Brown, E. A., 428.Brown, F., 464.Brown, H.C., 101, 222,229, 239, 258, 274, 300,301.Brown, H. W., 211.Brown, J. E., 552.Brown, J. M., 250, 416.Brown, J. R., 515, 517.Brown, K., 274, 377, 385.Brown, K. D., 430.Brown, K. S., 405, 407,Brown, L. H., 507.Brown, M. S., 300.Brown, P., 334, 475.Brown, R., 453.Brown, R. A., 322.Brown, R. D., 203.Brown, R. K., 283, 284,Brown, R. L., 58.Brown, R. T., 405.Brown, S. C., 59.Brown, T. H., 29, 46, 47,198, 200, 400.Brown, T. L., 116, 126, 129,133, 592.Brown, T. M., 157.Brown, W. A. C., 354, 364,Brown, W. G., 105.Brubaker, C. H., 154.Brubracher, L. J., 296.Bruce, J. M., 220.Bruck, P., 216, 241.Bruckner, K., 414.Briigmann, G., 426, 427.Brufani, M., 604.Bruice, T. C., 291, 292, 295,Brummer, S. B., 89, 96.159, 160, 345.175.426.300, 512.602, 610.296INDEX OF AUTHORS’ NSMES 623Brunner, E., 31.Brunner, H., 524.Bruno, J.J., 278.Bruylants, A., 294.Bruzzesi, M. R., 443.Bryan, R. F., 191,239,573,593, 600.Bryce-Smith, D., 280, 304,313, 329, 333, 335, 341,342, 383.Bryden, J. H., 582.Brzostowska, M., 83, 84.Buben, N., 41.Bublitz, D. E., 286, 340.Buchanan, J., 497.Buchanan, J. G., 434, 440.Buchholz, R. F., 240.Buchi, G., 360, 369.Buchman, O., 276.Buck, H. M., 241.Buck, K. R., 275.Buck, K. T., 400.Buckingham, A. D., 189,Buckley, A., 297.Buckley, N. C., 228.Buckmaster, M. D., 308.Bucourt, R., 426.Bucovaz, E. T., 472.Buddecke, E., 496, 497.Budding, H. A., 395.Budenz, R., 145.Budevsky, O., 551.Budke, C.C., 555.Budzikiewicz, H., 212, 368,396, 400, 412.Buchi, G., 404, 406.Buchler, W., 540.Buchner, W., 117.Bueding, E., 442.Buehler, C. A., 331.Bidder, E., 449.Biirger, H., 129, 152, 155,Biirgle, P., 332.Buffagni, S., 163.Bugg, C., 596.Buisson, G., 577.Buka, M. R., 158.Bukun, N. G., 83, 98.Buley, A. L., 28.Bull, J. R., 412.Bull, W. E., 163.Bullock, E., 393.Bu’Lock, J. D., 315.Bumgardner, C. L., 136,270.Bumpus, F. M., 524.Bunce, S. C., 230, 276.Bunker, P. R., 205.Bunnenberg, E., 411, 412.Bunton, A., 297.Bunton, C. A., 222, 229,Burakevich, J., 368.Burbank, R. D., 571.BUChmdtf, O., 391.202.161.250.Burch, H. B., 470.Burckatter, J. H., 290.Burckhardt, U., 328, 352.Burdett, J. L., 288.Burdon, J., 97, 279, 333.Burdon, R.H., 453.Burg, A. B., 119, 137, 140.Burger, I., 538.Burger, M., 506.Burgher, R. D., 299.Burgstahler, A. W., 328,Burhop, E. H. S., 58.Burke, J. F., 502.Burke, K. E., 537.Burke, N. I., 379, 426.Burkhardt, G., 132.Burling, E. D., 283.Burlingame, A. L., 402.Burn, D., 415,416.Burnelle, L., 25.Burnett, C. H., 488.Burnett, D., 549.Burns, D. A., 519.Burns, J. H., 140, 572.Burns, J. J., 469.Burpitt, R. D., 341.Burrous, M. L., 302.Bursey, M. M., 387.Burstein, R. Kh., 94, 97.Burstein, S. H., 416.Burwell, R. L., 99, 106,Burzlaff, H., 582.Busch, D. H., 165, 173.Busetti, V., 603.Busev, A. I., 529, 534.Busfield, D., 468.Busfield, W. K., 218.Bush, E. T., 557.Bush, J. B., 203.Bush, R.P., 130.Bushick, R. D., 240.Busmann, E., 570, 575.Butcher, J., 541.Butcher, S. S., 205.Butler, A. R., 296.Butler, D. N., 322, 386.Butler, I. S., 179.Butler, M. E., 417.Butler, T. C., 474.Buttery, S. H., 441.Buyle, R., 302, 309.Buyske, D. A., 471, 475.Bycroft, B. W., 405.Bykhovakii, V. K., 56.Bynum, E., 476.Cabib, E., 451.Cadogan, J. I. G., 262, 324,Cady, G. H., 143, 145.Cagliotti, L., 300, 415, 420,Cainelli, G., 415, 422.426.107.Buu-Ho~’, N. P., 302, 312.336.422.Cakes, R., 574.Cairns, J., 454.Cairns, T., 220.Calabretta, P. J., 133.Calame, J. P., 426.Caldera, R., 481.Calderazzo, F., 187.Calderbank, A., 343.Caldwell, R. A., 270.Calf, G. E., 105.Califano, S., 219.Callahan, S. W., 464.Callear, A.B., 52, 53,54, 56.Calleri, M., 612.Calloman, J. H., 15, 23, 24,Callow, R. K., 419.Calvert, D., 85.Calvet, E., 61.Cambie, R. C., 363, 412.Camerman, A., 597.Camerman, N., 141, 608.Cameron, D. W., 341, 343,Cameron, N., 582.Camier-Ribereau-Gayon,Campbell, B. J., 521.Campbell, C. D., 336, 382.Campbell, G. W., jun., 120.Campbell, I. D., 314.Campbell, I. G. M., 133.Campbell, R. W., 323.Campbell, W. E., 109.Campbell, W. M., 183.Canady, W. J., 74.Canby, J. P., 481.Canceill, J., 421.Cannon, P. L., 562.Canonica, L., 362.Cantrall, E. W., 420.Canziani, F., 173, 190.Caple, R., 259.Caplow, N., 289.Capon, B., 234, 249, 288,295, 436, 439.Capps, J. C., 499.Caputo, A., 443.Carayon-Gentil, A., 309.Carazzolo, G., 603.Carbon, J.A., 449.Cariati, F., 179.Carley, F. B., 541.Carlin, R. L., 162, 164, 173.Carls, G. A., 390.Carlson, A. A., 385.Carlson, C . G., 286, 331.Carlson, D. M., 432.Carlson, R. M., 330.Carnevale, A., 103, 547.Caro, L., 501.Caron, A., 590, 595, 607.Carpenter, F. H., 515.Carpenter, G. B., 125, 581.Carpenter, J. G. D., 220,25.392.M., 319.385624 INDEX OF AUTHORS’ NANESCarr, J. B., 214.Carr, M. D., 250.Carrii, S., 256.Carr-Brion, K. G., 545.Carriel, J. T., 182.Carrier, W. L., 447.Carrington, A., 27, 29, 30,31, 35, 36, 37, 198, 199,200.Carrington, T., 49.Carron, G. J., 582.Carson, A. S., 70.Carson, N. A. J., 482.Carson, N. J., 482.Carsten, M. E., 493.Carter, F. L., 347.Carter, H. E., 441.Carter, J. L., 106.Cartledge, F.K., 132.Cartledge, G. H., 98.Carubelli, R., 496.Carver, R. J., 546.Case, J. R., 145.Casini, G., 437.Casinovi, C. G., 364.Cason, J., 208, 320.Caspi, E., 286, 330.Cassidy, J. E., 531.Castagnoli, N., jun,, 374.Castellan, G. W., 93.Castellucci, N. T., 329, 349.Castor, W. W., 533.Castro, C. E., 255, 313.Casu, B., 430.Caswell, L. R., 108.Catterall, R., 36.Caughlan, C. I?., 357, 610.Cava, M. P., 213, 327, 380,386, 387, 400, 404, 405.Cavasino, F. P., 162.Cave, A., 427.Cave, G. C. B., 540.Cavell, R. G., 71, 137, 140.Came, P. A., 558.Cezcherelli, P., 364.Ceder, O., 321.Cei, J. M., 507.Celeste, J. R., 303.Cerfontain, H., 276.Cerny, M., 429.Cerny, V., 426.Cervantes, A.; 330, 418.Cesani, F. A., 18.Chabrier, P., 309.Chakrabarti, C.L., 529,562.Chakravorty, A., 165.Chalenko, V. Q., 110.Chalk, A. J., 183.Chalmers, R. A., 527.Chambant, A. M., 509.Chamberlain, N. F., 285,Chamberland, B. L., 118,Chamberlin, J. W., 368.Chambers, C., 126.553.120.Chambers, L. M., 88.Chambers, M. J., 268.Chambers, R. D., 384.Champ, H. A. J., 150.Champernois, A., 478.Chan, K. S., 376.Chan, S. I., 389, 456.Chan, W. R., 365.Chandrasekar, B. K., 453.Chang, C. W. G., 344.Chang, F. C., 306, 309.Chang, H. W., 44.Chang, M. Y., 410.Chang, P., 433.Chanley, J. D., 426.Chan-Ming Hu, 433.Chao, G. Y., 583.Chao, M. S., 89.Chapat, J. P., 229.Chapmm, C. D., 58.Chapman, D. J., 156.Chapman, N. B., 246, 297.Chapman, 0.L., 207, 350,Chapovsky, Yu. A., 121.Chappel, C. I., 467.Chargaff, E., 446, 451, 455.Charles, R. G., 561.Charlot, G., 81.Chmravanti, D., 319.Chaston, S. H. H., 323.Chatt, J., 160,165, 166,181,Chatterjee, A., 557.Chatterjee, A. N., 505.Chaudhari, IVI. A., 188.Chaudhry, M. T., 333.Chauveau, J., 500.Chauvet, J., 507.Chawla, I. D., 159.Clhaykovsky, M., 306, 308.Chazin, J. D., 549.Chechak, A. J., 318.Clheema, Z. F., 225.Cheeseman, G. H., 116.Clheeseman, T. P., 588.2heft,el, C., 493.Zhemerda, J. M., 414.Zhen, C. C., 509.Shen, C.-Y., 208, 220.Zhen, H. Y., 553.Zhen, P. S., 532.Zhernick, C. L., 71, 116.Zhernov, H. I., 467.Zhernykh, L. V., 68.Jhemut, D. B., 44, 200.2hester, R., 547.Zhesterfield, J.H., 387.Zheung, K. K., 361.Zheutin, A., 219.Zhia, Y. T., 120.Zhiancone, E., 443.Zhia Tang Lu, 611.2hibber, 5. S., 237.Xiidester, J. L., 453.:hien, P.-L., 426.393.190.Chiesa, A., 190.Chiesara, E., 467, 468, 470.Chi-Hsiang Wong, 599.Child, K. J., 468.Childers, M., 289.Childress, S. J., 394.Childs, B., 482.Chinn, L. J., 420.Chiotis, E. L., 557.Chirkov, Yu. G., 97.Chisholm, M. J., 319.Chismadzhev, V. A., 97.Chisolm, J. J., 482.Chiswell, B., 163, 173.Chiu, G., 542.Chiu, Y., 200.Chiu, Y.-N., 45.Chizhov, 0. S., 430, 559.Chizmadzhev, Yu. A., 83.Chkheidze, I. I., 41.Chladek, S., 451, 452.Chloupek, F. J., 222, 229.Cho, E., 467.Choi, S., 197.Chopin, J., 219, 391.Chosson, A., 492.Chou, C. Y., 156.Chou Kung-du, 577.Chow, H.W., 328.Chrambach, A., 519.ChrBtien-Bessihre, Y., 299,Christ, H., 185.Christensen, B. G., 414.Christensen, J. E., 437.Christensen, J. J., 74.Christensen, N. H., 276.Christensen, R., 62.Christenson, I., 297.Christian, G. D., 542.Christie, J. H., 88.Christie, W. W., 319.Christman, D. R., 258.Christmann, K. F., 306.Christol, H,, 347.Christov, S. G., 90, 94.Christyakova, E. M., 564.Chu, B., 103.Chu, F. S., 521.Chu, S. Q., 509.&ua, J., 450.Zhudzynska, H., 146.Chun, E. H. L., 452.Chung, A. L. H., 196.Churchill, M. R., 186, 339,Cliadelli, F., 325.siampolini, M., 73, 74, 165,Cliba, J., 535.Zicero, C., 273.Jid-Dresdner, H., 578.Xuentes, L., 489.zignarella, G., 250.&nitti, M., 205.Xnbollek, G., 423.301.591.167INDEX OF AUTHORS’ NAMES 625Claassen, A., 539.Claassen, H.H., 116.Clagett, D. G., 348.Clamp, J. R., 490, 493.Clapp, J. W., 471.Clar, E., 330.Clardy, J., 336.Clark, C. T., 462.Clark, G. F., 123.Clark, H. C., 71, 132, 157,Clark, J., 370.Clark, L. W., 273, 276.Clark, M., 94.Clark, R. D., 255.Clark, R. J., 160.Clark, R. J. H., 171, 172,Clark, S. L., 121.Clark, V. M., 312, 323.Clarke, E. A., 399.Clarke, E. W. C., 9.Clarke, R. L., 61.Clark-Lewis, J. W., 388.Clarkson, D., 337.Claus, P., 301.Clauser, H., 496, 509.Clavilier, J., 87.Clayton, B. E., 481.Clayton, J. E., 490.Clayton, R. N., 563.Claxton, T. A., 205.Clearfield, A., 151.Clemens, D. F., 126.Clement, C., 206.Clement, G.E., 296.Clement, M. J. Y., 21.Clement, W. A., 270.Clement, W. H., 306.Clifford, A. F., 115.Cline, M. J., 453.Closs, G. L., 275, 324, 347.Closs, L. E., 324.Closson, W. D., 233.Clouet, D. H., 467.Clovis, J. S., 282.Cluett, M. L., 538.Cnotka, H.-G., 135.Coad, P., 281.Coad, R. A., 281.Coates, G. E., 74, 117, 123,Coats, A. W., 534, 560.Cobble, J. W., 66.Coburn, R. A., 328.Cochran, E. L., 41, 199.Cochran, G. W., 453.Codell, M., 536.Codey, G., 416.Coe, G. R., 325.Coe, J. S., 166.Coe, P. L., 333.Coffey, C. E., 190.Coffey, D., jun., 209.Coffey, J. A., 519.Coffman, D. D., 145.592.175, 176.127, 168.Cogan, D. G., 481.Coggins, R. A., 431.Cohen, A. I., 391.Cohen, A. J., 419, 471.Cohen, D., 150.Cohen, J.A., 516.Cohen, J. S., 457.Cohen, M. D., 265, 567.Cohen, M. S., 121, 122.Cohen, R. L., 276.Cohen, S. G., 336.Cohen, S. S., 464.Cohen, S. T., 140.Cohen, T., 248, 277.Cohen, W., 516.Cohnen, E., 428.Colburn, C. B., 18, 19.Colcleugh, D. W., 250.Cole, I., 444.Cole, R. D., 515.Cole, T., 38, 199.Cole, T. W., jun., 353.Cole, W., 234.Coleman, D. J., 63.Coleman, J. S., 149.Coles, J. A., 325.Colgrove, F. D., 59.Colin, R., 77.Collat, J. W., 118.Coller, B. A. W., 297.Collier, F. N., 158, 159.Collier, R. E., 384.Collinge, R. N., 128.Collins, A. G., 548.Collins, C. J., 225.Collins, D. J., 414.Collins, P. M., 249,431,439.Collis, M. J., 257.Collongues, R., 113.Colombo, A., 603.Colomine, M., 63.Colpa, J.P., 45, 46,Cotter, Allan K., 248.Colthup, E. C., 313.Colthup, N. B., 204.Colton, R., 149, 158,Colucci, D. F., 471.Colvin, C. B., 178.Comb. D. G., 453.199.160.98,59,Comer, F., 363, 412.Comisarow, M. B., 224,238,Comoy, P., 417.Cone, N. J., 406.Conia, J.-M., 348.Connett, B. E., 288, 436.Conney, A. H., 469.Connolly, J. D., 361, 364.Connolly, J. W., 129.Connor, D. S., 348.Connor, J. A., 148.Connors, L. J., 452.Conocchioli, T. J., 178.Conrew, C., 426.241.Considine, W. J., 133.Constantine, J. W., 524.Convert, O., 302.Conveur, C., 407.Conway, €3. E., 82, 86, 87,92, 94, 95, 96.Cook, G. M., 164.Cook, H. D., 86.Cook, L., 466.Cook, M. C., 436.Cook, R. J., 37, 38, 40, 199.Cooke, R.E., 482.Cooke, W. D., 554.Cookson, R. C., 33,, 346,Cooley, G., 415.Coon, J. B., 17, 18.Cooper, D. Y., 460.Cooper, R. D. G., 318.Cooper, R. L., 187.Cooper, W. B., 268.Coops, J., 310.Cope, A. C., 246, 351, 356.Cope, 0. J., 301.Copley, D. B., 137, 155.Coppens, G. A., 255.Coppens, P., 598.Coppinger, G. M., 23.Corbett, G. E., 334.Corbett, J. A., 529.Corbett, J. D., 142, 148,Corbett, R. E., 361.Cordes, A. W., 146.Cordes, E. €I., 287,289,293,Cordey-Hayes, M., 131.Corey, E. J., 234, 249, 304,306, 308, 329, 335, 348,358, 369, 372.Corey, E. R., 589.Corey, H. S., jun., 305.Corfield, G., 214.Corfield, M. G., 216, 217.Cori, G. T., 480.Cornblath, M., 478, 479.Cornet, D., 107, 111.Cornu, P. J., 417.Coronelli, C., 428.Correia, J.S., 311.Corrodi, H., 343.Corse, J., 559.Corsing, P., 241.Cort, J. H., 520.Corvaja, C., 34.Costain, C. C., 205.Cotter, M. L., 305.Cottier, P., 486.Cotton, F. A., 65, 73, 114,158, 159, 162, 169, 171,176, 179, 182, 192, 573,584, 585, 585.Cottrell, T. L., 48, 49, 57.Cottrill, E. L., 122.Coughlin, J. P., 70.Coull, J., 533.348, 415.574.296626 INDEX OF AUTHORS’ NA:Coulson, C. A., 10, 18, 19,26, 116, 196, 200, 218,337, 395.Coulson, D. R., 305.Coupe, R., 310.Courduvelis, C., 295.Courteney, K. D., 468.Cousins, M., 187.Coutsogeorgopoulos, C.,Couvillion, J., 602.Cowan, G. C., 49.Cowell, D. B., 538, 544.Cowell, G. W., 324.Cowell, R. D., 32.Cowley, A. H., 140.Cox, A. P., 128.Cox, B.C., 533.Cox, B. G., 290.Cox, D. A., 389.Cox, J. D., 64, 79.Cox, M., 60.Cox, R. A., 458.Coxon, B., 430, 438, 439.Coxon, J. M., 414.Coyle, T. D., 125.Crabbe, P., 204, 412.Craft, L., 342.Craft, M. K., 522.Craig, A. D., 136.Craig, D. P., 197.Craig, J. M., 483.Craig, L. C., 508, 524.Craig, N. C., 210.Craig, R. M., 302.Cram, D. J., 229, 269, 336.Cramer, F., 451, 452.Cramer, J. M., 472.Cramer, R., 183.Cramer, R. 31. R., 42.Cramp, W. A., 437.Crampton, M. R., 277, 332.Crandall, J. K., 234, 235,Crane, R. K., 478.Craske, J., 486.Craven, B. M., 605, 606,Crawford, B., jun., 212.Crawford, E., 105, 106.Crawhall, J. C., 485, 489.Creaven, P. J., 463.Creemers, H. &I. J. C., 132.Crerner, S., 355.Crestfield, A.M., 511.Crevecoeur, C., 574.Criegee, R., 326, 349.Crisp, P. C., 255.Cristol, S. J., 231, 263.Critchfield, F. E., 545, 562.Croft, M. K., 522.Cromartie, R. I. T., 343,Crombie, L., 321, 370, 390.Cromer, D. T., 569, 570,452.258.609.392.571, 573, 576.Cromwell, N. H., 255.Croy, P., 294.Crosby, D. G., 309.Crosby, N. T., 553.Cross, A. D., 330, 416, 418.Cross, B. E., 369.Cross, R. J., 131, 192.Crow, W. D., 382, 410.Crowell, T. I., 287.Crowley, K. J., 315.Cruickshank, D. W. J., 593.Cruickshank, F. R., 576.Cruikshank, P., 297.Csapilla, J., 249.Cseh, G., 249.Cua, J. T., 519.Cukor, P., 549, 556.Culbertson, T. P., 417.Cullen, W. R., 141, 182,582.Culvenor, C. C., 398.Cumbo, C. C., 301.Cummings, W. A.W., 374.Cummins, C., 498.Cumins, R. A., 132, 133.Cunningham, J., 433.Cunningham, K. G., 450.Cunningham, L., 517.Cunningham, W. L., 441,Cupas, C., 227,286,353.Curcumelli-Rodostano, M.,Curl, R. F., jun., 205, 208.Curnuck, P. A, 209.Curry, J. D., 165.Curry, N. A., 596.Curry, R. H., 549.Curtin, D. Y., 213.Curtis, N. F., 159, 165.Curtis, R. F., 380.Cusack, N. J., 303.Cushen, D. W., 572.Cusworth, D. C., 480, 482.Cuthrell, R. E., 540.Cutler, D., 35.Cutshall, T. W., 273, 380.Cuvigny, T., 310.Cvetanovic, R. J., 60.Cyganski, A., 143.Cymerman Craig, J., 286.Czerkawski, J. W., 510.493.409.Daehlie, G., 147.Diihne, S., 211.Daen, J., 52.Daeniker, H. U., 250, 382.Daglish, M., 558.Dagnall, R. M., 530, 550,Dahl, L.F., 571.Dahl, L. P., 567.Dahlberg, J., 430.Daldig, W., 311.Dahlmann, J., 128, 141.Dahlquist, A., 478.Dahmen, E. A. M. F., 538.551.ESDa.hmer, L. H., 535.Dahms, H., 86, 88, 96.Dahne, W., 571.Dailey, B. P., 201.Dais, C. F., 31.Dalby, F. W., 21.Dale, J., 351.Dallavalle, F., 158, 584.Dallner, G., 461.Dalrymple, D. J., 245.Dalton, A. J., 501.Daly, J. J., 137, 582.Daly, L. H., 204.Dalziel, J. A. W., 534.Damaskin, B. B., 82,83,84,Damodoran, V. A., 333.Damow, P. L., 93.Dancis, J., 483.Dandh, K. V., 156.Daneck, K., 451.D’Angeli, F., 371.Danh, T. V., 535.Daniel, H., 249.Danieli, N., 219, 424.Danieli, It., 244.Daniels, J. M., 75.Daniels, M., 447.Daniels, W. E., 313.Danielsen, J., 584.Danielson, J., 601.Daniher, F.A., 436, 450.Danishefsky, I., 435.Dankert, M., 532.Darling, S., 478.DaRooge, M. A., 214, 450.Darwish, D., 242.Das, A., 442.Das, G., 551.Das, K. G., 406.Dates, G. P., 441.Dathe, C., 142.Datta, A. P., 322.Dat Xuong, N., 312.Dauben, W. G., 360, 420,Daudel, R., 203.Dave, K. G., 329.David, D. J., 550, 561.David, M. E., 481.Davidson, E., 503.Davidson, E. A., 430.Davidson, J. A., 270.Davidson, J. C., 400.Davidson, J. M., 166.Davidson, M., 219.Davidson, N., 169, 2i6.Davies, D. I., 263.Davies, G. T., 202.Davies, J., 70, 456.Davies, J. V., 66.Davies, K. W., 432.Davies, M., 214.Davies, M. O., 94.Davies, M. T., 416.Davies, W., 536.85.425INDEX OF AUTHORS’ NAMES 627Davies, W. D., 70.Davis, A., 549.Davis, A.C., 374.Davis, B. J., 519.Davis, B. R., 303.Davis, C. M., 537.Davis, F. A., 373.Davis, G. G., 288.Davis, H. E., 341.Davis, H. M., 554.Davis, J., jun., 456.Davis, J. B., 93, 318.Davis, J. C., jun., 209.Davis, K. E., 275.Davis, L., 534.Davis, M. J., 213.Davis, R. A., 135.Davis, T. C., 266.Davison, A., 171, 172.Davisson, C. W., 553.Dawallu, A., 109.Dawson, J. W., 124, 125.Daxe, J., 60.Day, A. C., 347.Day, P., 176.Day, R. J., 95, 553.Dayagi, S., 213.De, A. K., 529.Deacon, G. B., 168.Dean, B. M., 489, 490.Dean, F. M., 342.Dearman, H. H., 198Debabov, G., 520.De Baun, R. M., 103.de Belder, A. N., 437.de Boer, E., 32, 36,46,199.de Boer, P. C. T., 52.De Boer, T. J., 211, 334.Debray-Sachs, M., 502.Debuch, H., 319.de Castiglione, R., 507.Decouvelaere, B., 414.de Dugros, E.C., 463.Dee, L. A,, 264.Deering, R. A., 446.Defay, R., 82.Defaye, J., 434.de Fernandee, F., 525.de Gelis, P., 156.Deghengi, R., 424.De Groot, C., 467.de Groot, M. S., 42, 200.Deguchi, Y., 34.de Haas, J., 488.De Haas, PIT., 45.Dehnicke, K., 135,153,158.Deinema, M. H., 319.Deitsch, A. G., 130.De Jongh, D. C., 430,559.De Jongh, R. O., 203.de Kemmeter, F., 294.Dekkers, H. P. J. M., 241.de Kock, W. T., 425.De Kowalewski, D. G., 208.Del’Acqua, A., 528.delaey, P., 486.Delahay, P., 91, 92.de la Mare, P. B. D., 276.Delaroff, V., 426.de Lederkremer, R. M., 429.de Levie, R., 97.DelGiacco, R., 502.Delimarskii, Yu.K., 81.Delius, A. E., 525.Delmau, J., 219.de Mayo, P., 352, 356, 360,367, 369, 390.Demitras, 0. C., 130, 145.Denault, G. C., 342.Den Boer, D. H. W., 218,den Boer, P. C., 218, 337.Denham, J. M., 347.den Hertog, H. J., 384.Deniville, L., 304.Denney, D. B., 140, 245,Denniston, J. C., 484.Deno, N. C., 222, 239, 240,Denot, E., 416.Dent, C. E., 480, 482, 485,Dent, W. T., 185, 308, 317.de Oliveira, M. M., 400.De Prater, B. L., 66.De Puy, C. H., 371.Derbyshire, W., 199.de Rodriguez, E. G., 290,Desai, N. B., 313.Desai, V. B., 330.Desalbres, H., 299.Desiderato, R., 596.Desiderio, D. M., 396.3e Silms, R. C., 396.Deslongchamps, P., 399,Desnuelle, P., 515.l e Souza, R., 440.Despic, A. R., 90.Dessy, R. E., 325.Desvoye, K-L., 219.Dettke, &I., 189.Deulofeu, V., 400.Dev, S., 216, 234, 358, 359,Devanathan, M.A. V., 83,Devenji, T., 518.ie Vita, C., 324.Devlin, P., 212.le Vries, A, 486.le ITries, D. B., 89.Devyatykh, G. G., 131.le Wald, H. A., 522.Dewald, R. R., 117.3ewar, D. H., 146.3ewar, M. J. S., 78, 196,203, 245, 256, 332, 370.Dewhirst, K. C., 187.Ze Witt, L., 82.337.324.241, 261.486, 489.297.408.361, 362.86, 87, 88, 93, 94.De Wolfe, R. H., 297.Dhaliwal, P. S., 141.Dhami, K. S., 217.Dhaneshwar, R. G., 543.Dhar, M. L., 321.Dhont, J. H., 531.Diana, G., 603.Diara, A., 368, 412.Dias, H. W., 604.Diaz, A. F., 243, 244.Diaz, J., 489.Dibeler, V. H., 207.Dick, D. M., 527.Dickens, J. C., 72.Dickens, P.G., 51, 56.Dickenson, R. E., 592.Dickerhofe, T. E., 281, 384.Dickerson, R. E., 126.Dickey, E. E., 443, 444.Dickinson, C. J., 489.Dickinson, J., 97.Dickinson, R. N., 158.Dickinson, W. B., 245.Dickson, F. E., 139.Dickson, R. S., 186, 339.Diehl, E., 128.Diehl, H. W., 439.Diehr, H. J., 323.Diekmann, J., 323, 342.Dierickx, L., 498.Dietl, H., 185.Dietrich, H., 592.Dietrich, M. W., 206, 553.Dietze, W., 118.Dietzler, D. N., 436.DiGeorge, A. M., 481.Dighe, S. V., 191.DiGiaimo, M. P., 275.Dijkman, G. J. C., 531.Dijkstra, R., 538.Dimroth, K., 370, 390.Din, P. T., 215.Dinan, F. J., 283, 384, 549.Dineen, D., 385.Dinh van Hoang, 515.Dinn6, E., 353.Dinsel, D. L., 530.Dinstl, G., 529.Dinulescu, I.G., 231.Dinwoodie, A. H., 277.Dippy, J. F. J., 217, 297.Dirkse, T. P., 89.Dirksen, H.-W., 310.Dirkx, I. P., 211.Dirlam, J., 231.Dische, Z., 493.Discher, C. A., 556.Dischler, B., 202.Dittmer, D. C., 290, 373.Dix, D. T., 270.Dixon, E. J., 532.Dixon, G. H., 517.Dixon, J. A., 279, 335.Dixon, R. L., 467, 470.Dixon, R. N., 11, 14, 15, 16,25, 26628 INDEX OF AUTHORS’ NAMESDixon, W. T., 28.Djaldetti, M., 486.Djerassi, C., 204, 212, 368,396, 400, 404, 405, 406,407, 411, 412, 421.Dmuchovsky, B., 107,259.Doak, G. O., 142.Doane, W. M., 432.Dobbie, R. C., 57.Dobias, B., 89.Dobinson, F., 335.Dobler, &I., 354.Dobratz, I. W., 544.Dobroserdova, N. B., 106.Dobrott, R. D., 120; 580.Dobson, N. A., 314.Dobyns, V., 219.Dodd, C.G., 546.Dodge, R. F., 184.Doe, J. B., 540.Doebel, K., 438.Doering, W. von E., 242,329, 349.Dorr, F., 31.Doerr, I. L., 448.Dorscheln, W., 381.Dogonadze, R. R., 83.Doi, J. T., 244.Dolby, L. J., 249, 404.Doleji, L., 396, 427.DoIeZal, J., 540.Dolfini, D. M., 385.D o f i i , J. E., 385.Dolgii, I. E., 311.Dolin, P. I., 98.Dolinsky, M., 553.Dolphin, D., 375, 376.Domange, L., 574.Dombrovskii, A. V., 305.Domer, F. R., 466.Dommain, K., 140.Domschke, G., 342.Donaldson, G. R., 112.Donaldson, J. D., 131, 132.do Nascimento, J. M., 426.Donganges, P. T., 494.Donnan, M. Y., 535.Donnay, J. D. H., 581.Donnell, G. N., 477.Donoghue, J. T., 175.Donohue, J., 590, 595, 607,Dorain, P. B., 45.Dorfman, A., 487, 504.Dorfman, L., 256, 398.Dormandy, T.L., 478.Dorn, H., 220.Dornberger-Schiff, K., 578.Dorofeenko, G. N., 305,439.Dorokhov, V. A., 125.Dorst, W., 203.Dose, K., 532.Dosta, K., 146.Doty, F., 458.Dougherty, R. C., 275.Dougherty, T. J., 249.612.Douglas, A. E., 12, 15, 16,Douglas, A. W., 206.Douglas, B., 400, 404, 405.Douglas, B. E., 184.Douglas, C. M., 138.Dousa, T., 520.Doyle, J. R., 183, 189.Dowbenko, R., 263.Downs, A. J., 127.Drabarek, S., 519.Drago, R. S., 133, 175.Drake, R. P., 119.Dratovskii, M., 147.Drazic, V., 96.Drefah, G., 215.Drefahl, G., 305.Dreger, L. H., 411.Dreiding, A. S., 286.Dressler, K., 10.Dreuth, W., 134.Dreux, J., 299.Drewer, R. J., 387.Drews, H., 559.Dreyer, D.L., 364.Dreyer, H., 111.Dreyfuss, M. P., 311.Drowart, J., 77, 78.Drozd, V. D., 340.Dryden, H. L., 330, 417.D’ Silva, A. P., 548, 549.Du, Y. C., 509.Dubbs, D. R., 464.Dube, S. K., 517.Dubeck, M., 191.Dubernard, L., 504.Dubnoff, J. S., 164.Dubois, I., 17.Dubois, J. E., 249, 259,272, 275.Dubois, J. T., 60.Dubois, R., 478.Dubrovskaya, L. B., 66.Duckworth, M. 154.Ducker, J. W., 415, 416.Duc-Nguyen, H., 498.Dudek, E., 188.Dudek, E. P., 210.Dudek, G. O., 165, 210.Dudinyak, R. S., 335.Dudykina, N. V., 300, 392.Duell, M. J., 99.Durn, H., 336.Dusing, G., 135.Dufau, F. A., 108.Duffield, A. M., 452.Duffin, G. F., 370.Duffy, M., 249.Dugan, R. E., 552.Dugdale, I., 93.Duggan, J. J., 367.Duke, B. J., 118.Dukes, C., 474.Dukes, C.E., 472.Dukes, E. K., 535.Dula,ney, E. L., 374.17, 22.Dulova, V. G., 131.Duncan, A. B. F., 23, 24.Duncan, J. L., 23.Duncan, L. C., 145.Duncan, W. G., 305.Dunitz, J. D., 364, 375,Dunken, H., 548.Dunlop, A., 229.Dunlop, J. H., 177.Dunn, P., 132, 133.Dunne, T. G., 162, 179.Dupont, J. A., 122.du Preez, J. G. H., 150.Duquesnoy, A., 564.Durbin, R., 441.Durham, L. J., 412.Durr, G. J., jun., 448.Durst, R. A., 92, 554.Durst, T., 323.Dutler, H., 423.Dutschewska, H. B., 400.Dutta, B. N., 578.Dutton, A. I., 350.Dutton, G. G. S., 432, 440,Dutton, G. J., 472.DUUS, H. C., 68.Duval, C., 560.du Vigneaud, V., 519, 521.Dvolaitzky, M., 421.Dvorak, J., 121.Dvornik, D., 467.Dwiggins, C. W., jun., 546.Dworkin, A.S., 76.Dwyer, J. L., 552.Dyatlovitskaya, E. V., 320,Dye, J. L., 117.Dyer, F. F., 558.Dyke, S. F., 336, 391.Dyrnova, T. N., 66, 118.Dyson, J., 139.Dzieciuch, M., 92, 96.Eaborn, C., 101,275,276.Eades, E. D. M., 433.Eakins, J. D., 158.Eason, R., 453.Eastham, J. F., 116.Eastman, J. C., 118.Easton, N. R., 465.Eaton, D. R., 34.Eaton, P. E., 351, 353.Ebel, H. F., 336.Ebeling, M., 543.Eberson, L., 297, 303, 333.Ebnother, A., 374.Ebone-Bonis, D., 509.Ebsworth, E. A. V., 148.Eckfeldt, E. L., 556.Eckroth, D. R., 245, 377.Eda, N., 38.Edelin de la Praudiere,P. L., 73.Edelstein, N., 171, 172.590.443, 531.531INDEX OF AUTHORS' NAMES 629Edgar, J. A., 388.Edison, D. H., 254.Edo, H., 443.Edwards, A.G., 284.Edwards, A. J.,' 53, 146,Edwards, D. A., 156.Edwards, K. D. G., 485.Edwards, J. T., 299.Edwards, 0. E., 355, 409.Edwards, R. O., 482.Eeles, W. T., 128.Effenberger, F., 33 1.Efhov, A. I., 73.Efhov, E. A., 81.Efron, M. L., 483.Egami, F., 507.Egan, B. Z., 125.Egan, T. J., 477.Egger, H., 340.Eggers, S. H., 388.Eglinton, G., 220, 313, 314,Ehlers, K.-P., 130.Ehlert, T. C., 77.Ehrenson, S., 249.Ehrenstein, M., 425.Ehrlich, R., 126.Ehrlich-Rogozinski, S., 545.Eichseldorfer, D., 144.Eick, H. A., 148.Eigenmann, E. W., 254.Eilers, K. L., 371.Einstein, F. W. B., 577.Eisch, J. J., 393.Eisele, W., 249.Eisenberg, M., 97.Eisenberg, R., 171.Eisert, B., 355.Eisinger, J., 45.Ekhardt, D., 219.Elad, D., 308, 309, 368.Elagina, N.V., 62.el A'ssar, M. K., 128.Elbein, A. D., 429.Elbert, W. C., 530.Elder, R. C., 158, 162, 584,Eley, D. D., 104.Elion, G. B., 464.Eliseev, S. S., 157.Eliseeva, N. G., 118.Elison, C., 463.Elix, J. A., 218, 339, 395.El Khadem, H., 429, 436,Elkins, J. S., 102.Elliorr, I. W., 300.Elliott, D. F., 522, 565.Elliott, H. W., 463.Elliott, I. W., 386.Elliott, R. L., 130.Ellis, B., 415, 416, 533.Ellis, I. A., 120.Ellis, R. J., 285.Ellison, R. A,, 408.571.328, 354, 394, 602.585.440.Elmes, B. C., 416.Elomaa, E., 319.Eloy, F., 302.Elsden, D. F., 494.Elsinger, F., 375.el-Tayeb, O., 428.Elvidge, J. A., 220, 376.Elving, P. J., 81, 97.Emelkus, H. J., 128, 134,Emerson, G.F., 185, 256.Emerson, K., 581.Emerson, M. T., 127, 357,Emerson. T. R., 388, 449.Emery, F. W., 119.Emmelot, P., 447.Emmett, P. H., 99, 110.Emmons, W. D., 323.Emmott, P., 548.Emovon, E. U., 255.Endicott, J. F., 178.End6, A., 304.Enemark, J. H., 174.Eng, K. Y., 560.Engberts, J. B. F. N., 249,Engebretson, G. R., 599.Engel, Ch.-R., 424.Engel, W. K., 480.Engelbrecht, A., 146.Engelhardt, M., 305.Engelman, K., 489.Engelrnann, C., 559.Engelsma, J. W., 331.England, D. C., 120.Englert, G., 202.Englin, B. A., 108.Engstrom, L., 570.Enke, C. G., 88.Enomoto, M., 472, 473.Enrione, R. E., 119.Ensinck, J. W., 510.Enslin, P. R., 425.Epstein, H. T., 453.Epstein, W. W., 425.Erdey, L., 560.Erdley, L., 540.Erdtman, H., 359, 364.Erinc, G., 550.Eriksson, G., 321.Erlanger, B. F., 516.Erlenmeyer, H., 172.Erlich, M., 483.Erhardt, F., 341.Erhart, G., 336.Erman, W.F., 251.Ermolaev, V. L., 60.Ernst, Z. L., 74.Ernster, L., 460, 461, 462.Ershler, A., 91.Ershov, V. V., 330.Erspamer, V., 507.Ertinghausen, G., 315.Erusalimchik, I. G., 81.Eschard, F., 108.135.610.324.Eschenmoser, A., 375.Eschinasi, E. H., 305.Espinosa, E., 499.Espinosa, E. Z., 551.Espy, H. H., 237.Esse, R. C., 345.Estabrook, R. W., 460.Etemadi, A. H., 320.Ettinger, R., 211, 218.Eudy, N. H., 417.Evans, A., 453.Evans, C., 469.Evans, D. A. P., 476.Evans, D. F., 174, 202.Evans, H. B., 546.Evans, J., 136.Evans, J. C., 125, 238.Evans, J. S., 210, 450.Evans, P.R., 134.Evans, W. M., 25.Eveleigh, D. E., 441.Evens, F. M., 564.Everett, G. W., 165.Everson, W. L., 542.Evstegneeva, E. IT., 66.Evstigneev, V. B., 98.Emald, A. H., 177.Ewan, G. T., 558.Eaart, G., 137.Ewing, V., 130, 583.Exner, O., 297.Eyerman, E. L., 480.Fabbri, E., 558.Faber, H., 565.Fabian, J., 323.Fackler, J. P., 153, 159.Fadda, R., 71.FBssler, A., 145.Fag'ley, T. F., 297.Fahey, R. C., 256.Fahmy, A. R., 474.Fahn, S., 480.Fahrenholtz, S. R., 228.Fairbrother, F., 137, 155.Fajkoi, J., 413.Falconer, W. E., 39.Fales, H. M., 397, 402.Falk, F., 306.Falk, M., 468.Fallon, H. J., 488.Falqui, M. T., 577.Fang, J. H., 576.Fanning, J. C., 167.Faragella, F. F., 490.Faraglia, G., 133, 532.Farber, M., 69, 75, 76.Farberov, M.I., 309.Farina, M., 613.Farkas, E., 391.Farkas, J., 449.Farmer, T. H., 531.Farnum, D. G., 238, 347.Farooqi, 31. I. H., 444.Farrar, D. T., 66.Farrar, T. C., 125630 INDEX OF AUTHORS' NAIFarrar, W. V., 132.Farrell, P. G., 276.Farrissey, W. J., 285.Farthing, E. C., 417.Fasolino, L. G., 70.Fassel, V. A., 212, 545, 549,Fateley, W. G., 206.Fattorusso, E., 377.Faucherre, J., 117.Faulkner, R., 519.Fauran, C., 303.Faure, F., 549.Faut, 0. D., 162.Favre, J. A., 533.Fawcett, F. S., 135.Fay, R. C., 163, 174.Feairheller, W. R., jun.,Fearn, J. E., 333.Feaske, R. F., 160.Feates, F. S., 98.Feather, P., 416.Fedeli, W., 604.Feder, H. M., 67, 68.Fedor, L., 291.Fedor, L. R., 296.Feenan, K., 154.FehBr, F., 69, 143.Fehlhaber, H.W., 398, 418.Feigl, F., 528.Feil, S. E., 158.Fein, M. M., 121, 122.Feinberg, R. S., 376.Feingold, D. S., 441.Feit, E. D., 544.Feld, R., 152.Feldmann, H., 454.Fell, B., 259.Fellows, R. E., 485.Feltham, R. D., 182, 183.Feltkamp, H., 255.Feltz, A., 115.Fennell, T. R. F. W., 544.Fennessey, P. V., 31 1.Fenninger, D., 519.Fenton, D. F., 245, 251.Feoktistov, L. G., 101.Ferguson, E. E., 59.Ferguson, G,, 363.Ferguson, J., 148.Ferguson, R. C., 552.Fergusson, J. E., 146, 159,Ferland, J. M., 299.Fernandez, J. E., 290.Ferrari, A., 158, 584.Ferrari, C., 409.Ferretti, A., 157.Ferrier, R. J., 204,429,432.Ferris, J. P., 251.Fery, L. P. A., 256.Fessenden, R. W., 27, 28,Fetisova, T.P., 271.F6tizon, M., 368, 412.564.216.573.29, 40, 46.Fetter, N. R., 117, 126.Fichtner, K., 140.Ficini, J., 311, 314.Field, A. E., 190.Field, B. O., 170, 171.Field, C. M. B., 482.Field, J. B., 479, 480.Fields, E. K., 305, 307, 559.Fields, R., 324.Fieser, L. F., 379, 426.Fieser, M., 426.Figgis, B. N., 161, 162, 585.Filbey, A. H., 179.Filby, R. H., 558.Filler, R., 300.Finan, P. A., 430.Finar, I. L., 219.Finch, N., 396.Finck, H. W., 172.Findeiss, W., 127.Findlay, F. D., 54.Finkelstein, J. D., 482.Finley, K. T., 308.Fioshin, M. J., 88.Fioshin, M. Ya., 97.Firl, J., 268.Firnhaber, B., 109.Firsanova, L. A., 81.Firsova, T. P., 128.Fischer, A., 249, 275, 331.Fischer, E. O., 180, 182,186, 187, 188.Fischer, F., 245, 249.Fischer, F.H., 30.Fischer, G., 370.Fischer, H., 28,46. 187,195,216, 317, 334.Fischer, H. P., 238, 249.Fischer, J., 150, 573.Fischer, P. H. H., 31, 33.Fish, R. W., 340.Fisher, D. J., 92Fisher, G. T., 156.Fisher, J., 479.Fishman, D. H., 279, 335.Fishman, W. H., 460.Fitton, P., 350.Fitton Jackson, S., 491.Fitzgibbon, G. C., 66, 71.Fitzi, K., 258.Fitzsimmons, B. W., 139.Fitzwater, D. R., 573.Flahaut, J., 574.F l a b , J. G., 464.Flaschka, H., 541.Flavian, S., 265, 567.Fleck, W. E., 379.Fleckenstein, L. J., 246.Fleischer, E. B., 353, 586,Fleischman, J. B., 493.Fleischmann, D., 475.Fleischmann, M., 80,92, 97,Fleming, I., 347.Fleming, M., 441.600, 604.98.ESFlengas, S.N., 151.Fletcher, A. P., 491, 492.Fletcher, H. G., 432, 438,Fletcher, H. G., jun., 449.Flett, M. St., C., 204.Flis, I. E., 72.Fliszrir, S., 290.Flitcroft, N., 191.Flogel, P., 141.Flood, S. H., 273, 276.Floria, J. A., 544.Flowers, H. M., 445, 498.Floyd, M. B., 376.Fluck, E., 144.Flygare, W. H., 209.Flynn, E., 245.Flynn, K. G., 298.Foch Fu-Hsie Yew, 216.Fohlisch, B., 332.Foppl, H., 575.Fogel, N., 161.Fogle, C. E., 147.Folkers, K., 344, 374,Folling, A., 484.Folting, K., 580, 598.Fong, C. T. O., 520.Foote, C. S., 224, 227, 304,Foote, J. L., 276, 331.Forbes, J. W., 23.Ford, C., 161.Ford, C. T., 139.Ford, T. A., 118.Forester, J. D., 116.Forman, A., 200.Forman, E. J., 542.Forney, L. S., 248.Forrest, H.S., 449.Forrester, J. D., 127, 149,171, 572, 577.Forrester, J. E., 579, 580.Forrette, J. E., 249.Forsberg, H. E., 572.Forster, D., 174.Forster, L. S., 156.Forster, T., 197.Forstner, J. A,, 119.Fort, R. C., 224, 238.FOSB, O., 577, 583.Foster, A. B., 438, 444.Foster, D. J., 263.Foster, J. F., 442.Foster, R. G., 376.Foster, W. E., 123.Fouassier, C., 134.Foucaud, A., 219.Fouquey, C., 364.Fourrey, J. L., 364.Fouts, J. R., 466, 467, 469,Fouty, R. A., 290.Fowler, J. S., 290.Fowles, G. W. A., 133, 151,439.450.335.470.152, 154, 157, 180INDEX OF AUTHORS’ NAMES 631Fox, J. J., 387, 448, 449.Fox, J. R., 246.Fox, M., 485.Fox, M. R., 586.Fox, W. B., 141.Foxwell, C. J., 471.Foy, P., 368, 412.Fozard, A., 386.Fradkha, T.P., 412.Fraenkel, G., 213, 270, 430.Fraenkel, G. K., 29, 30,31, 35, 36, 37, 46, 199,200, 217.Frampton, V. L., 347.Francis, H. J., jun., 543.Francis, R. J., 397.Frank, G. A., 305.Frank, M., 486.Frank, W. A., 529.Franke, K., 83.Franklin, E. C., 493.Franks, A., 546.Franks, N. E., 430, 432.Franz, G., 143.Franzini, M., 586.Franzus, B., 216, 268, 351.Fraser, G. W., 138.Fraser, J. W., 543.Fraser, R. R., 466.Fraser-Reid, B., 434.Frasson, E., 165, 686.Frater, R., 507.Fray, G. I., 342.Frazer, M. J., 136.Frazer, R. T. M., 178.Frazier, S. E., 137.Frederick, E. W., 400.Frederiksen,’S., 450.Freed, J. H., 35, 36, 37, 45.Freedman, H. H., 238, 239,Freedman, L. D., 142.Freeland, L. T., 557.Freeman, E.S., 561.Freeman, H. C., 166, 586.Freeman, J. P., 270.Freeman, M., 478.Freeman,, P. I-., 262, 317.Freeman, R. A., 202.Freeman, T. S., 52.Frei, R. W., 552.Freidlin, L. Kh., 106, 107,Freidlina, R. Iih., 153.Freifelder, M., 299, 385.Fremery, M. I., 305.French, D., 440, 442.Fresco, J. R., 458.Fresnet, P., 272.Frey, H. M., 285, 347.Fricke, G., 140.Fricke, H., 334.Fried, J., 302,419,421,428.Friedberg, S. A., 176.Friederich, K., 130.Friedman, A. R., 396.338, 353, 601.108.Friedman, L. B., 120, 580.Friedman, M., 260.Friedman, N., 240.Friedman, 0. M., 447.Friedman, S. M., 456.Friedrich, E. C., 227, 242.Friederich, H. J., 338.Friederich, L. E., 360.Frigerio, N. A., 552.Frilette, V. J., 103.Frimpter, 0.W., 481, 485.Frisch, M. A., 61, 411.Frish, S. E., 59.Frisone, G. J., 247.Fritz, H., 406.Fritz, H. P., 134, 187.Fritz, J. S., 532, 539.Fritz, P., 124, 125.Fritzell, S., 484.Frodyma, M. M., 552.Froesch, E. R., 477, 478.Frolov, I. A,, 131.Fromage, F., 117.Frontino, G., 470.Frorath, F.-K., 575.Frosch, R. P., 198.Fruchart, R., 576.Fruchter, R., 511.Frumkin, A. N., 82, 83,84, 85, 88, 91, 93, 94, 95,98.Fry, E. M., 385.Frymoyer, J. W., 475.Fuchs, A., 362.Fuchs, J., 552.Fujita, T., 440.Fujimoto, G. I., 415.Fujimoto, J. M., 468.Fujinaga, M., 435.Fujinaga, T., 34.Fujita, T., 363.Fujiwara, S., 211, 536.Fukawa, H., 100.Fukin, K., 203.Fuks, M. Ya., 100.Fuks, R., 309, 314, 329.Fukuda, K., 509.Fukuda, M., 94.Fukui, K., 38.Fukui, Y., 321.Fukunaga, T., 327, 354.Fukushima, F., 593.Fukushima, I<., 214.Fuller, W., 454.Fullington, J.G., 296, 297.Fulmor, W., 219.Fulton, M., 333.Funakoshi, K., 386.Funakoshi, R., 448.Funderburk, L., 270.Funke, P., 406.Fuqua, S. A., 305.Furata, T., 414.Furberg, S., 607.Furin, G. G., 333.Furst, H., 103.Furth, E., 485.Furth, J. J., 453.Furukawa, Y., 451.Furusaki, A,, 608.Furuseth, S., 153.Furuta, S., 214.FUSCO, R., 388.Fusizaki, Y., 304.Fuson, R. C., 310.Futaki, R., 286.Futterman, S., 477.Gabbe, D. R., 564.Gabe, E. J., 603.Gabel, A., 151.Gad, A. M., 319.Gadzhiev, 8. N., 77.Gaertner, V. R., 372.Gaffredo, O., 507.Gafner, G., 597.Gaines, D. F., 119, 120, 124.Gaitonde, M., 234.Gajewski, J.J., 226.Gal, S., 560.Galanda, V., 486.Gal’chenko, G. L., 68.Gale, D. M., 246.Gale, I. A. D., 375.Galliland, A. A., 72.Gallo, G. G., 250, 430.Galloway, W. J., 249.Galt, R. H. B., 369.Games, D. E., 390.Gampolini, M., 162.Ganchev, N., 531.Ganellin, C. .R., 356, 376.Ganis, P., 594, 603.Gans, P., 149.Ganter, C., 423.Gaoni, Y., 218, 276, 339,355, 392.Garabediztn, M. E., 68.Garbws, C. F., 305.Garbini, L. J., 547.Garbisch, E. W., jun., 215.Garcia, E. E., 389.Garcia-Blanco, S., 578.Garcia-Fernandex, H., 114.Garcia-Sharp, F. J., 335.Gardais, A., 504.Gardella, L. A., 391.Gardiner, J. A., 118.Gardner, A. W., 97.Gardner Sumner, G., 179.Garegg, P. J., 433.Garfinkel, D., 461.Garforth, J.D., 160.Garg, C. P., 301.Garg, H. G., 435.Garner, B. J., 301, 304.Garner, C. D., 170.Garnett, J. L., 104, 105.Garralda, B. B., 532, 539.Garren, L. D., 469.Garrett, A. B., 119.Garrett, J. M., 303632 IlriDEX OF AUTHORS' NAMESGarrett, P. N., 120, 122.Garrido, M. L., 544.Garrod, A. E., 484.Gagid, M., 304, 422.GaspariE, J., 281.Gasser, G., 490.Gassinan, P. G., 290, 351.Gates, P. N., 125.Gatlin, L., 456.Gatos, H. C., 87.Gaudemer, A., 364.Gaudry, R., 423, 424.Gault, F. G., 107, 111.Gaur, H. C., 554.Gausset, L., 12.Gautheron, €3.. 340.Gautschi, F., 216:Gavin, R. BI., juii., 127,Gavory, R., 467.Gavrilenko, V. V., 127, 302.Gavrilova, V. A,, 98.Gaydon, A. G., 52.Gaye-VuillGme, 5. F., 330.Gayhart, R.B., 163.Gazda, E. S., 542.Gebauer, P. A., 147.Gebauhr, W., 558.Gebelt, R. E., 145.Gebert, E., 573.Gee, W., 124.Geele, E. J., 34.Gehrmann, W., 138.Geissler, M., 554.Geissler, W., 88.Geissman, T. A., 407, 426.Gelboin, H. V., 470.Geldard, J. F., 166, 586.Gelin, R., 307.Geller, K., 548.Geller, L. E., 421.Geller, S., 574.Gelli, G., 305.Gemmell, M. W., 358.Gempeler, H., 343.Gendell, J., 35.Generalov, N. A., 52.Geneste, P., 354.Gentsch, H., 104.George, G. &I., 554, 555.George, P., 73, 161.George, R. S., 149.Georgian, IT., 268.Gerber, N. N., 451.Gerding, P. G., 72.Gerhart, F., 144.Gerische;., H., 98.Gerken, R., 154, 155.Gerloch, M., 161, 162, 186,Germain, G., 603.Germain, J. E., 102, 106,Gerovich, 31.A., 83.Gerovich, V. M., 85, 86.Gerrans, G. C., 399.592.585, 591.108.Gerrard, W., 122, 136, 249,Gerratt, J., 166.Gerritsen, T., 482.Gershenzon, I. M., 45.Gershoff, S. N., 490.Gerson, F., 30, 31.Gerstein, J., 296.Gerteis, R. L., 116, 126,Gesi, I<., 40.Geske, D. H., 90, 218.Gesser, H. D., 530.Gestblom, B., 387.Geyer, R., 536, 554.Geymayer, P., 124, 129.Ghadimi, H., 481.Ghose, S., 689.Ghosh, B. C., 295.Ghosh, D. K., 38.Ghwh, P. B., 382.Ghuysen, J. M., 498.Giacin, J., 245.Giacomello, G., 604.Giacometti, G., 34, 46.Gianni, M. H., 371.Gibbons, W. A., 216, 334.Gibmeier, H., 94.Gibor, A., 453.Gibson, D. T., 220.Gibson, X I . S., 263.Gibson, W. K., 378.Giddings, J. C., 532, 533.Giddings, S.A., 187.Giddings, W. P., 231, 240.Gidley, G. C., 214.Gielen, M., 272, 310.Gifford, E. M.. 452.Gigg, R., 433.Gigg, R. H., 441.Gil, V. M. S., 201.Gilbert, A., 304, 341, 312.Gilbert, B., 400, 406.Gilbert, J. R., 118.Gilbert, M. E. A., 400.Gilbert, W., 456.Gilbertson, T. J., 396.Gilby, A. C., 15.Gilchrist, M., 296.Gilde, H. G., 97.Gilden, R. V., 455.Gileadi, E., 90, 92, 96.Gill, N. S., 73.Gill, P. S., 75.Gillard, R. D., 162, 163,176, 177, 190.Gillard, R. S., 167.Gilles, P. W., 76.Gillespie, A. S., jun., 557.Gillespie, L., 523.Gillespie, R. J., 142, 146,147, 216, 240.Gillet, P., 478.Gillette, J. R., 460, 466.Gilman, H., 128, 132, 373.Gilman, S., 88, 89, 96.311.592.Gilmore, J. T., 559.Gilson, T., 123, 130.Gimesi, O., 540.Giner-Sorolla, A..389.Ginsberg, A. ' P.,* 189, 190,569.Ginsberg, S., 495.Ginsburg, V., 498, 500.Ginzburg, V. L., 550.Girardi, F., 558.Girina, G. P., 97.Gitterman, C. O., 374.Giustiniani, M., 532.Givner, &I. L., 465.Gjertsen, L., 153.Gjessing, L. R., 481, 484.Glacet, C., 310.Glaeser, H. H., 178.Glarum, S. H., 33, 46.Glaser, L., 498, 506.Glasky, A. J., 453.Glasner, A., 551, 580.Glass, M. A. W., 328.Glasser, F. P., 576.Glaswick, C. E., 330.Glatz, A. C., 142.Glazer, A. N., 516.Gleicher, G. J., 260.Gleiter, R., 331.Glemser, O., 136, 143, 144,Glemser, Oskar, 136.Glen, A. T., 416.Glick, M., 503.Glockling, F., 131, 188, 192.Glotter, E., 368, 425.Glovadsky, Ya., 649.Glover, D., 422.Glover, G.I., 293.Glukhov, I. A., 157.Gnauck, G., 115.Gnoi, O., 419.Gnusin, N. P., 87.Goaman, L. G. G., 601.Gochaliev, G. Z., 98.Godfrey, L. E. A., 370.Godfrey, M., 197, 203.Godman, G. C., 501.Godtfredsen, W. O., 360.Godtfredson, W. O., 426.Goebel, P., 241, 327.Goedd, H. W., 483.Goedde, €1. W., 475.Gohr, H., 80.Golitz, D., 145.Goerdeier, J., 281.Goering, H. L., 237, 243,Gorler, K., 232.Goth, H., 381.Goetze, W., 138.Goggins, A. E., 33.Gohda, M., 425.Gokhale, M. V., 319.Gokhale, S. D., 128, 136.Golberg, L. A., 476.154.244INDEX OF AUTHORS’ NAMES 633Gold, A. H., 517.Gold, E. H., 241.Gold, V., 272,274,275, 277,Goldbacher, J. E., 309.Goldberg, I. H., 454.Goldberg, M., 532.Goldberg, S.I., 254.Goldbloom, R. B., 486.Goldfarb, T. D., 131.Goldfinger, I?., 77, 78.Goldfish, E., 595.Golding, B. T., 321.Golding, R. M., 39.Goldman, J. A., 538, 540.Goldman, L., 457, 505.Goldman, N. I,., 286.Goldsmith, G. J., 60.Goldstein, E. J., 129, 324.Goldstein, H. L., 121.Goldstein, H. W., 127.Goldstein, I. J., 440.Goldstein, 3. H., 456.Goldstein, M. S., 103.Goldwhite, H., 263.Golebiewski, A., 200.Golfier, M., 368, 412.Golinkin, H. S., 249.Golob, H. R., 214.Golocastikov, N. I., 567.Golomb, D., 17.Golova, 0. P., 434.Golovina, A. P., 549.Gomatos, P. J., 453, 459.Gompper, R., 251.Goncalves, I. R. J., 532.Goncan, H., 529.Goneim, F. B., 110, 111.Gonikberg, M. I., 334.Gonis, G.. 391.Good, W. D., 63, 65, 66,Goodall, D.M., 386.Goode, G. C., 555.Goodfriend, P. L., 18.Goodgame, D. M. L., 164,Goodman, L., 202,437,438,Goodrow, M. H., 124.Goodwin, E. S., 534.Goodwin, T. H., 218, 337.Goodwin, T. W., 318.Goodyear, J., 574.Goralski, C. T., 276, 331.Gorban’, A. K., 310.Gorbunov, A. I., 103.Gordon, C. N., 451.Gordon, E. I., 59.Gordon, J. E., 279.Gordon, L., 534.Gordon, M., 386.Gorgonova, E. P., 96.Gorin, G., 63.Gorin, P. A. J., 440.Gorini, L., 456.332.67.174.449, 450.Gorman, M., 404, 406.Gorodetsky, M., 416.Gorodyskii, A. V., 81.Goroshko, N. N., 62.Gorsuch, J. D., 539.Gosselck, J., 296.Gosselink, E. P., 324, 351.Gosser, L., 269.Gossner, K., 99.Gostienskaya, I. V., 106.Got, R., 494.Got6, H., 546, 547.Goto, R., 207.Goto, T., 360, 456.Gottardi, G., 578.Gotthardt, H., 373.Gottlieb, M.H., 96.Gottlieb, 0. R., 425.Gottschalk, A,, 496.Goubeau, J., 118, 142.Gough, J., 344.Gough, S. T. D., 313.Gough, T. E., 33.Gougoutas, J. Z., 388, 608.Gould, E. S., 178, 583.Gould, S. E., 481.Goulden, R., 534.Goutarel, R., 299, 407, 420,Gouteman, M., 45, 198,Gouverneur, P., 543, 544.Govindachari, T. R., 360,Gower, A., 201.Goy, G. A., 75.GOZZO, F., 64.Grabowich, P., 421, 428.Graddon, D. P., 158.Graf, E., 391.Graftstein, D., 121, 122.Graham, D. L., 531.Graham, E., 361.Graham, E. R. B., 496.Graham, J. B., 488.Graham, R. J. T., 531.Grahame, D. C., 82, 83,Gramera, R. E., 436, 438.Grandolini, G., 364.Granger, M.R., 270.Granger, R., 229.Grant, D. F., 601.Grant, D. M., 202, 206.Grant, D. W., 533.Grant, P. T., 496.Grantham, D. H., 86.Grantham, P. H., 472, 473.Gras, M. A. M. P., 419.Graselli, P., 420.Grasselli, J. G., 135, 186.Grasselli, P., 300.Grasshof, H., 429.Grassmann, W., 522.Gratzer, W. B., 458.Grau, G., 313.426, 427.200.403.84.Zraul, E. H., 483.Zraveland, A., 314.Gray, A. L., 559.Gray, D. W., 108.Gray, E. D., 455.Gray, H. B., 114, 160, 171,Gray, P., 135.Gray, S. L., 258.Gray, W., 536.Gray, W. R., 514.Grayzel, A. I., 488.Grdenic, D., 529, 589.Gream, G. E. G., 236.Greasly, P. M., 275.Grebner, E. E., 441.Green, D. M., 388.Green, H., 532.Green, J., 122, 282.Green, J. H. S., 63.Green, L., 453.Green, L.G., 69.Green, M., 86, 88, 96, 185,Green, M. L. H., 184, 187.Green, S. E. I., 325.Greenbaum, M. A., 69, 76,Greenberg, B., 586Greene, E. F., 52.Greene, F. D., 31, 258, 372.Greene, M. L. H., 313.Greene, P. D., 69.Greene, P. &I., 246.Greene, R. N., 249.Greenfield, S., 548.Greenwood, C. T., 429.Greenwood, H. H., 26.Greenwood, J. M., 359.Greenwood, X. ;?lT., 123, 127,Greenzaid, P., 260.Gregor, I. K., 162.Gregorowicz, Z., 535.Gregory, B., 393.Gregory, H., 507.Gregory, J. D., 494, 495.Gregory, R. A., 459, 507,Greig, C. G., 472.Greiner, A., 306.Grenthe, I., 72.Greuther, F., 423.Grey, P., 540.Griasnom, G., 300.Gribi, H. P., 375.Gribova, Z. P., 207.Griddle, W. J., 532.Griesbaum, K., 263, 265,Griffin, B.E., 452.Griffin, B. P., 321.Griffin, C. E., 305, 306.Griffin, G. W., 265.Griffin, R. W., jun., 328.G r a n , W. J., 489, 490.172.322.77.146.523.316, 347634 INDEX O F AUTHORS' NAIG r a t h , H. O., 200.Griffith, 0. H., 39.GrBth, R. K., 130.Griffith, W. P., 161.Griffiths, J. E., 131, 220.Griffiths, T. R., 167.Grigat, E., 322.Grigorenko, A. A., 305.Grigor'ev, A. I., 117.Grigoriev, N. B., 85.Grigoryan, A. N., 321.Grigoryev, N. B., 84.Grimison, A., 447.Grimme, W., 339, 353, 354.Grimmelikhuysen, J. C.,Grinberg, P. L., 373.Grinberg, Ya. Kh., 76.Grindstaff, W., 161.Grinter, R., 197, 203.Griswold, A. A., 350.Griswold, E., 162, 174.Grob, C. A., 238, 249, 285,Grobe, J., 181.Groger, D., 397.Groeger, H., 139.Grohmann, I., 108.Grsnbaek, R., 590.Gronowitz, S., 379, 387.Grsnvold, F., 575, 576.Gros, E.G., 396.Gros, P. H., 436.Grosjean, M., 276.Gross, J. B., 486.Gross, J. M., 33.Gross, P., 68, 69.Gross, P. H., 435.Grosse, A. V., 115.Grossman, II., 189.Groten, B., 583.Groth, P., 601, 604.Grove, J. F., 322, 390.Grovenstein, E., 273.Grover, P. K., 286, 330.Grover, P. L., 471, 472.Grubb, P. W., 265.Grubb, 'CV. T., 112.Gruber, H. L., 103.Gruen, D. M., 176.Gruen, L. C., 290.Gruger, E. H., jun., 319.Grunberg-Nanago, M., 456.Grundmann, C., 318.Grundon, M. F., 385, 399.Grundy, H. A., 64.Grundy, K. H., 155.Grunewald, G. L., 330, 353.Grushkin, B., 139.Gschwend, H., 375.Guarino, A. J., 451.Guerchais, J.E., 578.Guglielmetti, L., 362.Guha, M., 309.Guidoni, A., 515.Guilbault, G. G., 562.304.419.Guild, L. V., 533.Guilleman, R., 522.Guilloux, E., 440.Guinn, V. P., 557.Guinsberg, A. P., 569.Gum, P., 594.Gunn, E. L., 546.Gunn, S. R., 68, 69, 70.Gunner, S . W., 438.Gunning, H. E., 60.Gunstone, F. D., 319.Gunter, C. R., 296.Gunther, W. H., 150.Gupta, K. C., 444.Gupta, S. K., 76.Gupta, V. D., 133.Gurevich, A. I., 345.Gurst, J. E., 368.Gusev, B. P., 315.Gut, J., 281.Gut, M., 419.Guthrie, R. D., 429, 435.Gutman, A. B., 447.Gutman, B., 488.Gutmann, V., 124.Gutowsky, H. S., 202.Gutzwiller, J., 360.Guzzetta, F. H., 74, 174.Guzzi, G., 558.Guzzo, A. V., 31.Haaf, W., 309.Haag, A., 328.Haage, K., 299.Haagensen, C.O., 601.Haake, P., 143.Haaland, A., 117.Haas, A,, 136.Haas, D. J., 364, 393,Haas, T. E., 119, 176,Haas, W., 564.Habermehl, G., 207.Habib, M. S., 388.Habraken, C. L., 380.Hackerman, N., 87, 89.Hackman, R. H., 532.Haddad, A. C., 108.Haddad, Y . M. Y., 302.Haddadin, M. J., 379.Hadik, G., 259.Hadjiioannou, S., 407.Hadjiioannou, T. P., 561,Hadley, W. B., 74, 174.Hliberlein, H., 255.Hliffner, J., 316.Haenni, E. O., 549.Haensel, V., 111, 112.Haerdi, W., 558.Hafner, K., 324, 327, 334,337, 338, 380, 393.Hagenmuller, P., 134.Haggerty, M., 116.Hagstrom, S., 547.611.192.562.ESHagstrom, J. W. C., 501.Hahn, G. A., 124.Hahn, H., 572.Hahn, V., 268, 3i9.Hahne, H.-D., 140.Haiduc, I., 128.Haight, G.P., 162.Haight, H. L., 183.Haines, J. A., 447.Hair, R. P., 552.Haisa, M., 608.Hakkila, E. A., 545.HalBsz, I., 533.Hale, J. D., 74.Hales, C. N., 511.Halevi, E. A., 297.Halford, D., 44.Hall, D., 150, 588, 589.Hall, D. M., 394.Hall, D. N., 263, 316.Hall, D. W., 308.Hall, G., 555.Hall, H. K., 300.Hall, J. H., 373.Hall, J. R., 140.Hall, L. D., 349, 430, 456.Hall, L. H., 581.Hall, R. H., 447, 451, 452.Hall, R. J., 552.Hall, R. S., 407.Hall, S. K., 144.Hall, W. F., 76.Hall, W. K., 104, 106.Hall, W. L., 254.Hallmann, N., 478.Hallot, A., 417.Halls, C. M. M., 366.Halmann, M., 23.Halpern, J., 189.Halpern, W., 108.Halsall, T. G., 365, 426.Halvorsen, S., 484.Ham, G. E., 249, 371.Hamana, M., 386.Hamenaka, E., 358.Hamblin, M.C., 276.Hambraeus, L., 486.Hameka, H. F., 201.Hamer, F. M., 370.Hamied, Y. K., 343.Hamilton, G. A., 462, 463.Hamilton, L. D., 484.Hamilton, P. B., 533.Hamilton, W. C., 116, 189,577, 585, 590, 598.Hamlin, A. G., 533.Hammatt, E. A., 546.Hammer, C. F., 344, 420,Hammer, H., 109.Hammer, J., 520.Hammond, G. S., 282, 335,Hammond, P. R., 341.Hammons, J. H., 247, 346.Hamon, D. P. G., 346,415.611.350, 391INDEX OF AUTHORS’ NAMES 635Hamor, M. J., 174, 584.Hamw, T. A., 174, 584.Hanack, M., 232, 237, 316.Hanawatt, P. C., 453.Hand, E. S., 275.Handa, B. K., 572.Handley, R., 63.Handley, T. H., 556.Hands, A. R., 322, 376.Hanessian, S., 498.Hannah, R. W., 552.Hansell, D. P., 371.Hansen, B., 109.Hansen, R.I., 86.Hansen, R. P., 319.Hansen, W. N., 552.Hanson, A. W., 614.Hanson, H. T., 306.Hanson, J. R., 362, 369.Hanson, R. W., 495.Hantsche, H., 255.HanuB, V., 396.Haq, M. Z., 408.Haq, S., 439.Haque, M. E., 274.Harada, Y., 217.Harbon, S., 496.Hardegger, E., 343, 421.Harder, N., 155, 179.Hardie, B. A., 273, 276.Harding, B. W., 461.Hardy, C. J., 170, 171.Hardy, F. E., 440.Hardy, R. A., jun., 219.Hardy, P. M., 459, 507.Harfenist, E. J., 524.Hargreaves, A., 599.Hargrove, W., 406.Harigaya, S., 430.Harley-Mason, J., 347, 377,Harmon, K. M., 147.Harmony, M. D., 19.Harmuth, C. M., 290.Harold, P. L., 119.Harper, R. J., 105.Harrar, J. E., 93.Harrell, S. A., 147.Harrick, N. J., 552.Harriman, J.E., 32.Harris, C., 263.Harris, C. B., 159.Harris, D., 392.Harris, H., 477, 481, 486.Harris, J. I., 517, 518,Harris, R. K., 215.Harris, R. L. N., 375.Harrison, D., 333.Harrison, W. A., 418.Harrison, W. F., 275, 392.Harrop, D., 63.Harryvan, E., 31‘4.Hart, C. R., 271.Hart, D. M., 147.Hart, E. W., 486.399.519.XHart, F. A., 148.Hart, H., 232,240,331,350.Hart, K. K., 527.Hart, L. G., 469, 470.Hart, L. H., 467.Ha,rt, P. A., 411.Hart, W. A., 137.Hartel, J., 533.Hartenstein, A., 324.Hartley, A. M., 555.Hartley, B. S., 296, 507,514, 515, 516, 517.Hartley, S. B., 68.Hartman, P. E., 476.Hartman, R., 329, 372.Hartman, R. E., 425.Hartmann, H., 128. 134.Hartmann, H. A., 472.Hartog, F., 108.Hartshorn, M.P., 413, 414,Hartsuck, J. A., 358, 609.Hartter, D. R., 250.Hartwell, G. E., 129.Hartzler, H. D., 324, 347.Harvey, J. F., 147.Harvey, W. W., 87.Hase, W., 576.Hasegawa, &I., 407, 426.Haselkorn, R., 453.Hasheymeyer, A. E. V.,Hashimoto, Y., 461, 496,Hashmi, M. H., 528, 535,Haskell, T., 498.Haslam, E., 343.Haslbrunner, E., 453.Hass, D., 141, 142.Hassan, M. M., 319.Hassel, J. A., 104.Hassel, O., 213, 601.Hassell, J. A., 106.Hassid, W. Z., 429, 432,Hassner, A., 257, 412, 418.Haszeldine, R. N., 185,255, 324, 384.Hata, Y., 351.Hatch, L. F., 299.Hatch, W. R., 530.Hatfield, W. E., 160, 164,Hathaway, B. J., 174Hatton, K., 119.Haucke, G., 548.Haug, A., 444.Hauge, S., 583.Haupt, H., 498.Hauptmann, Z., 147.Hauser, C.R., 286, 392.Hauser, D., 249, 422.Hauser, H., 324, 372.Hausser, K. H., 31.Hausty, J., 594.416, 418.457.497.552.498.167.Hauth, H., 402.Havel, M., 385.Havel, S., 303.Havings, E., 203.Hawkins, A. E., 538.Hawkins, B. D., 297.Hawkins, J. T., 442.Haworth, J. C., 479.Hawthorne, M. F., 119,120,Hay, R. W., 296.Hayano, M., 419.Hayashi, K., 39.Hayashi, M., 453.Hayashi, M. N., 453.Hayashi, R., 418.Hayatsu, H., 448.Hayatsu, R., 408, 419.Hayduk, U., 141.Hayek, E., 531.Hayman, C., 68.Haymovitz, A., 481.Haynes, L. J., 400, 429.Hays, G. E., 110.Hayer, R. G., 164, 181,Haywood, A. M., 455.Hazan, I., 532.Hazel, J. F., 561.Eazell, A, C., 154, 583.Hazen, G. G., 420.Heacock, C.C., 257.Head, A. J., 63, 64.Headridge, J. B., 532.Healey, M. E., 393.Heaney, H., 336.Heathcock, C., 412, 415.Hecht, F., 529, 530.Hecht, H. G., 41.Heck, H. d’A., 296.Heck, R., 252.Heck, R. F., 188.Heck, W., 128.Hecker, E., 286, 330, 418.Hedayatullah, M., 304.Hedberg, K., 126, 130, 583.Hedges, R., 377.Hedgley, E. J., 432.Hedrick, C. E., 532.Hedrick, R., 295.Hedrick, R. I., 295.Heffelfinger, J. C., 484.Heffer, J. P., 166.Hefferman, M. L., 378, 380.Hefter, R. W., 469.Heftmann, E., 531.Hegge, E., 318.Hegenbarth, J. J., 600.Hehre, E. J., 443.Keide, K., 498.Heideman, M. L., 510.Heidrich, H. G., 522.Heilbronner, E., 31, 195,196, 197, 203, 338.Heim, P., 300.Hehburger, N., 498.122.190636 INDEX OF AUTHORS’ NAMESHein, F., 188.Heinbach, P., 285.Heine, H.W., 371.Heininger, C., jun., 532.Heino, W. L., 173.Heinonen, J., 468.Heinrich, G., 172.Heins, J. T., 559.Heinzel, M., 229.Heischkel, R., 415.Heit, M. L., 563.Heitmann, W., 378.Helgstrand, E., 275.Heller, C., 38, 199.Heller, D., 448.Heller, K.-H., 281.Heller, M., 417.Nellmayr, W., 135.Hellner, E., 575, 582.Helmer, F., 384.Helmkamp, G. K., 255,372,389, 456, 458.Hemmens, W. F., 451.Hempel, R., 522.Henbest, H. B., 302.Henchman, M., 39.Henderson, D. J., 546.Henderson, J. F., 463, 464.Henderson, R., 364, 365.Henderson, W. W., 322.Hendess, R. W., 389.Hendler, R. W., 455.Hendlin, D., 374.Hendrick, C. A., 363.Hendrickson, J. B., 370.Heners, J., 151.Henkle, L.P., 291.Henn, D. E., 335.Hennessy, D. G., 321.Henning, J. C. M., 199.Henrick, C. A., 361.Henry, A. J., 527.Henry, M. C., 336, 378.Henry, W. M., 559.Hentschel, P. R., 146.Hentz, F. C., jun., 134.Henze, G., 536.Hepler, L. G., 74.Heppel, L. A,, 455.Herberg, R. J., 557.Herbert, R. E., 388, 397.Herbison-Evans, D., 206.Herbstein, F. H., 597.Hercules, D. M., 98, 539,Herfurt, W., 315.Hergenbrother, W. L., 304,Herman, G., 496.Herman-Boussier, G., 496.Hermann, R. A., 103.Hermannsdorfer, K.-H.,Hermes, M. E., 323.Hermes, 31, F., 135.Hermis, M. E., 300.549.306.132.Hem, D. L., 499.Hernandez, G. J., 26.Herndon, W. C., 268.Herout, V., 357, 359, 360.Herring, D. L., 138.Herricgton, J., 555.Herriott, D.R., 59.Herrmaizn, H., 377.Hers, H. G., 478, 480.Herschberg, I. S., 551.Hersch, P., 555.Hershaft, A., 574.Hertler, W. R., 119, 120,Herz, J. L., 295.Herz, W., 357, 610.Herzberg, G., 8-10, 12, 13,21, 25, 26.Herzfeld, K. F., 49, 50, 52.Herzog, S., 148.Meslop, R. B., 140.Hesp, B., 343.Hess, G. P., 522.Hess, H., 581.Hess, H.-J., 369.Hess, J. A., 524.Hess, L. D., 264.Hesse, M., 402.Hesse, R., 587.Hetman, J. S., 538, 555.Heublein, G., 215.Heusler, K., 249, 303, 421,Hewertson, W., 139.Hewgill, F. R., 336.Hewlett, C., 139.Key, D. H., 262, 334, 335.Heydkamp, W. R., 301.Keying, T. L., 120,121,122.Heyman, H., 498.Eeyne, H., 100.Keyns, K., 430.Heyrovsky, J., 81.Heyrovsky, M., 98.Hibbert, P. G., 336.Hibbits, J.O., 563.Hibbs, J. M., 564.Hickinbottom, W. J., 276.Hickling, A., 93, 98, 534.Hiclmott, P. W., 308.Hicks, G. P., 561.Kieber, W., 180.Higashi, T., 461.Higgins, J., 551.Higginson, W. C. E., 163,165, 178, 586.High, D. F., 517, 612.Highet, R. J., 391, 397, 398,Etiguchi, J., 43, 45, 46, 198,Tikino, H., 356, 357.Zikino, Y., 357.Zildebrand, D. H., 76.lildebrand, G. P., 533.iileman, 0. E., jun., 534.342.422.402.199, 200.Hilgetag, G., 220.Hill, A. G., 527.Hill, A. S., 303.Hill, C. C., 564.Hill, E. A., 270.Hill, H. A. O., 280, 333.Hill, J. H. M., 229,281, 387.Hill, R. K., 284, 330, 379,Hiller, G., 307.Hiller, J. J., 276.Hiller, J. J., jun., 331.Hillman, M., 121.Hills, G. J., 84.Hills, K., 139.Hilmer, W., 578.Hindley, J., 519.Hine, J., 255.Hinerman, D.L., 481.Hinman, R. L., 261, 376,Hinson, W. H., 550.Hinton, J. F., 249.Hinz, U., 315.Hipps, G. E., 422.Hiramaya, K., 450.Hirano, S., 445, 564.Hirao, K., 304.Hirata, T., 143.Hirata, Y., 360, 410.Hirokawa, K., 546, 547.Hirokawa, S., 595.Hironaka, Y., 105.Hirose, Y., 448.Hirota, E., 105.Hirota, K., 104, 105.Hirota, N., 41.Hirs, C. H. W., 493, 511,Hirschmann, R., 414.Hirschmann, R. P., 212.Hirshberg, Y., 266, 567.Kirst, D. M., 196.Hirst, E. L., 441, 444.Rirst, J., 280.Hiscock, A. K., 416.Hitchings, G. H., 464.Hitchman, M. L., 164.Hoard, J. L., 174, 584.Hoare, J. P., 89.Hobbs, J. J., 414.Hobey, W. D., 200.Hobrock, D. L., 64.Hochheimer, B.F., 135.Hochstein, F. A., 369.Hochstrasser, R. M., 197.Hock, A. 0. S., 262.Hockaday, T. D. R., 400.Yodge, J. D., 240.?lodge, N., 150.3odge, P., 374.Xodges, R., 356.Bodgeson, J. A., 205.Bodgkin, J. H., 410.qodgkinson, A., 490.Soedeman, W., 544.391.377.513INDEX OF AUTHORS’ XAMES 637Hofler, M., 191.Hoeg, D. F., 249.Hoeksema, H., 450.Hoekstra, H., 150.Hoppe, R., 115.Horhammer, L., 391.Hoff, J. E., 544.Hoffer, M., 448.Hoffman, C. J., 146.Hoffman, P., 494, 496.Hoffman, R. A., 387.Hoffmann, H., 323.Hoflmann, H. M. R., 245,Hoffinann, K., 465, 474,Hoffniann, R., 123, 196,Hoffmann, R. W., 324, 336,Hoffmann, S., 300.Hoffmann-Berling, H,, 453.Hoffsommer, R. D., 303.Hofman, H. J., 276.Hofnian, W., 215.Hofmann, J.E., 255, 2’73,Hofmann, T. H., 507.Hofmeister, H. K., 113.Hogan, V. D., 561.Hoganson, E. D., 393.Hogeveen, H., 244, 270.Hoggan, D., 547.Hoiberg, J. A., 560.Hoijtiiik, G. J., 31, 200.Hojvat, N. L., 196.Hoki, N., 290.Holah, D. G., 174.Holbrook, W. B., 92.Holden, K. G., 374.Holeysovsky, V., 507.Holker, J. R., 430.Holland, R. V., 589.Ho’llas, J. M., 21, 22, 217.Holley, C. E., jun., 66, 71.Holliday, A. K., 123, 126.Holliman, F. G., 388.Kolling, H. E., 479.Hollis, D. P., 211.Holloway, C. E., 152.Holloway, J. H., 161, 571.Holloway, W. W., 60.Hollstein, U., 400.Holly. F. W., 450.Hollyhead, W. B., 279.Holm, A., 322, 383.Holm, R. H., 165, 171, 172,Holm, T., 254.Holmes, J. L., 256.Holmes, P.J., 81.Holmes, R., 49.Holmes, R. E., 448.Holmes, W. S., 68.Holness, N. J., 227.Holoubek, K., 345.246.512.238.372.329.171.Holper, J. C., 453.Holt, E. L., 101.Holt, J. M., 54i.Holt, L. E., 483.Holt, S. L., 164.Holtrust, G., 241.Holzel, A., 476, 478.Homburg, F., 423.Wonda, E., 290.Honecker, O., 249.Honeyman, J., 429.Honjo, I%., 451.Hood, F. P., 215.Hood, F. P., tert., 349.Hoodless, R. A., 151, 134.Hooft, C., 486.Hooker, W. J., 55.Hooks, H., 139.Hoopor, P. R., 545.Hoover, F. W., 323.HOOZ, J., 276, 333.Hope, D. B., 481, 519, 521.Hope, H., 615.Hopkins, C. Y., 319.Koppe, R., 168, 571, 575.Hopps, H. B., 300, 328.Hordvik, A., 577..Horecker, B. L., 460.Iioribe, I., 357.Horii, Z., 410, 608.Horiuti, J., 89, 90, 94.Horn, D.B., 551.Horner, F. A., 481.Horner, L., 108.Horner, S. M., 151, 153,158.Horner, W. W., 158, 159.Hornig, A. W., 42.Hornig, D. F., 49.Horning, E. S., 4i4.Horomitz, A., 260.Horowitz, BI., 495.Horowitz, R. M., 275.Horrocks, D. L., 557.Horrocks, W. D., 180.Horton, C. A, 447.Horton, D., 429, 434, 435,436, 437, 438, 442, 444.Horton, E. W., 522.Horton, J. A., 552.Horvatli, C., 533.Morvei, K. F., 443.Horvutli, E., 518.Horm-ith, M., 481, 485.Hosaka, S., 317.Hoshino, H., 560.Eoskins, B. F., 167.Hospital, &I., 594.Hoste, J., 558.Hota, N. K., 1.41.Hougen, J. T., 25, 26, 205.I-Iough, L., 456.Houghton, R. P.. 296.House, D. A., 165.House, E., 479.House, H. O., 305, 309.Houser, J.J., 240.Houston, R. J., 103.Horvorka, F., 94.Howard, 3’. B., 448.Howard, T. J., 282.Howard-Flanders, P., 447.Howarth, 0. W., 1’74.Howden, M. E. H., 346.Howell, C. F., 219.Hoxell, M., 330.Howell, R. R., 481, 188.Iiu, S. C., 509, 577.Huang, C. C., 509.Huang, F.-T., 281.Huang, K., 509.Huang, R. C., 455.Huang, W. T., 509.Hubbard, S., 521.Hubbard, W. K,, 66,67,68,Huber, C. O., 539, 540.Huber, E. J., jun., 66, 71.Huber, K. P., 17.Hudec, J., 346, 415.Hudson, B. E., 263.Hudson, F. M., jun., 302.Hudson, H. R., 249, 311.Hudson, P., 594.EIudson, R. F,, 137, 219,Hudson, W. R., 453.Hiibel, W., 187.Huebiier, C. F., 267, 335.Hiickel, W., 229, 2-19, 255.Hiilsmann, W. C., 479,480.Hunig, S., 252, 338.Iluet, J., 311.Huttel, R., 185.Huttmann, H., 152.Huff, J.R., 100.Huffman, J. W., 420.Huggins, D. K., 191.Hughes, E. D., 245, 246,Hughes, R. C., 493, 497.Hughes, R. E., 596.Eughes, S. R. C., 217.Hughes, T. C., 558.Hughes, T. R., 103.Hughes, T. V., 146.Huguley, C. M., 488.Huidobro, H. V., 525.Huijing, F., 4i9, 480.Huisgen, F., 352.Huisgen, R., 229, 267, 373,Huisman, H. O., 220, 311,Huisman, R., 576.Huitric, A. C., 214, 219.Hull, D. E., 559.Wulme, R., 29, 146, 166,Nume, D. hT., 92, 542, 548,Humer, P. W., 43.Humfrey, E. F., 533.411.254, 290.271, 281.381, 3S6.419.572.554, 564638 INDEX OF AUTHORS’ NAMESHumiec, F. S., 164.Hummel, J. P., 511.Humphreys, D. G., 158.Humphries, C. M., 18, 22.Hundeshagen, H., 483.Hunt, J.C., 524.Hunt, J. P., 178.Hunt, R., 591.Hunter, A., 481.Hunter, G. L. K., 359.Huntress, W. T., 164.Huntsman, W. D., 107,299.Hurd, R. M., 90.Hurle, I. R., 52.Hurley, R. G., 545.Hurley, T. J., 147.Hurst, D. T., 387.Hurst, C. L., 135.Hurst, P. L., 483.Hurwitz, B. M., 382.Hurwitz, H., 111.Hurwitz, H. R., 82.Hurwitz, J., 453.Hurwitz, J. P., 450.Husbands, J., 302.Huse, Y., 595.Husemann, E., 442.Hussek, H., 128, 130.Hussey, A. S., 107.Huston, J. L., 116.Hutchinson, D. W., 312,Hutchinson, J., 384.Hutchinson, J. H., 189.Hutchinson, S. A., 362.Hutchison, C. A., 41.Hutchison, J. D., 245.Hutson, D. H., 429, 440.Hutton, H. M., 208, 346.Hutzler, J., 483.Hu-Yu Yang., 469.H-San Tsai, J., 163.Hsia, D.Y., 477.Hsui-Chu Hsu, I., 396.Hsu, C. C., 509.Hvoslef, J., 606.Hwang, B., 327.Hyde, A. F., 128.Hyde, J. S., 42, 47.Hyepock, J., 281.Hyman, C., 68, 69.Hymcw, H. H., 115.Hyne, J. B., 249.Iball, J., 567.Ibbitson, D. A., 220.Ibers, J. A., 116, 171, 179,189, 573, 576, 577, 590,592.323.Ibershof, M. L., 451.Ibuka, T., 401.Ichikawa, Y., 461.Iczkowski, R. P., 97.Idrestedt, I., 577.Ievin’sh, A. F., 158.Igano, K., 304.Igarashi, S., 560.Iitak, Y., 610.Iitaka, Y., 363, 572, 575,Ijzermans, A. B., 540.Ikeda, S., 541, 547.Ikeda, T., 363.Ikehara, &I., 450.Illuminati, G., 274, 280,Imado, S., 410, 608.Imai, S., 108.Imai, Y., 465.Imamura, S., 317.Immer, H., 422.Imoto, E., 308.Impastato, F. J., 270.Inch, T.D., 438.Ingells, R. B., 46.Ingle, T. R., 437, 438.Ingold, (Sir) C., 269, 271,Ingram, M. D., 98, 534.Ingram, V. M., 454.Ingri, N., 578.Inhoffen, E., 313.Innes, K. K., 14, 23.Inokuchi, H., 217.Inokuchi, N., 377.Inoue, M., 168.Inoue, Y., 281.Inouye, H., 357.Inouye, T., 477.Insole, J. H., 276.Insole, J. M., 277, 394.Interrante, L. V., 95.Inubushi, Y., 366, 367, 401,Inuzuka, M., 414.Iofa, Z. A., 83, 88, 89.Ioffe, B. V., 380.Ioffe, S. L., 300.Ireland, R. E., 361.Iriarte, J., 423.Irie, H., 363.Irie, T., 425.Irish, D. E., 220.Irmscher, K., 414.Irreverre, F., 482.Irving, C. C., 472, 473.Irving, H., 147.Irving, R. J., 72, 74.Isaacs, P. B., 576.Isbell, H. S., 289, 290, 431.Isenhour, T. L., 558.Ishida, M.R., 452.Ishido, Y., 449.Ishikawa, M., 129.Ishikawa, Y., 306.Ishitobi, H., 230, 275.Ishizaki, M., 404.Isler, O., 318.Ismail, S. M., 102.Isoi, K., 315.IsraBli, Y. J., 19, 26.Isselbecher, K. J., 476, 478.595.370.281.410.Issleib, K., 137, 138, 151,Itatani, H., 161.Itazaki, H., 303.Ito, E., 505.Ito, S., 319, 357, 426.Ito, Y., 324.Itoh, K., 37.Itoh, T., 450.Itzel, J. F., jun., 126.Ivanoff, C., 335.Ivanova, N. G., 336.Ivanova, R. V., 84.Ives, D. J. G., 81.Iveson, G., 533.Iwai, I., 449.Iwamoto, T., 410.Iwane, S., 108.Iwasaki, H., 450, 593.Iwata, K., 366.Iwata, S., 213.Iyer, N. T., 426.Izatt, R. M., 74.Izawa, K., 555.Izawa, M., 453.Izmailov, N. A., 81.Iunanova, T. A., 564.Izumi, Y., 100, 103.Izzo, J.L., 511.Izzo, M. J., 511.Izzo, P. T., 347, 348.Jack, K. H., 168.Jackman, L. M., 318, 378,Jackson, J. B., 75.Jackson, R. A., 206.Jackson, W. J., jun., 305.Jackwerth, E., 530.Jacob, T. M., 452.Jacobs, E. S., 555.Jacobs, W. D., 529.Jacobsen, S., 260.Jacobson, K. B., 533.Jacobson, M., 469.Jacobson, R. A., 603.Jacoby, G. A., 481.Jacox, M. E., 21, 209.Jacox, R. F., 475.Jacquenod, P. A., 521.Jacques, J., 421.Jacques, J. K., 68.Jacques, R., 203.Jaeger, H., 99.Jiiger, H., 426.Jaffe, H. H., 197, 337, 370.Jagenburg, 0. R., 484.Jagger, H., 404.Jaggi, H., 608.Jahn, W., 141.Jahnberg, L., 576.Jaimni, J. P. C., 537.Jain, S. R., 168.Jakobsen, H. J., 307.Jakonbkovs, M., 532.Jamieson, J.C., 500.161.391INDEX OF AUTHORS’ NAMES 639JanetikovB, E., 385.Janiak, P. St., 269.Jankowski, E., 248.Janot, M.-M., 299, 357, 404,407, 420, 426.Janota, H. F., 552.Jansen, C. J., 406.Jansen, E. F., 516.Jansen, G., 69.Jansen, K. A., 370.Janssen, M. J., 132.Janssen, M. T., 134.Januszeski, R. L., 96.Jam, G. J., 81, 143.Jaques, B., 234.Jaques, D., 250.Jardetzky, C. D., 456, 457.Jardetzky, O., 456.Jaret, R. S., 402.Jarolimek, P., 320.Jarreau, F.-X., 426.Jarrett, H. S., 27.Jarski, M. A., 588.Jart, A., 260.Jary, J., 436.Jasinski, R. J., 100.Jastrow, H., 315.Jastrzebska, J., 83.Jatzkewitz, H., 487.Javan, A., 59.Jayle, M.-F., 500.Jean, M., 203.Jeanloz, D. A., 445.Jeanloz, R. W., 445, 491,492, 493, 497, 498.Jeelani, N.A., 303.Jefferies, P. R., 361, 363.Jefferson, A., 283.Jefford, C. W., 367.Jeffrey, G. A., 570,579,586,Jeffrey, J. A., 606.Jeger, O., 249, 422, 423.Jeitschko, W., 570.Jelenic, I., 589.Jellinek, F., 158, 185, 574,Sen, M., 205.Jencks, W. P., 287,289,291,Jenitzch, J., 307.Jenkins, R. D., 180.Jenkins, S. R., 450.Jenne, H., 124.Jennings, A. L., jun., 218.Jennings, J. P., 458.Jennings, P. P., 128.Jensen, A,, 319.Jensen, F. R., 271.Jensen, G. B., 600.Jensen, K. A., 322.Jensen, L. H., 596, 606.Jensen, S. L., 318, 330.Jenson, E. D., 240.Jenson, F. R., 351.Jenson, K. A., 383.613.576.296.Jensovsky, L., 430.Jepson, J. N., 486.Jeremid, D., 304.Jerkeman, P., 439.Jerslev, B., 598.Jervis, G.A., 484.Jesch, C., 84.Jesse, R. E., 31, 200.Jeunehomme, M., 23, 77.Jevons, F. R., 523.Jewett, J. G., 246.JBzhquel, A.-M., 501.Jiang, R. Q., 509.Jicha, D. C., 173.Jiracek, V., 437.Joassin, G., 478.Job, V. A., 212.Joesten, M. D., 175.Johanson, L. N., 112.Johansson, G., 542.Johansson, I., 440.Johns, J. W. C., 9, 11, 14,Johns, W. F., 417, 420.Johnson, A. P., 304, 391.Johnson, A. W., 272, 334,375, 376, 377, 389, 393.Johnson, B. F. G., 159,179,182.Johnson, C. B., 321.Johnson, C. D., 335.Johnson, C. R., 300.Johnson, D. A., 177, 373.Johnson, E. A., 276.Johnson, E. G., 543.Johnson, F., 385.Johnson, F. A., 18, 19, 136.Johnson, G. K., 69.Johnson, H. E., 309.Johnson, H. W., jun., 356.Johnson, I. S., 406.Johnson, J.H., 136.Johnson, J. S., 158.Johnson, J. W., 96.Johnson, L. F., 47, 214,Johnson, L. N., 607.Johnson, M. F. L., 103.Johnson, M. K., 471.Johnson, N. P., 160, 165,Johnson, P. N., 41.Johnson, R. M., 278, 384.Johnson, S. L., 291.Johnson, W. H., 65, 68, 72.Johnson, W. S., 61, 65, 234,235, 258, 411, 420.Johnston, D. B. R., 329.Johnston, F. J., 249.Johnston, W. D., 576.Jokl, V., 532.Jollgs, P., 496.Jolly, W. L., 65, 128, 136,Jommi, G., 362.Jon&& J., 359.15, 20.430.181.180.Jonassen, H. B., 167.Jones, D., 174, 186.Jones, D. A. K., 255.Jones, D. N., 413.Jones, D. S., 507.Jones, D. W., 593.Jones, (Sir) Ewart, 315,418Jones, F. N., 392.Jones, F. W., 418.Jones, G., 386.Jones, G. R., 49.Jones, H.C., 92.Jones, H. O., 305.Jones, I. L., 548.Jones, J., 274.Jones, J. D., 486.Jones, J. K. N., 436, 438,Jones, J. P., 534.Jones, J. W., 447.Jones, K. W., 453.Jones, M., 284.Jones, M. E., 246.Jones, M. M., 66, 156, 174.Jones, M. T., 32, 44.Jones, P. G., 342.Jones, P. J., 149, 155.Jones, R., 555.Jones, R. A., 374, 376.Jones, R. A. Y., 385.Jones, R. G., 208.Jones, R.. L., 210, 374.Jones, R. S., 444.Jones, V. K., 305.Jones, W. M., 347.Jones, W. J., 210.Jordaan, J. H., 434.Jordan, D. E., 537, 544.Jordan, E. D., 559.Jordan, J., 561.Jordanov, B., 207.Jlirrgensen, C. K., 163.Jortner, J., 19, 20, 26, 71.Jose, P., 586.Joseph-Nathan, P., 379.Joshi, B. S., 343, 360.Joshi, K. K., 137, 180,Joshi, K.M., 83.Joska, J., 413.Jost, K., 519, 520.Joule, J. A., 379, 404, 406.Joullie, M. M., 219.Jourdian, G. W., 502.Jovin, T., 519.Jovscheff, A., 207.Juan, C., 202.Jucker, E., 374.Judeikis, H., 60.Juergem, W., 498.Julia, M., 262, 311.Julia, S., 232, 414, 420.Jullien, J., 290.Jung, D., 206.425, 426.443.187.Jost, K.-H., 578640 INDEX OF AUTHORS’ NAMESJungreis, E., 528, 552.Junta, B., 428.Jursa, S. A., 12.Just, G., 229.Justi, E. W., 101.Justin, J., 560.Jutz, C., 241, 337.Juvet, R. S., 533.Juvinall, G. L., 188.Juza, R., 135, 151.Kaabak, L. V., 302.Kabanov, B. N., 87.Kabasakalian, P., 421Kabat, E. A., 443, 497.Kabe, T., 107.Kaczka, E. A., 374, 391,Kaczmarczyk, A., 130.Kaden, R., 66.Kadijk, F., 576.Kiigi, D., 423.Kaerner, H.C., 453.Kiiser, H., 486.Kaesz, H. D., 191.Kafalas, J. A., 87.Kagan, H. B., 373.Kaganovich, R. I., 85, 86,Kagi, H. H., 387.Kahmann, K., 172.Kahn, M., 249.Kainz, G., 543.Kaiser, A., 249.Kaiser, E. M., 302.Kaiser, E. T., 457.Kaiser, G. V., 265.Kaiser, W., 237, 380.Kaistha, K. K., 611.Kakisawa, H., 360, 363.Kakudo, M., 598.Kalb, G. H., 118.Kalckar, H. M., 476.Kale, M. N., 256.Kalechits, I. V., 109.Kalenda, H., 378.Kalish, T. V., 93.Kallenbach, L. R., 533.Kallmann, S., 563.Kalow, W., 575.Kalvoda, J., 249, 303, 421,Kalvoda, R., 81.Kamachi, M., 331.Kamada, H., 564.Kamet, V. N., 360.Kambe, H., 560.Kamemoto, Y., 558.Kametani, T., 331.Kamin, H., 460.Kamiyama, S., 492, 494.Kampffmeyer, V.H., 463.Kampmann, F.-W., 540.Kan, C., 427.Kana’an, A. S., 113.Kanai, Y., 451.450.94.422.Kanamoto, S., 363, 414.Kanfer, J. N., 487.Kanfer, K., 487.Kant, A., 78.Kantor, M. L., 356.Kapadi, A. H., 362.Kaplan, F., 208.Kaplan, L., 328, 449.Maplan, L. A., 300.Kapustinskii, A. F., 71,Karabatsos, G. J., 206, 212,Karabinos, J. V., 304.Karachevtzer, G. V., 560.Karapetyan, M. G., 345.Karasek, M., 453.Karbstein, B., 128.Karicowski, F. M., 220.Karipides, A, G., 177.Karkowski, F. M., 385.Karl, G., 57.Karlan, S., 122.Karle, I. L., 399, 594, 600,Karle, J., 399, 607, 609.Karlsson, L., 379.Karn, F. S., 109.Karns, T. K. B., 398.Karp, H. S., 561.Karplus, M., 46, 47, 198,199, 201, 202, 457.Karpukhin, 0.N., 98.Karraker, D. G., 150.Karrer, P., 402.Kartha, G., 364, 611.Kartona- Soeratinam, H.,Karttunen, J. O., 546.Karyakin, A. V., 529.Kasafirek, E., 519.Kasami, K., 608.Kasenally, A. S., 190, 191.Kashelikar, D. V., 298.Kashiwagi, M., 38.Kasper, C. B., 507.Kassel, B., 507.Kasturi, T. R., 212.Katagi, T., 430.Katagiri, K., 450.Katarao, E., 410.Katchalski, E., 493.Kateman, G., 543, 563.Katner, A. S., 377.Kato, M., 167, 428.Kato, R., 467, 468, 470.Kato, T., 384.Katon, J. E., 208, 216.Katritzky, A. R., 219, 220,274, 377, 380, 382, 385,390, 456.74.217, 248, 280.607, 609.144.Katsion, V. V., 555.Katsoyannis, P. G., 509.Katz, J. J., 275.Katz, L., 262.Katz, S., 453.Katz, T. J., 29, 30, 241,Kauer, J.C., 322.272, 337.Kauffman, G. B., 163.Kauffman, J. M., 122.Kauffmann, D. L., 296,507.Kauffmann, T., 302.Kaufman, S., 463.Kaul, K. N., 444.Kaup, D. J., 546.Kamp, Yu. Yu., 106, 107.Kaverzneva, E. D., 492.Kawaguchi, K., 367.Kawahara, S., 425.Kawanabe, K., 530.Kawanami, J., 528.Kawanisi, M., 303.Kawano, K. I., 381.Kawasaki, A., 287.Kawasaki, Y., 133.Kawashima, K., 360.Kamazoe, Y., 363.Kay, I. T., 376.Kaya, A., 547.Kaya, I<., 24.Kayser, W. V., 272.Kazanski, B. A., 106.Kazantseva, V. Bl., 109.Kazarinov, V. E., 87, 88.Ke, L. T., 509.Kealey, D., 534.Keane, W., 544.Kearns, G. L., 560.Keat, R., 139.Keberle, H., 465, 474.Keblys, K. A., 191.Keefer, R. M., 273.Keeffe, J. R., 268.Keeler, C.E., 549.Keen, G., 426.Keenan, C. W., 189.Keib, G., 573.Keii, J., 93.Keii, T., 90.Keil, B., 507.Keiley, H. J., 542.Keisler, J. E., 300.Keith, C. D., 103.Keith, J. N., 143.Kelbys, K. A., 301.Keller, C., 148.Keller, H., 44.Keller, J., 422.Keller, R. A., 533.Keller, R. E., 206, 553.Kelley, C. A., 555.Kelley, M. T., 92.Kelliher, J. M., 265.Kelly, D. H., 301.Kelly, D. P., 328.Kelly, R. B., 453.Kelly, R. C., 327, 354.Kelly, R. E., 109.Kelsh, D. J., 86.Kemball, C., 99, 105, 106,112INDEX OF AUTHORS’ XAMES 641Kemp, R. J., 43.Kemula, W., 97.Kende, A. S., 298, 335, 347,Kendig, E., 479.Kennard, C. H. L., 167.Kennedy, C. D., 263.Kennedy, J., 250.Kenner, G. W., 459, 507.Kent, P. T., 495.Kent, P. W., 491.Kent, R.A., 130.Kerber, R. C., 250.Kerrigan, 5. V., 118.Kershaw, J. W., 377.Kessick, M. A., 272.Kessler, H., 334.Kestigian, M., 60.Ketcheson, B. G., 426.Kevill, D. N., 255.Keys, L. L., 143.Kezdy, F., 296.Kezdy, F. J., 516.Khachadurian, A. K., 478.Khairallah, P. A., 524.Khalaf, A. A., 249.Khaleeluddin, K., 249.Khaletskii, A. M., 382.Khan, M. K. A., 219.Khan, N. H., 408.Khananashvili, L. M., 128.Khattab, S. A., 191.Khitrov, A. P., 316.Khomutov, N. E., 90.Khoobiar, S., 111.Khorana,, H. G., 451, 452.Khorlin, A. J., 439.Khorlina, I. M., 302.Khotsyanova, T. L., 597.Khuong-Huu, Q., 407, 426.Khusainova, N. G., 314.Kiamuddin, M., 274.Kida, S., 175.Kidwai, A. R., 407, 426.Kiedaisch, W., 334.Kiefer, H., 352.Kiely, D.E., 357.Kienzle, F., 430.Kier, L. B., 219.Kiese, M., 463.Kieslich, K., 317.Kiil, R., 484.Kiji, J., 317.Kikuchi, T., 407, 426.Kikuchi, Y., 325.Kilbourn, B. T., 191, 593.Kilch, G., 154.Kilday, M. V., 68, 72.Kilheffer, J. V., 296.Kiljakova, G. A., 188.Killander, J., 531.Killick, R. A., 558.Killip, K. A., 124.Kilmurry, L., 356.Kim, Y. K., 265.Kim, Y. T., 453.348.Kinibrough, R. D., jun.,Kimmel, J. R., 507.Kimura, K., 582.Kimura, M., 462.Kimura, Y., 315.Kindt-Larsen, T., 260.King, A. B., 206.King, F. E., 324, 345.King, G. W., 212.King, J. F., 255, 323.King, J. P., 66.King, R. B., 179, 182, 183,185, 187, 189.King, R. W., 207.Kingsbury, C. A., 279.Kingston, D. G. I., 343.Kingston, E.G. I., 343.Kinosehita, J., 481.Kinsinger, J. B., 133.Kinson, K., 550.Kiosse, G. A., 567.Kioussis, D., 109.Kirby, A. J., 312, 323.Kirby, G. H., 16.Kirby, G. W., 400.Kirk, D. N., 413, 414, 415,Kirk, J. T. O., 453.Kirkien-Kanasiewiez, A.,Kirkman, H. N., 476.Kirkpatrick, J. L., 404.Kirkmood, J. G., 82.Kirkwood, S., 439.Kirmse, W., 221, 305, 324.Kirner, H., 153.Kirsanova, J., 290.Kirsch, J. F., 291.Kirsten, W. J., 543.Kirwin, J. B., 168.Kiryanov, K. A,, 84.Kiselev, V. G., 301.Kiseleva, I. G., 98.Kiser, R. W., 64, 137, 212.Kisor, W., 485.Kishida, Y., 413.Kishita, M., 168.Kiss, J., 431, 438.Kistner, C. R., 189.Kit, S., 464.Kita, H., 90.Kitagawa, T., 376.Icitahara, Y., 361, 362.Kihahonoki, K., 368.Ritai, R., 510.Kitaigorodskii, A. I., 597.Kitao, T., 286.Kitaoka, Y., 286.Kitchiner, B.C., 217.Kitching, R., 550.Kitzinger, C., 61.Kiun-Rouo Ou, 310.Kivelson, D., 27, 36, 46.Kiyokawa, M., 437.Kiyomoto, A., 430, 435.381.416, 418.280, 297.Kiyono, M., 303.Kjaer, A., 323.Kjner, J., 109.Kjekshus, A., 147, 153.Kjellin, K. G., 558.Kjennerud, V., 297.Klamann, D., 136.Klaus, I., 295.Klavins, J. V., 482.Klee, W. A., 510.Klein, J., 488.Klein, M. J., 119.Klein, R. N., 117.Kleinberg, J., 162, 174.Kleine, K.-M., 315.Kleinman, D. S., 484.Kleinstuck, K., 576.KIeipool, R. J. C., 559.Kleman, B., 15.Klement, R., 140.Klemperor, W., 58.Klenk, E., 319, 486.Klenow, H., 450.Kletzke, P. G., 287.Klimova, N.S., 118.Klinenbcrg, J. R., 489.Klingenberg, M., 461.Kloden, D., 398.Kloprnan, G., 196, 254.Klose, W., 151.Kloss, P., 309.Klostermeyer, H., 508, 509.Kluepfel, D., 428.Klug, H. P., 179, 591.Klug, J. T., 371.Klumpp, E., 182.Klundt, I. L., 450.Klutch, A., 469.Klyachko, Y. A., 564.Klyne, W., 368, 411, 458.Knaack, W. F., 426.Knack, W. F., 407.Knackmuss, H.-J., 381.Kneser, H. O., 52.Knight, B., 98.Knight, C. A., 453.Knight, M. H., 390.Knight, S. C., 428.Knipprath, W., 319.Kniseley, R. N., 212, 548,Knobler, C., 603.Knobler, C. B., 587.Knoblock, E. C., 542.Knoche, W., 82.Knoepfel, H. P., 343.Knop, B., 140.Knorr, C., 88.Knorr, C. A., 89.Knoth, W. H., 120.Knowles, C. J., 537.Knowles, C. R., 575.Knowles, P., 220.Knox, K., 189, 569, 613.&ox, W.E., 484.KO, R., 530.549642 INDEX OF AUTHORS’ NAMESKobata, A., 502.Kobayashi, H., 414.Kobayashi, T., 377.Kober, E., 139.Kobosev, N. I., 101.Koch, C. W., 116, 577.Koch, D. F. A., 87, 94.Koch, H. F., 270.Koch, M., 357.Kocharyan, A. A., 543.Kochetkov, N. K., 430,439,Kochwa, S., 486.Kocourek, J., 429,430,437.Kodama, M., 357.Kodera., T., 93.Koegler, S. J., 480.Kohl, H., 179.Koehler, K., 287.Kohn, S., 315.Konig, E., 156.Konig, H., 310, 319.Konig, J., 132.Konig, K., 132.Kopf, H., 133.Kopf, K., 133.Korner, H., 66.Koerts, K., 575.Koster, R., 122, 132, 300,325, 370.Koev, K., 531.Koga, T., 414.Kohl, F. J., 187.Kohli, 5. M., 407, 426.Kohnstam, G., 246.Koidara, S., 399.Kojima, M., 218.Kojima, T., 205.Kokko, J.P., 456.Kokkoros, P. A., 580.Kokot, E., 168.Kokoulina, D. V., 98.Kokovin, G. A., 71.Kolaczkowski, R. W., 156.Kolbel, H., 109.Kolbin, N. I., 78.Kolditz, L., 117, 128, 154.Kolesov, V. P., 64.Kolka, S., 436.Kolker, P. L., 29.Kolobova, N. E., 191.Kolomnikov, I. S., 191.Kolosov, M. N., 345.Kolotyrkin, Ya. M., 87, 98.Kolthoff, I. M., 152, 563.Komano, T., 445.Komatsu, S., 100.Komeno, T., 368.Komitsky, F., 430, 437.Komiyana, Y., 585, 588.Komorniczyk, K., 128, 134.Komrower, G. M., 476,490.Komura, M., 133.Kondratiev, V. N., 45.Konigsberg, W., 508, 524.Konita, T., 410.559.Konoshita, J. M., 477.Kooyman, E. C., 255, 331.Kopelman, R., 205.Kori, S., 556.Korkisch, J., 532.Kornblau, M.J., 596.Kornblum, N., 250, 322.Kornegay, R. L., 215, 349.Kornfeld, R., 500, 502.Kornfeld, S., 500, 502.Kornilov, A. N., 66.Korobko, V. G., 345.Korol’chenko, G. A., 439.Korolev, A. K., 96.Korst, W. L., 569.Korte, F., 213, 383, 543.Koryta, J., 91, 93.Koser, W., 136.Koshland, D. E., 295, 512,Koski, W. S., 37, 581.Kost, A. N., 302.Kostir, J., 430.Kostka, V., 515.Kosuge, T., 363.Kotloby, A. P., 122.Kotova, M. S., 73.Kotrlf, S., 541.Kottis, P., 42.Kouwenhoven, H. W., 183.Kovacic, P., 305.Kovacs, o., 245.Koval, L., 552.Kovalenko, L. N., 435.Kovba, L. D., 93.Kowalewski, V. J., 208.Kowalski, Z., 87.Kowanko, N., 531.Koyama, Y., 319.Kozaki, N., 245.Kozima, K., 213.Kozima, S., 133.Kozima, T., 363.Kozina, M.P., 62.Kozlov, V, V., 328.Kozmin; P. A., 573.Kozuka, S., 286, 384, 386.Kriimer, H., 345.Kriimer, J. M., 414.Kraevskii, A. A., 320.Krager, R. T., 129.Krainov, E. P., 213.Kramer, D., 315.Kramer, D. N., 562.Kramer, J. K. G., 530.Kraml, M., 467.Kramm, D. E., 545.Krapcho, A. P., 260.Krasso, A. F., 431.Kratochvil, B., 536.Kratzer, R., 138.Kratzl, K., 301.Kraus, M. H., 543.Kraus, W., 225.Krause, H. H., 160.Krause, J. G., 281.516.Krause, L., 58.Krauss, D., 306.Krauss, H.-L., 152.Krauss, S., 500.Kraut, J., 571, 601, 612,Kray, W. C., 255.Kraychy, S., 428.Krbechek, L. O., 342.Krech, F., 137.Kreevoy, M. M., 256, 272.Kreil, G., 519.Kreveva, R. A., 453.Ki.epinsk9, J., 369.Kresge, A.J., 272.Kresheck, G. C., 75.Krespan, C. G., 334.Kresze, G., 268.Kretchmer, R. A., 272.Kretzschmer, G., 306.Krichmar, S. I., 93.Kriek, E., 447.Krisch, K., 464.Krishna, P., 570.Krishnan, R. S., 21 1.Krishnan, V. R., 556.Krisman, C. R., 442.Krivi, A. F., 542.Kriz, G. S., 247.Krohnke, F., 378, 387.Kroke, H., 390.Kroll, M., 543, 563.Krone, E., 144.Krooth, R. S., 477.Kropp, P. J., 423.Krote, H. W., 25.Krouse, P., 94.Krsek, J., 543.Kruck, T., 155, 160, 180,182, 191.Krudener, J., 542, 544.Kriiger, C., 129, 130.Kriiger, G., 91.Kruger, J., 87.Kruse, F. H., 149, 168.Kruze, D., 531.Krylov, V. S., 82, 84.Krylova, L. M., 106.Krynicki, K., 207.Krystik, F., 479.Kryukova, T. A., 87.Ksenzhek, 0. S., 97.Ku, V., 108.Kubo, J., 433.Kubo, M., 168.Kubota, T., 363, 425.Kucharska, H.Z., 387.Kuchen, W., 123, 170.Kucherov, V. F., 315.Kuchner, E. C., 528.Kuck, A. M., 400.Kuczkowski, R. L., 145.Kudryashova, N. F., 73.Kuehne, M. E., 376.Kuemmel, D. F., 319.Kiihltau, H. P., 449.Kugler, F., 343INDEX OF AUTHORS’ NAMES 643Kuhn, D. A,, 381.Kuhn, R., 317, 381.Kuhn, S. J., 125, 273, 275,Kuivila, H. G., 132, 272,Kukis, A., 321.Kukral, J. C., 499.Kula, &I.-R., 132.Kulibekov, M. R., 310.Kulichenco, L. B., 551.Kulkarni, A. B., 345.Kumada, M., 129.ICumamoto, T., 313.Kumar, A. N., 540.Kumar, K. S. V. S., 296,Kumler, W. D., 216.Kummer, J. T., 104.Kummerow, F. A., 532.Kum-Tatt, L., 536.Kunchar, N.R., 589.Kunchur, N. R., 169.Kung, J.-F. T., 533.Kung, Y. T., 509.Kunin, R., 532.Kunnmann, W., 157.Kuntzman, R., 469.Kupchan, S. M., 367, 407,Kupchik, E. J., 133.Kurahashi, K., 476.Kuran, W., 306.Kurbanov, A. R., 78.Kurita, J., 38.Kurita, Y., 38.Kuriyama, K., 399.Kurland, R. J., 216, 218.Kuroda, T., 311.Kuroya, H., 585.Kursanov, D. N., 131.Kurzer, F., 370, 389.Kusaka, M., 440.Kusaka, N., 384.Kusch, P., 15.Kushev, V. V., 453.Kushida, T., 38.Kushlefsky, B. G., 133.Kuta, J., 93.Kutanina, L. K., 555.Kuthan, J., 385.Kutney, J. P., 405.Kutoglu, A., 575.Kutsche, H. D., 529.Kutsev, V. S., 66.Kuwabara, T., 481.Kuwajima, I., 309.Kuwana, T., 98.Kuznetsov, V. G., 573.Kuznetsova, L. A., 18.Kuzub, V.S., 89.Kuzyakov, Yu. Ya., 18.Kwart, H., 253, 255, 262.Kwass, G., 419.Kwiatkowski, G. T., 233.Kwiram, A. L., 39.276, 331.276, 301.607.426.Kwon, J. T., 132.Kybett, B. D., 69.Kyukina, L. D., 85.Laane, J., 133.Labhart, A., 477, 478.Labler, L., 407, 426.Lacher, J. R., 70.Lacina, J. L., 65, 66.Lack, R. E., 263, 427.La Count, R. B., 327.Ladd, J. A., 116.Ladenberger, V., 253.La Du, B. N., 460,481.Laessig, R. H., 538.Lafferty, W. J., 206.La Fleur, W. J., 87.Lafont, D., 347.Lagercrantz, C., 31, 34.Lagerqvist, A., 12.Lagoev, B. B., 207.Lagowski, J. J., 124, 540.Lagowski, J. M., 449.Lahiri, S. C., 74, 523.Lahr, T. N., 206.Laidler, J. B., 150.Laidler, K. J., 74, 297.Laiho, S. M., 402.Laing, M., 604.Laitenen, H.A., 88, 89.Lake, D. B., 140.Lakeman, J., 419.Lakue, T. A., 552.LaLancette, E. A., 306.LaLancette, R. A., 32.LaLonde, R. T., 248, 346.Lam, F.-L., 254.Lam, L. K. M., 270.Lamaty, G., 289, 290, 354.Lamb, R. C., 261.Lambert, B. F., 398, 403.Lambert, D. G., 274.Lambert, J. B., 206, 242.Lambert, J. D., 53, 58.Laming, F. P., 148.Lamm, B., 258.Lamola, A. A., 391.Lampman, G. M., 348.Lamure, J., 156.Lancaster, J. E., 184.Land, D. G., 318.Landa, S., 317.Landau, L., 50.Landgrebe, J. A., 229.Landheer, C. A., 319.Landor, P. D., 313.Landor, S. R., 313.Landrum, B. L., 17.Landsberg, R., 88.Lane, A. P., 137.Lane, C. A., 290.Lane, N., 501.Lanford, C. A., 213.Lang, J., 376.Lang, L. K., 245.Lang, N., 470.Lang, W., 182.Langdon, R.G., 510.Lange, A., 141.Lange, E., 80.Lange, G. L., 208, 320Lange, R. M., 276, 331.Lange, W., 140.Langenbeck, W., 300.Langer, H. G., 132.Langford, C. K., 172, 178.Langford, P. B., 255.Lsnglois, S., 297.Langmyhr, F. J., 575.Langridge, R., 457, 607.Lanigan, P. G., 154.Lansbury, P. T., 270, 290.I,anztzfame, F. If., 532.Lanzilotti, A. E., 505.La Paglia, S. R., 12, 24,Lapidot, Y., 451, 452.La Pierre, J. C., 286, 331.La Pietra, R. A., 93.Lapin, H., 310.La Placa, S. J., 179, 189,590, 592, 598.La Planche, L. A., 210.Lapluye, G., 101.Lappe, F., 575.Lappert, M. F., 123, 132.Larbig, W., 300.Lardy, I. A., 314, 391.Larsen, B., 444.Larsen, E. H., 307.Larson, A. C., 569, 570,571,Larson, M.L., 157.Lasker, M., 477.Laskin, A. I., 428.Laskowski, M., 507.Laslett, R. L., 374, 376.Lassner, E., 537.Lmter, L., 482, .488.Laszlo, I., 351.Laszlo, P., 210, 216, 351,Latham, J. V., 384.Latimer, W. M., 65.Latjaeva, V. N., 188.Latner, A. L., 551.Lauderman, R., 524.Lauer, G., 88.Laugg, P., 420.Laughton, P. M., 270.Launiala, K., 478.Laurent, A., 595.Laurent, T. C., 494, 495,Laurie, V. W., 207.Laursen, R. A., 448.Lautsch, W. F., 66.Laver, G., 88.Lavie, D., 368, 425.26.301.573, 576.Lash, J., 503.368.531.Lavaux, J.-P., 232, 414644 INDEX OF AUTHORS' NAMESLa Villa, R. E., 170, 687.Lavintman, N., 442.Law, D. A, 408.Law, P. A., 232.Lam-esson, S. O., 307.Lawler, R. G., 29, 200.Lawley, P. D., 447.Lawrence, A.R., 212.Lawrie, W., 397.Laws, E. Q., 553.Lawson, K. D., 219.Lawton, E. A., 136.Lawton, R. G., 233.Lazarov, D., 89.Lazarow, A., 470, 511.Lazdins, D., 286.Lazebnik, J., 486.Lazzarini, E., 558.Leatherwood, J., 434.Leaver, D., 378, 383.Lebedev, Ya. X., 41.Lebedev, Yu. A., 66.Lebedeva, I. V., 139.Lebedeva, N. V., 537.LeBel, N. A., 233, 252.Leblond, C. P., 501.Lebreton, P., 219, 391.Lechevalier, H. A,, 451.Lecocq, P., 570.Leddicotte, G. W., 556.Ledeen, R. W., 415.Le Demezet, M., 302.Leden, I., 72.Leder, P., 456.Lederberg, J., 559.Lederer, E., 320.Lederer, M., 532.Ledger, R., 249, 255Ledouble, G., 404.Ledwith, A., 144, 324.Lee, C. C., 224, 276.Lee, E. E., 443.Lee, K. Y., 447.Lee, M.H., 453.Lee, P., 447.Lee, R. I€., 162.Lee, W. W., 449, 450.Lee, Y. C., 441, 494.Leeney, T. J., 377.Lees, P., 336.Leete, E., 372, 376, 396,Lefebvre, R., 42, 198.Le FGvre, R. J. W., 208,216, 217, 220.Leff, J., 453.Leffler, A. J., 124.Leftwick, A. P., 416.Legatt, T., 416.Leggetter, B. E., 300.Legh-Bouille, M ., 498.Le Goff, E., 327, 346.Legoff, R., 302.Legrand, M., 426.Le Guyader, M., 302.Legvold, S., 53.397.Lehman, C., 423.Lehmann, H.-N., 66.Lehmann, J., 438.Lehmkuhl, H., 126.Lehn, J. M., 367.Lehn, W. L., 133.Lehr, W., 138.Lehtinen, T., 319.Leibman, K. C., 468.Leigh, T., 340.Leikis, D. I., 83, 84, 87.Leikis, D. V., 98.Leiserowitz, L., 265, 567.Leisten, J. A., 250.Leites, L. A., 131.Leitich, J., 330.Leloir, L.F., 429, 498.Le Mahieu, R., 303, 416.Lemal, D. M., 324, 350, 351,Le Men, J., 357, 404, 427.Lemieux, R. U., 430,434.Lemieux, R. V., 456, 457.Lempert, K., 381.Lengy-el, I., 371.Lenhard, R. H., 417.le Noble, W. J., 249, 251.Lenton, M. V., 139.Lentz, C. W., 129.le Ny, G., 237.Leonard, N. J., 371, 382,394, 448.Leone, A., 259.Leong, P. C., 536.Leonidov, V. Ya., 66.Leonova, A. I., 106.Lepe M, J., 268.Lerch, B., 451.Lerkkh, R., 86.Lerner, H., 97.Lesbre, M., 131.Leslie, R. T., 528.Letchford, B., 333.Lethan, D. X., 389.Lethbridge, J. W., 140.Lethuillier, C., 107.Letsinger, It. L., 278, 295,Letters, R., 451.Lettre, H., 418.Leusink, A. J., 395.Lever, A. B. P., 175.Levi, A. A., 352.Levi, D.L., 68.Levi, F., 529.Levich, V. G., 81, 84.Levin, B., 478, 480.Levin, M. S., 555.Levina, S. D., 93.Levine, S., 85.Levine, X. G., 417.Levisky, J. A., 276, 331.Levitt, B. P., 49.Levitz, M., 483.Levshin, L. V., 549.Levy, A. A., 249, 439.381.333.Levy, D. H., 31.Levy, E., 416, 580.LBvy, J., 404.Levy, J. F., 243.Levy, M., 60.Lewandowski, K. M., 233.Lewey, S., 530.Lewicki, E., 259, 333.Lewin, R., 5Sl.Lewis, B., 139.Lewis, B. A,, 439.Lewis, C. P., 209, 559.Lewis, E. S., 270, 276,Lewis, G. B., 63.Lewis, G. E., 218, 330, 387,Lewis, G. P., 94, 522, 523.Lewis, J., 175, 180, 182,Lewis, J. R., 303.Lewis, J. W., 301.Lewis, K. E., 285.Lewis, M. E., 553.Leyshon, K., 276.Li, N. C., 296.Libergott, E., 528.Li Ch'ih-Fa., 134.Lichstein, B.M., 122, 1%.Lichti, H., 357.Liddle, L., 488.Lide, D. R., 19, 23.Lide, D. R., jun., 205.Lidstrom, L. J., 546.Liebau, F., 151.Liebman, A. A., 396.Liedmeier, F., 69.Liefliinder, M., 492.Lieh Min Lap, 94.Lielmezs, J., 205.Lienherd, K., 130.Lifshitz, C., 64.Light, A., 507.Light, K. K., 374.Lillien, L., 249.Lin, C. C., 161, 205.Lin, K., 351.Lin, W. C., 40.Lin, Y. S., 338, 352.LinarBs, H., 420.Linck, W., 66.Lincoln, A. J., 103, 547.Lind, M. D., 174, 584.Lindahl, C. B., 180.Lindahl, U., 495.Lindall, A. W., jun., 470.Lindberg, B., 433, 439,440, 441, 442.Linde, H., 362.Lindner, H. H., 187.Gindqvist, I., 75.Lindsay, D. G., 379.Gindstrom, F., 93.Lineback, D. R., 430.Linfield, M.P., 256.Linford, H. B., 93.277395.183, 190INDEX OF AUTHORS’ NAMES 645Lingafelter, E. C., 586, 588.Lingane, J. J., 539, 556.Lingens, F., 387.Linke, K.-H., 143.Linker, A., 444.Linnett, J. W., 56, 116, 196.Linneweh, F., 483.Lions, F., 166, 173, 586.Liplrin, D., 448.Lipinann, F., 454.Lipowitz, J., 277.Lippard, S. J., 159.Lippincott, E. R., 216.Lipscomb, R. D., 135.Lipscomb, W. N., 118, 119,120, 122, 189, 338, 353,580, 581, 598, 601.Liptay, G., 560.Lis, H., 493.Lissitzky, S., 493.List, D., 141.Lisbon, T. V., 333.Li-Tao Huang., 72,Litovitz, T. A., 49.Littau, V. C., 455.Littel, R., 420.Littire, W., 154.Little, R., 146.Little, W. F., 340.Litvin, E. F., 106, 108, 334.Liu, C. F., 166, 173.Liu, C. H., 173,539.Liu, R.S. H., 350.Livingstone, J. R., jun.,Livingstone, S. E., 163, 323.Livshits, D. M., 550.Li \Ven-chou, 101.Lletvellyn, D. R., 298.Lloyd, D., 337.Lloyd, D. A., 564.Lloyd, D. M. G., 327.Lloyd, H. A., 399.Lloyd, J. B. F., 276.Lloyd, J. E., 122.Lloyd, K. O., 497.Lloyd Jones, H., 370.Lo, G. Y., 210.Lobbett, E. J., 549.Locchi, S., 572.Lock, C. J. L., 160.Loclryer, R., 550.Loeb, H., 478.Loewsnstein, A., 21 1.Logan, N., 148, 170.Lohmann, A., 484.Lohmann, D. H., 166.Lohr, L. L., 189.Lohrmann, R., 449, 452.Lomste, J. S., 276.Lombard, R., 304.Lomer, P. D., 659.Lomer, T. R., 601.Lomonte, J. N., 545, 552.London, D. R., 486.394.Lo, Y. s., 210.Long, A. G., 388.Long, F. A., 64, 275.Long, G.G., 142.Long, L., 433.Long, L. E., 554, 555.Long, R., 185, 308, 317.Long, R. F., 183.Longeray, R., 299.Longevialle, P., 396, 407,Longo, F. R., 230.Longobucco, R. J., 546.Longone, D. T., 328.Longuet-Higgins, H. C., 26,20, 31, 36, 196, 197, 205.Longworth, J. TtJ., 45.Loodmaa, IT. R., 93.Loog, B. K., 93.Loopstra, B. O., 569, 576.Lopez-Cast’ro, A., 586, 602.Lorberth, J., 132.Lord, R. C., 213.Lorenc, L., 304, 422.Lorenz, D., 305.Lorenz, W., 82, 86, 91.Lorenzi, G. P., 325.Lorincz, A. E., 387.Lorse, G., 297.Loselroot, G., 480.Losev, S. A., 51.Lossing, F. P., 327.Lotlikar, P. D., 473.Lott, P. F., 549, 556.Lottes, K., 179.Lotz, M., 488.Loudon, J. D., 245, 280,Loughridge, L. W., 485.Lovald, R.A., 381.Love, J., 443.Loveland, B. A., 274.Lovell, F. M., 609.Lovering, E. G., 202.Lowe, B. E., 315.Lowe, G., 296, 315, 388.Lowell, S., 245.Lowery, J. A., 345, 531.Lowry, L. L., 368.Loyd, C. M., 18.Lu, J. Y., 509.Lucas, R. A., 398.Lucchesi, P. J., 106.Luce, C. C., 533.Luche, J.-L., 373.Lucke, W. E., 442.Lucken, E. A. C., 31, 34,Luckhurst, G. R., 34, 37.Ludi, A., 572.Ludwick, J. D., 557.Ludwig, H.-B., 109.Ludwig, W., 163.Lueschow, H. M., 74.Luttringhaus, A., 355.Luttringhaus, H., 310.Luijten, J. G. A., 133.426.370.116, 185, 217, 592.Lukas, G., 357.Luke, C. L., 545.Lukianycheva, V. I., $9.Lukovtsev, P. D., 94.Luksha, E. A., 158.Lukton, A., 295.Lundgren, F. O., 546.Lundgren, G., 57%Lundin, R.E., 254, 559.Lunn, V i . H., 258.Lupin, M. S., 185.Lush, D. J. L., 453.Lusinchi, X., 299, 420.Lusk, D. I., 249.Lustig, M., 136, 145.Lutinski, F. E., 104.Luttinger, L. B., 313.Lutz, C. A., 119.Lutz, E. F., PGG.Lutz, R. E., 379.Luzzati, V., 458. 607.L’vova, L. A., 94.Lwowski, W., 324, 378.Lyall, J. &I., 387, 456.Lydon, J, E., 189, 592.Lykkma, J., 87.Lyle, R. E., 383.Lynch, H. J., 485.Lynch, J., 505.Lynden-Bell, R. M., 44,200.Lynds, L., 77.Lyness, W. I., 273.Ma, J. C. K., 387.Ma, T. S., 544.Maaser, M., 163.Maass, D., 498.Maat, R. J., 112.Maatman, R. W., 103.Mabry, C. C., 454.McArdle, B., 480.&Bride, D. W., 188.McCaa, D. J., 51.McCaffery, A. J., 177, 204.Maccagnani, G., 270.McCaldin, D.J., 397.McCallum, A., 330.McCammon, C. S., 599.McCapra, F., 363, 407, 412.McCasland, G. E., 214.RlcCarley, R. E., 163, 157.filecarthy, C. F., 485.NIcCarthy, W. C., 219.McChesney, E. W., 472.McChesney, J. D., 362.Macchi, P., 236.Macchia, B., 248.Maccioni, A., 305.McClain, J., 57.McClanahan, J. L., 139.RIcClean, R. T. B., 65.McClelland, A. L., 118.UcCleskey, J. E., 549.McCleverty, J. A., 182.McCloskey, J. A., 357, 396.McClure, D. S., 73646 INDEX OF AUTHORS’ NAMESMcClure, J. H., 544.Maccoll, A., 255, 256, 280,McColl, D. H., 539.McCollum, J. D., 204.McConnel, J. F., 609.McConnell, H. M., 36, 44,45, 198, 199, 200, 202.McConnell, J. F., 605.McCorkindale, N. J., 250,McCormick, J. R. D., 305.McCoubrey, J.C., 49, 53,McCoy, E. F., 197.McCoy, R. E., 68.McCrae, W., 313.McCrindle, R., 361, 362,McCullough, J. D., 583,615.McCollough, J. P., 63, 65,McCurdy, W. H., 534.MeDaniel, D. H., 147.McDevitt, N. T., 210.MacDiarmid, A. G., 124,129, 130, 145, 212.MacDonald, A. C., 591.McDonald, C. C., 45, 162.Macdonald, C. G., 105.MacDonald, D. L., 432.McDonald, I. R., 389.McDonald, J. E., 66.Macdonald, J. J., 95.Macdonald, J. R., 83, 84.McDonald, R. N., 258, 372.McDonald, R. R., 573.McDonagh, P. M., 214.McDonough, J. M., 143.McDowell, C. A., 9, 27, 30,NcEwan, D. J., 533.McEwen, W. E., 426.McFadden, W. H., 559.McFall, I. E., 189.McFerland, J., 542, 544.McFarlane, N., 144.Macfarlane, R. M., 154.McGarrahan, J. F., 502.McGarvey, F.X., 532.MacGee, J., 470.McGovern, T. P., 304.McGrady, M. M., 132.McGrath, W. D., 13.Macg-regor, P. T., 335.McGuire, F. J., 358.Mach, K., 126.McHale, 282.McHenry, K. W., 103.Machin, D. J., 156.Machleidt, H., 428.Maciera-Coelho, A., 477.McInnes, C. A. J., 558.McIntyre, J. S., 238.Macintyre, W. M., 600, 605,297.400.68.364, 365.66, 67.33, 40.606.McKay, H. A. C., 149.Mackay, H. M. M., 480.Mackay, K. M., 131.McKechnie, J., 137.McKee, D. W., 101, 105.McKeever, L. D., 277.MacKellar, F. A., 553.McKenna, J., 249, 255.MacKenzie, D. R., 116, 577.Mackie, A. M., 496.McKinney, P. S., 554.McKinnon, A. J., 588.McKinnon, D. M., 383.Mackle, H., 65, 79.Mackor, E. L., 32, 36, 46.McKusick, V.A., 475.McLachlan, A. D., 37, 45,46, 198, 199, 200.MacLaren, R. O., 147.McLauchlan, K. A., 202,McLaughlan, K. A., 335.McLaughlin, C. S., 454.McLay, D. B., 209.MacLean, D. B., 409.McLean, J., 416.McLean, S., 400.Macleay, R. E., 290.McLeish, J., 453.MacLeod, J. K., 459, 507.MacLeod, W. D., jun., 369.McMahon, R. E., 465,466.McNahon, M. A., 230, 276.McMeekin, W., 423.McMichael, K. D., 244.Macmillan, H. R., 530.MeMorris, T. C., 359.McMurray, W., 406.McMurray, W. C., 480.McNabb, W. M., 561.McNeil, D. A. C., 183.McOmie, J. F. W., 335,387.McPhail, A. T., 358, 364,Macpherson, I. A., 330.Macqueen, H. R., 87.McQuillan, G. P., 130.McRae, E., 197.McRae, E. G., 197.McTaggart, F. K., 151.McTigue, P. T., 290.McTurk, G., 143.McWeeney, R., 195.McWhinnie, W.R., 167,Madden, J., 503.Madden, M., 564.Madison, N. L., 107, 299.Maccagnani, G., 244.Madeda, F., 546.Maeland, A. J., 118.Magee, P. N., 447.Magee, P. S., 252.Magee, R. G., 550.Magee, R. J., 528, 529, 552,456.610.175.553.Maggio, F., 162.Magi, M., 420.Magnuson, W. L., 174.Magnusson, B., 570.Magrill, D. S., 400.Mague, J. T., 159, 162,573.Maguire, R. G., 119.Mahajan, J. R., 358.Mahapatra, G. N., 447.Maher, J. P., 189, 202.Mahler, J. E., 185, 256.Mahler, R. J., 510.Mahler, W., 136.Mahony, J. D., 559.Mai, V. T., 234, 268.Maickel, R. P., 460.Maier, G., 124.Maier, L., 137.Maier-Borst, W., 326, 349.Maina, G., 415.Maine, F. W., 380.Mair, €3. J., 216.Mairanovsky, S.G., 91, 92.Maire, G., 111.Maitland, R., 168.Maitte, P., 311.Majer, J. R., 64.Majumdar, A. K., 551.Mak, T. C. W., 599.Maki, A. H., 30-32, 38, 42,47, 171, 172.Maki, N., 161.Maki, T., 437.Maki, Y., 387.Makin, S. M., 310.Makino, M., 491.Makisumi, Y., 283, 386.Makrides, A. C., 89, 96.Makula, D., 307.Malatesta, L., 179.Maley, F., 502.Malhotra, S. C., 126.Malhotra, S. K., 288, 413,Malik, A. A., 166.Malisheva, A. V., 188.Mallan, J. M., 302, 310.Mallory, F. B., 330, 382.Malm, J. G., 115, 116.Malm, J. L., 116.Malmstadt, H. V., 561, 562.Malofsky, B. M., 367, 610.Mal’tsev, A. N., 101.Mal’tseva, N. N., 101.Malf, E., 543.Mamantov, G., 140.Mammi, M., 603.Mamuzib, R. I., 304.Manabe, Y., 325.Manakow, M. N., 129, 324.Manastyrskyj, S.A., 179.Manchand, P. S., 318.Manche, E., 544.Mandel, J., 552.Mandel, M., 453.Mandell, L., 456.418INDEX OF AUTHORS’ NAMES 647Mander, L. N., 361, 412.Mandlestan, M., 505.Mangold, D. T., 121.Mangravite, J. A., 276.Manhas, M. S., 412.Manitto, P., 362.Manley, K. A,, 475.Mann, C. B., 510.Mann, D. E., 19, 195, 209.Mannan, K., 593.Mannering, G. J., 466, 467.Manners, D. J., 440-442Manniello, AX., 498.Manning, R E., 404,406.Manshar, H., 579.Mansharan, P. T., 585.Mansfield, G. H., 425.Mgnsson, M., 65, 67.Mantikyan, M. A., 111.Mantione, R., 307.Manuel, G., 131.Manzoor-I-Khuda, M., 303.Mapper, D., 558.Marcinkus, D., 543.Marcq, M., 106.Marcus, R. A., 89.Mareschal, J., 577.Marezio, M., 579.Margoliash, E., 519.Margrave, J.L., 61, 62, 64,67, 69, 77, 113, 411.Margreth, A,, 473.Margulis, T. N., 579, 611.Mariani, C., 598.Marini, J. L., 153.Marion, F., 564.Markgraf, J. H., 286.Markin, M. I., 560.Markin, V. S., 97.Marko, B., 191.Marko, L., 182, 191.Markov, B. F., 81.Markovec, L., 317.Markowitz, M. M., 560.Markowitz, S. S., 559.Markus, G., 510.Marmo, F. F., 17.Marmur, J., 447, 453, 607.Mars, P., 100.Marsh, F. D., 323.Marsh, R. E., 599, 605, 612.Marshakov, I. K., 93.Marshall, J. H., 33.Marshall, L. M., 553.Marshall, R. D., 513, 519.Marsico, J. W., 457.Marsili, A., 366.Martin, D. S., 178.Martin, F. H., 115.Martin, H. A., 185.Martin, J., 354, 558, 602.Martin, J. C., 216, 219.Martin, J.F., 63.Martin, R. B., 288.Martin, R. L., 152, 168,177.Martin, T. C., 559.Martin-Smith, M., 360.Martinez, A. P., 449.Martinez, L., 497.Martinez-Camera, S., 606.Marton, A. V., 467.Marumo, S., 450.Maruyama, K., 212.Maruyama, T., 519.Maruyama, Y., 218.Marx, W., 504.Mary, N. Y., 286.Marzluff, W. F., 158.Masamune, S., 329, 363,Masamune, T., 425.Masazza, F., 71.Mascarenhas, Y., 605.M a s h , D. N., 302.Mashova, A. F., 555.Mason, D. T., 523.Mason, G. W., 530.Mason, H. S., 460, 461.Mason, L. S., 70.Mason, R., 161, 162, 186,339, 585, 591, 596, 602.Mason, S. F. 177, 197, 204.Masotti, R. E., 484.Massey, A. G., 119, 126.Massey, H. S. W., 58.Massey, V., 516.Masson, F., 458.Mastafanova, L. I., 305.Masui, M., 288.Mesumune, S., 349.Mateescu, G.D., 231.Mateos, J. L., 290.Matheny, N. P., 311, 421.Matheson, A. J., 57.Mathews, C. K., 464.Mathews, D., 273.Mathias, A., 544.Mathiasson, B., 387.Mathieson, A. McL., 609.Mathieson, D. W., 391.Mathieu, A., 560.Mathis, A., 458.Mathiesen, H., 595.Mathur, K. B. L., 280.Mathur, N. K., 534.Mathur, R., 296.Mathur, S. C., 559.Matland, C. G., 56.Matson, F. A., 59.Matson, J. M., 93.Matsubara, I., 206.Matsuda, G., 519.Matsuda, K., 437.Matsufuji, K., 369.Matsuhashi, M., 436.Matsui, M., 307, 401, 529.Matsumoto, J., 410.Mat,sumura, C., 410.Matsushima, Y., 435.Matsuura, S., 456.Matsuura, T., 363.409.Mattes, R., 589.Matteson, D. S., 272.Matthews, B. W., 603.Matthews, C.W., 14.Matthews, F. S., 457.Mattocks, A. R., 398.Matula, D. W., 113.Matuszko, A. J., 212.Matveev, V. V., 117.Matwiyoff, N. A., 133.Mauli, R., 360.Maurel, R., 106, 108.Maurice, A., 319.Maurice, M. J., 551.Mauser, H., 288.Mawby, R. J., 180.Maxirnadshy, A., 31.Maxted, 33. B., 102.May, P. J., 388.May, S. C., 516.Maya, W., 136.Mayahi, M. F., 260.Mayitma, M., 450Mayell, J. S., 90.Mayer, I., 580.Mayer, I. P., 570.&layer, L., 23.Mayer, R., 307, 309, 323.Mayer, W. J., 290.Mayes, N., 121, 122.Maynert, E. W., 475.Mayntz, R., 543.Mayweg, V., 172.Mazel, P., 463, 464.Mazerolles, P., 131.Mazhar-ul -Haque , 3 5 9.MaziGres, C., 560.Mazur, J. H., 385.Mazur, P., 82.Mazur, Y., 301, 415, 416,Meadow, P., 505.Meakins, G.D., 418.Means, R. E., 321.Mechoulam, R., 367, 392.Meckel, W., 339, 354.Meckle, F. H., 556.Medcalf, D. G., 442.Medes, G., 484.Rleditsch, J. O., 535.Medvedev, V. A., 69.Medvedeva, A. A., 300.Medvedeva, L. A., 87.Medvedeva, Z. S., 76.Meehan, E. J., 542.Meek, D. W., 164.Megaw, H. D., 578.Megerle, G. H. 248.Mehl, W., 88.Mehltretter, C. L., 429.Mehner, L., 66.Mehrotra, R. C., 127, 133,Mehrotra, R. K., 127.Mehta, A. S., 351.Melita, T. N., 319.424.538648 INDEX OF AUTHORS’ NAMEShleiklehzni, V. F., 142.Meienhofer, J., 508, 509.Meier, J., 549.Meier, W. M., 578.Meinschein, W. G., 321.Meinwald, J., 257.Meinwald, Y. C., 257.Rleise, W., 407, 426.Mei-Sie Lin, 400.Meister, W., 126.Meites, L., 538, 540.Nelby, L.R., 172.Melchior, D., 378.Melera, A., 211, 339, 361,Meller, A., 124.Mellinger, T. J., 549.Mellish, C. E., 158.Mellman, W. J., 477.Mellon, E. K., jun., 124.Mellor, J. M., 360.Melmon, K., 523.Melnick, L. M., 561.Meloche, H. P., 450.Meloun, B., 517.Meloy, G. K., 208.Melton, C. E., 110.Melville, D., 361.Menard, J. -M., 100.Nlenashi, J., 74.Menchaca, H., 290.Mendoza, C., 489.Mengel, G. D., 450.Menkes, J. H., 483.Menten, M. L., 487.Mercer, E. E., 183.Merchant, J. R., 330.Merenyi, R., 187, 286, 326,Merer, A. J., 17, 25.Merijanian, A., 142.Meriwether, B. J., 517.Merlis, N. M., 434.Merola, L., 481.Merola, L. O., 477.Merrall, G. T., 257.Memifield, R. B., 522.Merritt, J., 546.lifers, R.G., 118.Merz, W., 543.Meshcheriakov, A. P., 311.Messer, C. E., 11s.Messer, M., 478.Messier, C., 180.Messinger, E. C., 484.Mester, L., 430.Metcalfe, J., 537.Meth-Cohn, O., 381.Metlesics, W., 394.Metzger, H., 310.Metzler, R. K., 552.Metzschker, H.-J., 66.Meuche, D., 337.Meyer, B., 143.Meyer, D., 494.Meyer, E. F., 107, 330,375.365, 426.350, 354.Bfeyer, H., 136.Meyer, H.-J. 343, 378, 574.Meyer, K., 494, 495.Meyer, K.-U., 153.Meyer, M. W., 286.Meyer, R., 95.Meyer, R. A., 560, 561.Meyer zu Rechendorf, W.,Meyers, C. de L., 428.Meyerson, X., 204, 248, 559.Meystre, C., 421.Mezzetti, T., 426.Micheel, F., 288, 492.Michel, A., 570, 576.Michelman, J. S., 380, 382.Michelson, A. M., 446, 451,MiEoviE, V.M., 304.Mietzsch, F., 267, 352.Mighell, A. D., 603.MihailoviG, M. L., 304, 422.Mikes, O., 507.Mikhailov, B. M., 125, 301.Mikheeva, V. I., 101.Mikkeleit, W., 548.Mikolojczak, K. L., 319.Mikulaschek, G., 144.Mikulska-Macheta, A., 453.Milazzo, G., 80.Milberg, M. E., 579.Mile, B., 40, 117.Miles, F. B., 250.Miles, H. T., 456.Millar, I. T., 336.Millard, M., 130.Miller, A., 601.Miller, B., 282.Miller, C. K., 586, 604.Miller, D. B., 334.Miller, E. C., 472, 473.Miller, F. A., 214.Miller, F. D., 555.Miller, G. W., 554, 555.Miller, H. C., 119, 120, 125.Miller, J., 280.Miller, J. A., 237, 472, 473.Miller, J. G., 63, 129, 212.Miller, J. M., 75, 125, 131.Miller, J. R., 137.Miller, J. T., jun., 122, 139.Miller, J.W., 467.Miller, K. S., 475.Miller, L. L., 499.Miller, M. C., 139.Miller, N. E., l l S , 120, 125.Miller, S., 483.Miller, S. I., 297.Miller, W. B., 143.Miller, W. T., 320, 324.Xiller, W. T., jun., 116.Millero, F. J., 74.Milligan, D. E., 21, 209.Millikan, R. C., 51, 55, 57.Mills, A. A., 547.Mills, I. M., 23.435, 436.452, 456.Mills, J. A., 431.Mills, 0. S., 184, 185.Mills, S., 567.Milne, M. D., 485, 486.Milner, G. W. C., 554.Milner, P. C., 90.Milward, R. C., 53.Mima, T., 546.Min-Hon Rei, 222.Minakawa, A., 4S2, 483.Minato, H., 357.Minc, S., 83, 84.Mingins, J., 85.Minh Truong-Ho, 405.Minnick, E. J., 543.Minot, M., 309.Miocque, M., 303.Mirkind, L. A,, 88.Mironov, G. S., 309.Mironov, V.E., 127.Mirskey, A. E., 455.Mirsky, A. E., 519.Mirzacva, A. K., 62.Mishutushkine, I. P., 86.Mislow, K., 328, 392.Misra, R., 361.Mitchell, J., jun., 544.Mitchell, M. J., 213.Mitchell, T. R. B., 302.Mitra, R. B., 249, 313, 369.Mitsch, R. A., 209.Mitsuhashi, H., 426.Mittsel, Yu. A., 549.Miwa, T., 441, 542.Miya, T. S., 460, 467.Miyagawa, I., 37.Miyahara, K., 105, 106.Miyake, K., 608.Miyashita, C., 441, 492.Miyazaki, M., 530.Miyazawa, T., 214.Miyoshi, Y., 357,Mizuba, S., 428.Mizuno, Y., 450, 451.Mladeck, M. H., 602.Mlodzikova, H., 299.Mnatsakanyan, V. A., 401.Mochizuki, M., 94.Mockler, G. M., 158.Mockus, J., 240.Moczar, E., 430.Modi, B. D., 429.Modler, R. F., 377.Modugno, G., 532.Mody, N. N., 444.Mobius, K., 31.Mockel, F., 86.Moedritzer, K., 113, 142.Moller, K.E., 308.Moller, W. J., 454.Moelwyn-Hughes, E. A.,Moersch, G. W., 417.Moffatt, J. G., 451.Moffatt, M. E., 273, 276.Mohilner, D. M., 82, 91.250INDEX OF AUTHORS’ NANES 64 9Mohyuddin, F., 480.Moir, R. Y., 399.Moiseev, I. I., 305.Mold, J. D., 321.Mole, M. F., 68.Mole, T., 126.Mollov, N. M., 400.Molnar, J., 499, 502.Molodkina, A. N., 128.Molotkovskii, Y. G., 321.Mommaerts, W. F. H. M.,Mondon, A., 410.Monhawa, T., 483.Nonkovic, I., 397.Monnier, D., 541.Xonostori, B. J., 215.Montagnier, L., 453.Montanari, F., 244, 270.Montgomery, J. a,, 390,Montgomery, L. K., 264.Montgomery, R., 492, 494.Monthbard, J.-P., 299.Monti, S. A., 404.Montijn, P.P., 314, 317.Montonnier, C., 414.Xontreuil, J., 492.Moodie, R. B., 274.Moody, G. J., 116, 532.Moon, S., 246.Mooney,E.F., 122,125,219.Mooncy, J. B., 547.Moore, B. P., 404.Moore, C. B., 211.Moore, D. W., 126, 385.Moore, F. L., 530.Moore, F. W., 157.Moore, H. W., 215, 344.Moore, J. A., 380, 394.Moore, L. E., 163.Moore, M., 419, 425.Moore, R. E., 344.Moore, S., 481, 510-512,Mootoo, B. S., 365.Morand, P. F., 423.Morawetz, H., 293.Morehouse, S. M., 166.Moretti, J., 500.Morgan, C. H., 567.Morgan, C. R., 511.Morgan, I. L., 558.Morgan, J. E., 54.Morgan, J. P., 205.Morgan, K. J., 219.Morgan, W. T. J., 441, 497.Morgenstein, J., 323.Morgenstern-Badarau, I.,Mori, H., 307, 415.Moriarty, R. M., 212.Morikawa, M., 317, 331.Morikawa, T., 213, 346,482.Morimoto, E.M., 249.Morimoto, N., 575.458.448.516, 523.576.Morino, Y., 213.Morisawa, S., 451.Morisawa, Y., 413.Moritz, A. G., 211.Moritz, K.-L., 334.Morizur, J.-P., 303.Morley, J. S., 459, 507.Morneweck, S. T., 305.Morokuma, K., 38.Moroshkina, T. M., 548.Morosin, B., 159, 584.Morozov, I. S., 134.Morozov, N. M., 110.Morozova, I. D., 198.Morozova, T. G., 128.Morozumi, S., 399.Morris, C. J. 0. R., 530.Morris, D. F. C., 156, 558.Morris, M. D., 556.Morris, P. J., 383.Morrison, A., 364.Morrison, G. H., 529, 558.Morrison, H., 317.Morrow, D. F., 417.Morrow, T., 13.Morse, R. S., 557.Mortenaen, O., 478.Mortimer, C. T., 61, 62, 66,Morton, J. R., 27, 38, 39,Morton, R.B., 342.Mosch, W., 136.MOSCOU, L., 112.Moser, E., 180.Moser, W., 131.Mosettig, E., 419.Mosevitskii, M. I., 453.Moshentseva, L. V., 302.Mosher, H. S., 325.Mosher, W. A., 303.Moshier, R. W., 534.MOSS, R. L., 99, 100.Mossel, A., 601.Mothes, J., 397.Mothes, K., 452.Mott, N. F., 85.Moule, D. C., 24.Moul6, Y., BOO.Mouray, H., 500.Mouty, M. A., 146.Mower, E. B., 103.Mower, H. F., 507.Moy, D., 127.Moyer, J. D., 545.Moza, B. K., 406.Mrskog, A., 479.Mudd, S. H., 482.Miiller, A., 154.Muller, E., 334, 415, 418.Muller, J., 188.Muller, K., 83.Muller, L., 95.Muller, O., 370.Muller, R., 142.MOWOW, s. I., 143.67.199, 204.Muller, W., 86, 102, 127.Mueller, W. A., 244.Mullhofer, G., 253, 254.Muenter, K.S., 207.Murset, G., 478.Muetterties, E. L., 118-120,125, 136, 145.Mugnoli, A., 598.Muir, H., 491, 494.Muir, K. W., 267, 335.Muir, R. D., 428.Muirhead, J. S., 24.Mujama, H., 331.Mukaiyama, T., 309, 313.Mukherjee, R. N., 127.Mukherjee, S., 443, 444.Mukherji, A. K., 534.Mukhtarov, I. A., 209.Mulay, L. N., 143.Mulder, R. J., 324.Muller, C. E., 546.Muller, J. -C., 20 6.Muller, N., 214.Muller, W. H. E., 109.Mulliken, R. S., 26.Munavalli, S., 360.Munch-Petersen, J., 260.Munemori, M., 561.Muneyuki, R., 275, 351.Munson, R. A., 88, 140.Mur, V. I., 370.Murdoch, H. D., 184, 185.Murman, R. K., 74, 168.Murphy, C. B., 534.Murphy, C. F., 402.Murphy, C. J., 311.Murphy, J. W., 529.Murphy, W. H., 496.Murphy, W.S., 301, 311.Murray, J. G., 130.Murray, K., 455.Murray, R. D. H., 361, 362.Murray, R. W., 42-44, 88,Murrell, J. N., 30, 195, 197.Murrill, J. B., 397.Murthy, A. R. V., 144, 145,Murthy, P. R., 153.Murti, V. V. S., 519.Murto, J., 279.Murty, V., 497.Musgrave, 0. C., 334.Musgrave, W. K. R., 384.Musha, S., 551.Musikas, M. C., 149.Iblusil, A., 565.Musker, W. K., 250.MUSSO, H., 341.Mutter, G. P. B., 435.Myamlin, V A., 98.Myers, R. B., 549.Myers, R. J., 19, 31.Myers, T. C., 447.Mykytiuk, D. P., 68.M d , M. E., 265.92, 200.201, 203650 INDEX OF AUTHORS' NAINaar-Colin, C., 120.Nace, H. R., 416.Nadel, M. E., 260.Naegeli, P., 399.Kaemura, I<., 317.Nagabhushan, T. L., 434.Nagai, Y., 276.Nagakura, S., 24, 218.Nagarajan, R., 430.Nagasampagi, B.A., 216.Nagashima, K., 536.Nagata, C., 203.Nagata, S., 108.Nagata, W., 215, 303, 409,Nagl, G., 530.Kagy, B., 321.Nagy, 0. B., 294.Nagy, P. L. I., 184.Kair, P. P., 557.Nakagawa, G., 536.Nakagawa, I., 213.Nakagawa, K., 304.Nakagawa, N., 317.Nakagawa, S., 205.Nakagawa, T., 368.Nakamura, G., 450.Nakamura, S., 441.Nakanishi, K., 359, 360,Nakanishi, Y., 551.Nakano, J., 410.Nakano, T., 407, 426.Nakashima, F., 554.Nakashima, T., 507.Nakata, H., 304.Nakayama, T., 25.Nakemura, T., 90.Nakhmanovich, A. S., 109.Nalbandyan, A. B., 45.Naldini, L., 179.Nalfandian, A. B., 45.Nanbu, H., 313.Nambury, C. N. V., 219.Namektin, N. S., 373.Namikawa, K., 206, 210.Nancollas, G.H., 178.Nande, W. J., 547.Narang, C. K., 534.Narang, S. A., 358.Narashimhan, N. S., 365.Narayan, K. A., 532.Narayan, S., 532.Narayanan, C. R., 365.Narayanaswami, K., 332.Nardi, N., 165.Narisada, M., 215, 409, 412.Narita, K., 519.Nash, J. R., 554.Nash, M. J., 356.Nasielski, J., 272, 276, 310.Nasipuri, D., 309.Naso, F., 244.Nast, R., 167, 179.Nathaus, N., 454.Nation, G. H., 535, 564.412.363.Natori, S., 366.Natsume, M., 363, 610.Natta, G., 613.Naughton, M., 519.Naughton, M. A., 508.Nault, L. G., 112.Naves, Y. R., 357.Navis, G. J., 466.Nayak, U. R., 358.Nazarenko, V. A., 537.Neale, R. S., 257.Nealy, D. L., 249.Needham, C. D., 210.Needham, D. M., 521.Nefedov, 0. M., 324.Nefedow, 0.M., 129.Nehme, M., 313.Nehring, D., 111.Neiding, A. B., 115.Neidle, P., 454.Neikam, W. C., 201.Neill, D. W., 482.Neill, K. G., 370.Neilson, A. H., 26.Neilson, T., 435.Nekrassov, L. N., 95.Nelander, D. H., 416.Nelander, L., 74, 75.Nelson, D. H., 461.Nelson, N., 472.Nelson, R., 212.Nelson, R. W., 319.Nelson, T. L., 484.Nelson, W. H., 155.Nenitzescu, C. D., 231, 331.Nenortas, D. R., 298.Nesket, R. K., 197.Nesmeyanov, A. N., 142,Nesmeyanov, N. A., 271.Nestler, H. J., 410.Nesvadba, H., 396, 520.Netter, K. J., 468.Neu, H. C., 455.Neuberger, A,, 491, 492,Neuenschwander, M., 337.Neufeld, E. F., 429, 498,Neugebauer, G. A., 64.Neuhaus, F., 505.Neuklis, W. A., 417.Neukom, H., 430.Neumair, G., 180.Neuman, R.C., jun., 346.Neumann, H. M., 157.Neumann, V., 154.Neumann, W. P., 132.Neumayr, F., 143.Neuner-Jehle, N., 396.Neurath, H., 296, 507.Neuss, N., 406.Neveu, M., 287.Newbold, G. T., 220.Newburg, N. R., 324.Newman, E. J., 552.191, 340.513, 519.502.E SNewman, H., 436.Newman, M. S., 295, 330.Newman, R., 60.Newmark, R. A., 209.Newmiller, R. J., 87.Newnham, R. E., 576.hTewton, J., 276.Newton, T. W., 154.Nichol, C. A., 467.Nicholls, D., 118, 151.Nichols, L. D., 69.Nicholson, C. R., 213.Nicholson, J., 336.Nicholson, M., 96.Nicholson, R. S., 554.Nickel, B., 288.Nickels, W., 572.Nickolskii, A. B., 70.Nickon, A., 247, 282, 346,Nicolaides, E. D., 522.Nicolaus, R. A., 377.Niedenzu, K., 123,124, 125.Nieder -Vahrenholz , H .- G . ,Niehues, K.-J., 155.Nielsen, A. T., 385.Nielsen, B., 340.Nielsen, M. L., 139.Nielsen, N. A., 450.Nielsen, R. P., 137.Nielson, A., 109.Niemann, R. L., 546.Nigal, K. G., 537.Niggli, A., 575.Niitsuma, T., 384.Nikicorov, G. A., 330.Nikiforova, A. V., 305.Nikitin, E. E., 51, 52, 55.Nikolaeva-Fedorovich,Nillson, R., 462.Nilsson, B., 360, 609.Nilzeki, N., 578.Nirenberg, M., 456.Nishida, G., 541.Nishida, H., 108.Nishikawa, H., 360.Nishimura, H., 450.Nishimura, S., 101, 533.Nishimura, T., 449, 450.Niskanen, E., 547.Nist, B. J., 214.Nitsche, R., 575.Nitschke, I., 151.Nitta, I., 39, 40, 46, 608.Nitzsche, R., 88.Nitzschke, M., 307.Nitzschmann, R. E., 180.Nivard, R. J. F., 189.Nix, P.S., 111.Nixon, J. F., 137, 140.Nixon, L. A., 133.Noack, M., 180.Noble, F. W., 532.Noble, P., 322.358.155.B. V., 85INDEX OF AUTHORS’ NAMES 651Noel, M., 450.Noel, Y., 370.Noth, H., 118, 123, 125,Nogare, S. D., 533.Nogi, T., 331.Nolan, C., 493.Noland, W. E., 377.Noller, H., 255, 256.Noltes, J. G., 132, 189,Nomura, K., 400, 405.Nomura, T., 426.Norbury, A. H., 150.Xord, G., 127.Nordio, P., 46.Nordling, C., 547.Nordman, C. E., 127.Norell, J. R., 323.Norin, T., 242, 356, 364.Norman, B. J., 177, 204.Norman, N., 595.Norman, R.. 0. C., 28, 462.Normant, H., 307,310, 311.Normant, J., 310.Ilforris, T. H., 146.Norrish, H. H., 533.Norrish, R. G. W., 52, 53,Norman, B., 387.Northcote, D. H., 429.Norton, D.A., 611.Norton, F. J., 101, 105.Norton, K. B., 425.Norton, P. M., 483.Nosaka, S., 357.Notani, G. W., 508.Nouvel, G., 507.Novikov, G. I., 78.Novikov, S. S., 300.Novikova, N. V., 142.Novoselova, A. V., 117.Nomacki, W., 575, 602.Nowak, A. V., 541.Nowothy, H., 570.Nowotny, D., 448.Noyce, D. S., 250.Noyes, R. M., 246.Noyes, W. A., GO.Noyori, R., 245, 324.Nozaki, H., 245, 324.Nozaki, Y., 428.Nozoe, S., 358, 417.Nozoe, T., 357.Niirnberg, H. W., 92, 93.Nugent, C. A., 488.Nui, C. I., 509.Numata, A., 363.Nunn, E. K., 116.Nuss, J. W., 130.Nussbaum, A. L., 421, 452.Nussim, M., 301, 415.Nutt, R. F., 450.Nuttall, R. H., 162.Nuttall, R. N., 175.Nyberg, K., 333.126, 132, 141, 144.395.54, 98.Nyburg, S.C., 165, 586.Xyce, J. L., 253, 262.Nye, M. J., 348.Nyhan, W. L., 482.Nyholm, R. S., 73,128,148,175, 160, 181, 182, 183,190, 191.Wyitrai, J., 381.Nykerk, K. AX., 175.Nyquist, R. A., 210.Oae, S., 270, 286, 384,Oakes, E. M., 434.Oasterbaan, R. A., 516.Oates, J. A., 523.Obata, K., 387.Oberender, H., 148.Oberholzer, V. G., 478, 480.Obol’nikova, E. A., 305.Obradovic, V., 530.O’Brien, D. H., 287.O’Brien, E. J., 457.O’Brien, P. J., 432, 502.O’Brien, R. J., 191, 592.O’Brien, T. D., 173.Obrucheva, A. D., 88.Ochoa, S., 453, 456.Ockenfells, H., 426.Ockerman, P. A., 479.O’Colla, P. S., 443.O’Connell, E. J., 265.O’Connor, C., 298.O’Connor, D. E., 273.Oda, R., 213, 310, 324,Odell, A. L., 176.Odievre, M., 481.O’Donnell, T. A., 539.O’Donoghue, J.D., 132.Oehlschlager, A. C., 249.Oei, T. L., 479, 480.Oetting, F. L., 63.O’Ferrall, R. A. M., 297.Offenhartz, P. O’D., 161.Ofri, S., 525.Ogahara, I., 564.Ogata, M., 220.Ogata, Y., 286, 287.Ogawa, S., 29, 40.Ogibenina, T. G., 127.Ogilivie, J. W., 297.Ogilvie, R. E., 546.Oguri, K., 468.Ohara, M., 133.O’Hara, M., 212.O’Hara, R. K., 272, 337.O’Hare, P. A. G., 65, 79.Ohashi, M., 359, 396, 404,Ohata, K., 417.Ohloff, G., 349.Ohme, R., 372.Ohmori, H., 288.Ohnesorge, W. E., 549.Ohnishi, S. I., 39, 40, 46.386.346.406.Ohno, A., 270.Ohno, M., 302, 354, 369.Ohrt, J. M., 611.Ohta, A., 388.Ohta, M., 399.Oka, T., 213.Okada, M., 557.Okamoto, M., 302, 354.Okamoto, T., 363.Okano, M., 324.Okawttrs, R., 133, 212.Okaya, Y., 587, 607.Okazaki, R., 436.Okazaki, T., 436.Okhlobystin, 0.Yu., 127.Okhuma, K., 450.Oki, S., 529.Okomora, T., 483.Oku, A., 213, 346.Okuda, R., 320.Okuda, S., 401.Okuda, T., 430, 508.Olmmara, N., 287.Okumura, T., 428.Olah, G., 275, 276.Olah, G. A., 125, 224, 238,241, 286, 331.Olsh, G. H., 273.Olberg, R. C., 134.Oldfield, D., 376.Oldham, C., 183.Oldham, K. B., 80.Olive, J. F. P., 552.Oliver, J. P., 74, 127.Oliveto, E. P., 416, 419.Olivier, L., 404.Ollapally, A. P., 437.Olliff, R. W., 176.Ollis, W. D., 364, 391.Oloffson, G., 75.Olofson, R. A., 380, 382.Olsman, H., 314.Olson, A. C., 237.Olson, C., 562.Olson, D. H., 131, 132.Olson, E.J., 518.O’Malley, R. F., 136.Omang, S. H., 554.Omori, T., 529.Omura, T., 461.Onak, T., 119.Ondik, H. M., 578.O’Neill, I. K., 434.O’Keill, M. J., 560.Ong, E. B., 516.Ongley, P. A., 276.Onken, H., 578.Ono, H., 439.Onodera, K., 445.Onoprienko, V. V., 345.Onwood, D. P., 272.Onyszchuk, M., 75, 125,Ooi, S., 585.Ooms, H. A., 478.Oosterhoff, L. J., 241.131652 INDEX OF AUTHORS’ NAMESOpitz, G., 323.Orchin, M., 166, 184, 191Orgel, L. E., 34, 200.Orioli, P. L., 586, 588.Orito, Y., 108.Orme-Johnson, W., 465.Ormerod, M. G., 41.Ornstein, L., 519.Orrenius, S., 460, 461, 462.’ Orville-Thomas, W. J., 208.Orzalesi, H., 229.Orzech, C. E., 248.Orzech, C. E., jun., 206.Osaki, K., 265, 567, 589.Osborn, J. A., 177, 190.Osborne, A.G., 181.Osburg, C. A., 57.Oshe, A. I., 93.Osipov, A. I., 51.Oski, F. A., 477.Osman, F., 319.Osman, S. F., 300.Ossicini, L., 532.Ossip, P. S., 248.Osteryoung, R. A., 88.Ostmann, E.-A., 492.Ostyn, M., 102.Oswald, A. A., 263, 316.Oswald, H. R., 572.Otero-Vilardeb6, L. R., 501.Oth, J. F. M., 286,326,350,Otomasu, H., 220.Ott, W. L., 530.Otterbach, D. H., 436.Ottinger, C. L., 189.Ottrnann, G., 139.Ouannes, C., 421.Oullette, R. J., 214.Ourisson, G., 358, 366.Ovchinnikov, Yu. A., 345.Overbeek, J. T. G., 87.Overberger, C. G., 380.Overchuck, N. A., 273,286.Overeem, J. C., 344.Overend, J., 210, 212.Overend, W. G., 249, 289,290, 431, 438, 439.Overgaard-Hansen, K., 450.Overmans, J. D., 78.Overton, K.H., 361, 364,Owen, A. J., 119.Owen, E. E., 485.Owen, N, L., 207.Owyang, R., 234.Oge, H. A., 176.Oyster, T. J., 535.Ozaki, A., 105.Ozaki, T., 554, 555.Pacak, J., 429.Pace, N., 430.Pacesova, L., 147.Pachapurkar, R. V., 365.197.354, 380.365.Pachler, K., 613.Pachler, K. G. R., 211.Pacini, P. L., 286, 383.Paciorek, K. L., 138.Packer, J., 275, 331.Packer, K. J., 125, 136.Paddock, N. L., 138, 139.Padgett, C. D., 143.Padgett, W. &I., 270.Padilla, J., 369.Padina, D. K., 145.Padwa, A., 329, 372.Paetzold, P. I., 124, 125.Paetzold, R., 143.Page, B. C., 555.Page, I. H., 524.Page, T. F., jun., 653.Pahil, S. S., 74, 544.Pai, B. R., 403.Painter, T. J., 441.Pakhoruliov, N. I., 74.Pakrashi, S.C., 396.Pal, P. C., 447.Paladini, A. C., 524, 525.Palatnik, L. S., 100.Palattao, L. G., 483.Palen&, G. J., 585, 588,Pallini, U., 415.Pal’m, U. B., 89, 93.Palmer, M. H., 259.Palmer, P., 41.Palmer, R. A., 174.Pamfilov, A. V., 89, 03.Panar, M., 457.Panattoni, C., 165, 586.Pande, C. S., 182.Pande, K. C., 257.Pandey, R. C., 216, 361.Pandit, A. L., 345.Pandit, U. K., 220.Panetta, C. A., 373.Pankratov, A. V., 136.Pankstelis, J. V., 371.Panouse, J. J., 417.Pansaro, V. S., 316.Pant, L. M., 586, 594.Pantani, F., 563.Paoletti, P., 73, 74.Fapa, A. J., 380.Papee, H. M., 74.Papetti, S., 121, 122.Papke, K., 528.Paquette, L. A., 250, 373,Parcell, A., 295.Pardo, M.-P., 674.Pnrdue, H. L., 562.?arecles, R., 215.Parello, J., 206, 396.?asham, W.E., 392.Faris, B., 160.?aris, J. P., 539.?arish, R. C., 308.>ark, B., 74.’ark, J. D., 70.595.393.Park, J. H., 517, 518.Park, J. T., 505.Park, R. B., 453.P&rk&nyi, C., 280.Parke, D. V., 463.Parker, J. G., 51.Parker, J . R., 538.Parker, W., 354, 358, 602.Parker, W. C., 501.Parkin, J. E., 23.Parmenter, C. S., 60.Parks-Smith, D. G., 53.Parry, G. S., 127.Parry, G. V., 397.Parry, J. M., 85.Parr, R. G., 205.Parr, R. M., 558.Parry, R. W., 119.Parsa, B., 559.Parshall, G. W., 175.Parsons, C. G., 62.Parsons, R., 82, 83, 85, 91,Partch, R. E., 304.Parthasarathy, R., 100.Parthe, E., 570.Partington, M. W., 481.Parts, L., 122, 139.Partridge, S. M., 494.Pasqualucci, C.R., 250.Pass, G., 145.Passannante, A. J., 371.Past, V. E., 89, 93.Past, V. I., 88.Pasto, D. J., 258, 301.Pastor, T., 539, 540.Pasynkiewicz, S., 306, 311.Paszek, L. I?., 403.Paszyc, S., 97, 98.Patchornik, A., 495, 513,Patel, C. C., 153.Patel, D. J., 346.Patel, M. B., 405.Patel, M. S., 255.Paternotte, C., 603.Pathak, S. R., 232.Patil, F., 366.Patil, J. R., 429.Path, D. L., 429, 441.Paton, A. C., 385.Patrick, A. D., 481.Patrick, C. A. R., 333.Patrick, C. R., 64, 279.Patrick, J. B., 321.Patterson, E. L., 428.Patterson, J. M., 534.Patterson, W. R., 112.Pattison, V. A., 270.Patton, D. S., 290.Paul, A. P., 275.Paul, E. G., 206.Paul, I., 127.Paul, I. C., 358, 609.?ad, R., 298.>aul, R. C., 74, 75, 544.96.545INDEX OF AUTHORS’ NAMES 653Paulett, G., 142.Paulett, G.S., 211.Pauling, L., 203.Pauling, P., 164.Paulsen, H., 430, 436.Paulsen, P. J., 544.Puuly, J., 558.Pauson, P. L., 180, 187.Paustian, J. E., 122.Pavan, 31. V., 46.Pavlis, R. R., 262.Pavone, D., 71.Pawellek, D., 330.Pawley, G. S., 338, 353,601.Bayne, D. S., 137.Payne, R., 84.Peacock, R. D., 115, 146,161, 571.Peacock, T. E., 24.Peacor, D. R., 578.Peal, W. J., 255.Pearce, A. A., 301.Pearce, C. A., 139.Pearlmann, R., 519.Pearson, C. A., 548.Pearson, D. E., 386.Pearson, M. C., 261.Pearson, R. G., 163, 177,Peat, F. D., 168.Peat, G. B., 330.Pebler, A., 569.Pechacek, R. E., 93.Pechet, M. M., 421.Peck, P. F., 531, 559.Peck, R.E., 111.Pedain, J., 132.Pedersen, B., 174, 584.Pederson, C., 370, 432.Pedley, J. B., 70.Pedone, C., 594.Peeling, E. R. A., 101.Peets, E. A., 475.Pei, P. T., 561.Beine, H. G., 306.Pelah, Z., 368, 412.Pelizzino, F., 362.Pell, A. S., 62, 83.Pelletier, S. W., 367, 409.Pelter, &4., 304, 391.Peltzer, B., 268, 491, 498.Pemberton, D., 53.Penfolcl, 13. R., 159, 573,Peng, C. T., 557.Penneman, R. A., 149, 150.Pennington, F. C., 275.Psnrose, L. S., 481.Pentimalli, L., 384.Pepekin, V. I., 66.Peppard, D. F., 530.Pepper, D. C., 276.Pepper, J. M., 330.Percheron, F., 440.Percival, D. F., 553.Percival, E., 429, 443, 444.180.577.Perez-Garcia, J. A., 130.PBrez-Ossorio, R., 63.Perfilova, I. L., 68.Pergiel, F.Y., 68.Perham, R. N., 517.Perheentupa, J., 478.Peri, J. A., 99.Perkins, €I., 498.Perkins, M. J., 334, 389.Perlin, A. S., 432.Perlman, R. L., 504.Perloff, A., 579, 580.Perlow, G. J., 116.Perlow, $1. R,., 116.Perone, S. P., 535.Perrin, D. D., 370.Perron, R., 560.Perrotta, A. J., 578.Perry, D. D., 126.Perry, M. B., 430.Perry, R. H., 285.Perschel, J., 392.Person, H., 219.Pesaro, M., 375.Pesin, V. G., 382.Peterlik, M., 340.Peters, C. R., 579.Peters, J., 441, 534.Peters, J. H., 475.Petersen, C. S., 607.Petersen, R. C., 278.Petersen, R. J., 348.Petersen, S., 342.Peterson, J. O., 290.Peterson, L. K., 129, 140.Peterson, M. R., 501.Peterson, P. E., 267.Peterson, S. W., 272.Petragnani, N., 320.Petranelr, J., 281, 544.Petree, H.E., 246.Petroff, C. P., 557.Petrov, A. A., 132.Petrov, A. K., 336.Petrov, A. V., 529.Petrov, I. N., 97.Petrova, V. A., 158.Petrovich, J. P., 224.Petrow, IT., 415, 416, 418,Petschik, H., 140.Pettit, F. H., 465.Pettit, R., 185, 256.Pettitt, D. J., 372.Pews, R. G., 255.Pfab, W., 543.Pfann W. G., 531.Pfannemuller, B., 442.Pffeiderer, W., 449.Pfiffner, A., 343.Pfister, V., 494.Pforr, G., 548.Phaff, H. J., 440.Phelps, A. V., 58, 59.Phelps, F. P.. 431.Phillip, A., 424.419.Phillips, C., 119.Phillips, C. S. G., 119, 124,Phillips, D. A., 119.Phillips, D. C., 607.Phillips, D. M. P., 519.Phillips, G. O., 429, 432.Phillips, G. T., 380.Phillips, L. F., 54, 60.Phillips, M. J., 105.Phillips, 137.D., 44,162,200.Phillipson, J. J., 106, 108.Phillips, T. R., 533, 543.Philpott, G. R., 489.Piacenti, F., 219.Piatelli, M., 3‘77.Piasek, E. J., 300.Piccolini, R. J., 203.Pichler, H., 109.Pickard, J., 504.Pickering, W. F., 563.Pickert, P. E., 103, 112.Piechaczek, H., 144.Piekarski, L. J., 464.Piel, E. V., 534.Pielrneier, G., 492.Pieper, H., 412.Pierce, L., 219.Pierce, J. G., 493.Pierce, T. B., 531, 559.Piers, E., 284, 405.Piers, K., 408.Piersma, B. J., 96.Pierson, W. G., 398.Pietri, C. E., 548.Pietrogrande, A., 545.Pietsch, R., 530.Pigman, W., 431, 435, 496,Pigman, W. 289.Pik, C., 482.Pilcher, G., 62, 63, 78.Pilling, R. L., 120.Pils, I., 255.Pilz, H., 487.Pimentel, G. C., 21 1.Pincock, R.E., 310.Pinder, A. R., 396.Pine, L. A., 553.Pines, H., 230, 269, 330.Ping-Lu Chien, 328.Pinhey, J. R., 369.Pinhey, J. T., 328.Pino, P., 325.Pinto- Scognamiglio, W.,Piper, T. S., 160, 167, 17.1,Piret, P., 603.Piringer, O., 103.Pisa, Z., 520.Pischel, H., 448.Pislrala, A., 281, 389.Piskovitina, G. A., 256.Pitirimov, B. Z., 73.Pitchfork, E. D., 389.128.497.466.177654 INDEX OF AUTHORS’ NAMESPitombo, L. R. M., 529.Pittman, C. V., 240, 241.Pittman, T. A., 477.Pitts, J. N., 264.Pitts, R. F., 488.Pitzer, R. M., 205.Plackett, P., 441.Plane, R. A., 156, 273.Plank, W. J., 330.Plat, M., 357.Plate, A. F., 62.Plato, M., 31.Plaut, W., 452.Plazek, E., 384.Plenat, F., 347.Plesch, P. H., 249.Pleshakov, M.G., 320.Pleskov, Yu. V., 98.Plettinger, H. A., 579.Pleumeekers, A. J. G., 533.Plieninger, H., 305, 326,Plimbley, W. T., 87.Plotkin, G. R., 478.Plotnikova, G. I., 305.Pluchett, H., 417.Plugina, L. A., 321.Plummer, T. H., 493, 513.Plummer, W. J., 333.Plunket, A. O., 383.Pocker, Y., 244, 246.Podkokwa, J., 108.Podlovchenko, B. I., 88, 95,Po& A. J., 178, 181.Pohloudek-Fabini, R.,Pointer, D. J., 296.Poisson, J., 403.Poiu, P., 576.Pokornf, J., 309.Polak, R. J., 121.Polanyi, J. C., 54, 57.Poliakova, L. A., 559.Polkovnikov, B. D., 101,Pollak, A., 387.Pollak, 0. J., 519.Pollard, C. J., 453.Pollmann, W., 449.Pollock, E. N., 552.Polonsky, J., 364.Polyachenok, D. G., 78.Polyanovskaya, N. S., 84.Pomerantz, M., 267, 329,Ponomarev, V.V., 75.Pontius, R. B., 87.Poole, C. P., jun,, 126.Poole, H. G., 23.Poole, M. D., 218, 395.Pooley, D., 44, 200.Pope, A. E., 62, 66.Popisilova, D., 517.Pople, J. A., 196, 197, 201,349.96.528.299.349.202.Popova, 0. S., 93.Popp, F. D., 97.Poppe, H., 541.Popravko, S. A., 345.Porta, P., 593.Porte, A. L., 356.Porter, G., 328, 335.Porter, I. H., 475.Porter, Q. N., 378.Porter, R. F., 76, 125, 280.Porter, R. J., 478.Porter, R. R., 493.Portsmouth, D., 437.Pcsey, F. A., 97.Poska, F. L., 110.Post, B., 570, 583.Post, W. R., 541.Postnikov, L. M., 98.Potenza, J. A., 122, 580.Potier, P., 427.Potoski, J. R., 290.Potrafke, K. A., 543, 563.Potts, J. T., 512.Potts, W. J., 204..Poutsma, M. L., 261.Povarov, Yu. M., 83.Powell, A. R., 166.Powell, H., 412.Powell, H. M., 191, 593.Powell, J. W., 365.Powell, P., 124.Powles, J. G., 35, 207.Poynter, R. L., 122, 581.Prader, A., 477, 478.Pradhan, S. K., 365, 416.Prahlad, J. R., 216, 358.Prasad, D., 432.Prasch, A., 155, 160.Prat, H., 61.Pratt, E. F., 304.Pratt, L., 211.Preiss, H., 128.Prentice, H. G. 319.Preobrazhenskii, N. A., 320.Press, E. M., 493.Pressman, D., 517.Preston, E. A., 242.Preston, J., 459, 507.Pettre, M., 100.Pretzer, W., 338, 394.Preuss, H., 26.Prevodorou-Demas, C., 152.Psibil, R., 537, 551.Pzibyl, M., 543.Price, IV. C., 25.Prichard, F. E., 217.Priddle, S. H., 20.Pridgen, H. S., 341.Pridham, J. B., 440.Prigogine, I., 82.Pringsheim, P., 57.Prins, R., 200.Prisch, M.A., 62.Pritchard, H. O., 75.Frivalova, N. M., 72.Prokai, B., 123, 301.Prokhorova, N. I., 334.Prokofeva, N. I., 213.Proll, P. J., 168.Prosen, E. J., 68, 72.Proskow, S., 369.Prosser, F., 202.Prosser, T. J., 324.Prugh, J. D., 219.Pryles, C. V., 483.Przybylska, M., 409, 608.Pshenichnikov, A. G., 97.Pua, R., 62.Pudovik, A. N., 314.Putter, R., 322.Pugachev, A. T., 100.Pulley, A. O., 442.Pullman, B., 97, 280, 615.Pullman, B. J., 137.Pulvcr, S., 245.Pump, J., 129.Purdy, W. C., 531, 542.Purohit, D. N., 537.Purushothaman, K. K.,Pusat, N., 49.Pusztai, A., 497.Puterbaugh, W. H., 286.Putnam, F. W., 493.Putseiko, E. K., 98.Puttner, R., 324.Pyle, J.T., 529.Pyryalova, P. S., 303, 308.Pysh, E. S., 20.355.Quagliano, J. V., 175.Quaglino, J. V., 163.Quan, P. M., 398.Quartey, J. A. K., 359.Quazi, A. R., 187.Qudrat-I-Khuda, M., 303.Queck, I., 315.Quin, L. D., 398.Quinkert, G., 423.Quinlin, W. T., 338.Quinones, N. Q., 219.Quiocho, F. A., 513.Qureshi, M., 528.Qurreshi, I. H., 359.Raasch, M. S., 120.Rabenau, A., 151.Rabiger, D. J., 219.Rabinovich, D., 265, 567.Rabinovitz, M., 284,454.Rabinowitz, I. N., 601.Rabkin, M. T., 490.Rabo, J. A., 103, 112.Rachaman, E. S., 441.Rachlin, A. I., 438.Radda, G. K., 462.Radlick, P., 241.Rady, G., 540.Rae, A. D., 150, 588,Rlitz, R., 139.589INDEX OF AUTHORS’ NAMES 655Raffauf, R. F., 400, 404,Raftery, M. A., 515.Ragle, J.L., 218.Ragsdale, R. O., 134.Rahaman, M. S., 529.Rahn, R. O., 45.Rajagopal, N. S., 319.Rajbhandary, U., 497.Raley, J. H., 302.Rall, D. P., 472.Ralls, J. W., 284.R,alph, R. K., 452.Ramachandran, S., 330.Raman, S., 577.Ramalingam, K. V., 444.Ramirez, F., 313.Rammler, D. H., 451, 454.Ramsay, D. A., 8, 10, 20,Ramsay, 0. B., 255, 278,Ramaseshan, S., 579.Ramuz, H., 397.Rand, M. J., 553.Randle, P. J., 511.Randles, J. E. B., 80.Ranft, J., 211.Ranganathan, R., 358.Rank, J. S., 106.Rankl, F. I., 145.Rao, C. N. R., 212, 219.Rao, C. V. N., 442, 444.Rao, D. S., 541.Rao, G. G., 539.Rao, K. V., 94, 357.Rao, M. B., 541.Rao, P. K., 539.Rao, P. N., 310, 414.Rao, S. B., 539.Rao, S. K., 541.Rao, V. M., 205, 208.Rao., V.S. R., 442.Rao, Y. S., 322.Rapkin, E., 557.Raphael, R. A., 250, 314,Rapoport, H., 293, 300,Rappoport, Z., 260.Rashid, A., 528, 552.Rasmussen, H., 520.Rasmussen, S. E., 584.Rassat, A., 367.Ratcliffe, C. T., 145.R,athbun, J. C., 480.Ratner, M., 467.Ratner, R., 549.Raudenbusch, W., 249.Rauenbusch, E., 229.Rauh, E. G., 78.Rausch, D. A., 135.Rausch, M. D., 113, 188.Rautian, 8. G., 59.Ray, D. S., 453.Ray, S. C., 380.405.21.333.328, 394.374, 396, 400.Raynor, J. B., 183.Rapes, W. T., 23.Razuvaev, G. A., 188.Read, A. J., 275, 331.Read, A. W., 57.Rechnitz, G. A., 549.Recondo, E., 532.Records, R., 411.Redoch, A. H., 34.Reddy, A. K. N., 87.Reddy, G. S., 456.Reddy, 5. M., 613.Redfern, J.P., 147, 534,Redfield, A. G., 36.Reeben, V. A., 93.Reed, A. H., 542.Reed, I. A., 118.Reed, R. I., 358, 430.Reed, W. L., 322.Rees, A. H., 342.Rees, C. W., 278, 289, 290,336, 370, 374, 376, 382,431.Rees, R., 370.Rees, R. G., 122.Reese, C. B., 379, 447,Rees, E. T., 441.Reese, R. M., 207.Rege, V. P., 441.Reggiani, M., 430.Regoli, D., 524.Reich, E., 453, 454.Reiche, A., 141.Reichert, V. R., 461.Reichle, W. T., 135.Reichstein, T., 412, 426,Reid, A. F., 187.Reid, D. H., 382.Reid, J. A., 121.Reid, W. E., 87.Reif, L., 276.Reilley, C. N., 92, 98, 533,Reimlinger, H., 324, 380.Rein, R., 280.Reiner, J. R., 121.Reinheckel, H., 299.Reinheimer, J. D., 245.Reinisch, R. M., 144.Reinmuth, W. H., 30, 89,Reinstein, M., 309,314, 329.Reisner, S.H., 478.Reiss, W., 128.Reitzer, B. J., 111.Relles, H. M., 140, 324.Remanick, A., 225.Remizova, T. B., 307.Remmer, H., 461, 468.Remsen, N., 532.Renfrow, W. B., 324.Renk, E., 249.Renner, U., 404, 406, 608.560.452.428, 431.563.92.Renschel, K., 128.Rentea, C. N., 390.Rentzeperis, P. J., 578,580.Repogle, L. L., 338.Repplinger, J., 315.R6rat, B., 603.RBrat, C., 595, 603.Ressler, C., 298.Rest, C. E., 432.Rettig, T. A., 350.Rewch, W., 303, 416.Reutov, 0. A., 271.Reuwer, J. F., 276.Reynolds, B. E., 385.Reynolds, C. A., 541.Reynolds, J. J., 367, 397.Reynolds, L. T., 163.Reynolds, W. F., 210.Reynolds-Warnkoff, P.,Rhaese, H. J., 451.Rhein, R. A., 143.Rhoads, S.J., 282.Riad, Y., 249.Rias-Ur -Rahman, 24.Ribeiro, O., 400, 404.Ricci, E., 558.Ricci, F., 558.Rice, F. J., 220.Rice, J. M., 335, 387.Rice, L., 504.Rice, M. R., 234.Rice, R. G., 139.Rice, S. A., 19, 20, 26, 71,Rich, A., 452, 455, 457.Richards, F. M., 510, 512,Richards, G. F., 183.Richards, J. H., 258.Richards, R. E., 174, 206.Richards, R. W., 321.Richards, S., 174, 584.Richey, H. G., 228.Richey, H. G., jun., 348.Richey, J. M., 348.Richie, R. H., 490.Richmond, J. E., 500.Richter, E., 483.Richter, H. J., 281, 386,Richter, P., 449.Rickard, C. E. F., 152.Rickards, R. W., 374, 386.Rickards, T., 432.Rickborn, B., 271, 411.Ridd, J. H., 252, 275, 331.Riddiford, A. C., 90, 93.Ridgewell, B. J., 219, 274.Ridley, D., 168.Ridley, H.F., 376.Rieche, A., 128, 303.Rieder, W., 343.Riedl, F. J., 112.Rieger, P. H., 30.Riemann, J., 286.225.197.513.557656 INDEX OF AUTHORS’ NAMESRiemschneider, R., 442.Rienacker, G., 168.Riera, J., 336.Riess, W., 408, 465, 474.Riezebos, G., 304.Rigden, J. E., 205.Riggs, G. M., 438.Rightmire, R. A,, 96.Rigny, P., 211.Rijkens, R., 133.Riley, F. L., 275.Riley, R., 124.Rinde, E., 472.Rinehart, K. E., jun., 340.Riney, J. S., 87.Ring, M. A., 581.Ring, S. A., 148.Ringold, H. J., 288, 413,Ringshaw, D. J., 297.Rim, H. W., 125.Ripamonti, A., 51.Ris, H., 452.Risalti, A., 309.Risi, S., 532.Risingcr, G. E., 303.Ritchey, W. M., 135, 186.Ritchie, C. D., 271, 300.Ritchie, R . K., 16, 18.Ritter, A., 433, 449.Ritter, J.D. S., 297.Ritter, J. J., 125.Rittersbaeher, H., 145.Riveiro, C., 463.Rivers, P., 300.Rivers, S. L., 488.Riviere, H., 304.Rivoir, L., 57s.Roark, E., 434.Robas, V. I., 597.Robben, F., 52.Roberts, J. D., 206, 232,Roberts, 5. S., 358.Roberts, M. W., 106.Roberts, R. M., 249, 276Roberts, R. M. G., 271.Roberts, W. W., 59.Robertson, A. IT., 427.Robertson, G. B., 164.Robertson, J. H., 594, 612.Robertson, R. E., 199, 249.Robeson, C. D., 318.Robin, M. B., 161, 613.Robins, M. J., 450.Robins, R. K., 280, 447,448, 449, 450.Robinson, A. D., 530.Robinson, B., 378, 599.Robinson, B. H., 159.Robinson, B. P., 330.Robinson, C. H., 419,421.Robinson, E. A., 144, 240.Robinson, F.P., 283.Robinson, G., 185, 567.Robinson, G. B., 499, 502.416.346.Robinson, G. W., 198.Robinson, M. A., 165, 173.Robinson, M. J., 481.Robinson, P. J., 255.Robinson, P. S., 149.Robinson, S. D., 190.Robinson, W. R., 159.Robinson, W. T., 159, 573.Robison, M. M., 398.Robson, H. E., 76.Robson, M., 297.Robson, R., 265.Rochester, C. H., 277, 278,Rochow, E. G., 124, 130.Rocktkschel, C., 128, 136.Roddy, 3. W., 153.Roden, L., 494, 495.Rodges, R., 377.Rodig, 0. R., 384.Rodin, J. O., 266.Roebuck, P. J., 131.Rochling, H., 383.Rohm, E., 449.Rohrborn, H.-J., 169.Ronsch, H., 408.Roesky, H. W., 136.Roesler, J. F., 533.Rost, E., 576.Rogan, 5. B., 232.Rogers, D., 359, 402, 608.Rogers, H. H., 136.Rogers, €1. J., 507.Rogers, L.A., 466, 467.Rogers, L. B., 533.Rogers, L. C., 273.Rogers, M. T., 37, 210, 288.Rogers, N. A. J., 288.Rognoni, F., 466.Rohmer, H., 69.Xohmer, R., 578.3oholt, 0. A., 517.Xohrer, J. C., 111.Xoitman, E., 483.3ojek, X., 108.Xolrach, J., 309.tokkones, T., 484.tokstad, 0. A., 273.2ollins, E. L., 434.tolston, 2. H., 310.tomagnoli, R. J., 533.tornazuk, M., 357, 369.torners, C., 598, 601, 603.tomersberger, J. A., 265.tomo, J., 379.tonaldson, J. W., 377.toncucci, L., 133.toobol, N. R., 240.toof, R. B., jun., 567, 569,tooney, J. J., 105, 111.tooney, R. C., 554.tooney, T. B., 533.toper, W. R., 142.toquitte, B. C., 268.losch, H., 575.332.570, 571.Roscoe, D. H., 447.Rose, G. A., 485.Roseman, S., 432, 502.Rosen, B., 12, 17.Rosen, F., 467.Rosen, W.E., 256.Rosenberg, L., 485.Rosenberger, M., 272, 337,Rosenblum, C., 556.Rosenblum, M., 340.Rosenburg, D. W., 420.Rosenheim, O., 419.Rosenkranz, J. E., 333.RosenthaI, D., 421.Rosenthal, I. M., 478.Rosenthal, O., 460.Rosenthal, W. A,, 430.Rosentsveig, S. A., 89.Rosich, R. S., 361, 363.Ross, A., 133.Ross, B. L., 186.Ross, H. H., 557.Ross, I. G., 177, 197.Ross, J. A., 417.Ross, J. M., 382.Ross, J. W., 92, 554.Ross, S. D., 278.Ross, W. J., 558.Rossetti, G, P., 153.Rossi, S., 388.Rossier, A,, 481.Rossi-Fanelli, A., 443.Rossignol, B., 496.Rossiter, R. J., 480.Rossmanith, K., 118.Rost, E., 153.Rotemund, G. W., 122.Roth, H., 477.Roth, H. D., 338, 354.Roth, W., 435.Roth, W.R., 241, 268, 285,Rothenbury, R. A., 142.Rothfus, J. A., 492.Rothrock, H. S., 323.Rothstein, E., 275.RouGche, A., 541.Rouiller, C., 501.Rout, M. K., 219.Rovery, M., 515.Rowe, G. A., 160.Rowe, 3. J. M., 442.Rowell, R. M., 437.Rowland, A. T., 418.Rowland, L. P., 480.Rowland, R. L., 96.Rowlands, J. R., 37, 38, 40,Roy, C. C., 486.Etoy, N. K., 319.30yal1, D. J., 245, 392.Ftoyen, P., 128.Royen, R., 136.Xoyer, R., 219.3ozek, A. L., 210.405.327, 351, 352.199IXDEX OF AUTHORS’ NAMES 657Rozental, K. I., 94.Rozhkov, I. N., 310.Rubin, A., 466, 467.Rubin, M. B., 218, 422.Rubin, M. R., 343.Rubstov, M. V., 305.Rudinger, J., 519, 520.Rudolph, R. W., 119.Rudorff, W., 571.Rudowski, A., 432.Rudzitis, E., 68.Ruedenberg, K., 205.Ruetschi, P., 94.Rufer, C., 416.Ruff., J.K., 136, 142, 145.Ruggles, A. C., 420.Ruhl, H. D., 552.Ruidisch, I., 131.Ruland, W., 351.Rule, L., 134.Rummens, F. H. A., 255.Runcone, A., 511.Rund, J. V., 163, 273.Rundle, R. E., 131, 132,142, 573, 588, 594, 599.Rupe, B. D., 467.RUSOV, M. T., 110.Russ, C. R,, 124.Russel, C. R., 432.Russell, D. W., 491.Russell, G. A,, 31, 215, 260,Russell, R. A., 34.Russell, R. K., 17.Russell, R. L., 276, 331.Rustad, N. E., 281, 386.Ruth, J. M., 321.Rutledge, P. S., 363.RiiiiEka, J., 529, 556, 557.Ryabov, A. N., 70.Ryan, D. E., 542, 563.Ryan, J. L., 150.Ryan, J. W., 259.Ryan, K. J., 437.Ryan, M. T., 208.Ryan, P. W., 302.Ryan, R., 126.Ryba, O., 544.Ryce, J.M., 447.Rychcik, W., 536.Rydon, H. W., 495.Ryhage, R., 321, 533.Rylander, P. N., 108.Ryle, A. P., 510.Ryschkewitsch, G. E., 119.Ityvarden, I,., 318.SaaEeld, F. E., 69.SaaEeld, H., 576.Sabata, B. K., 219.Sabet, C. R., 311.Sabo, E. F., 419,421.Sacco, A., 190.Sacconi, L., 73, 165, 167,Sacher, E., 297.413.586.Sachyan, G. A., 45.Sackmann, H., 571.Sadagopan, V., 570.Sadana, Y. N., 157.Sadeh, T., 495.Saeed, M. A., 413.SSinger, IT., 451.Safe, S., 399.Sager, R., 452.Saha, J. G., 384.Sahoo, B., 149.Sainsbury, M., 391.Saito, A., 303.Saito, K., 560.Sait6, M., 304.Saito, S., 410.Saito, T., 93.Saito, Y., 593.Sajgo, M., 518.Sakagami, Y., 450.Sakai, H., 450.Sakai, S.I., 404.Sakamoto, K., 286.Sakamoto, Y., 461.Salahuddin, M., 391.Salaun, J., 348.Salem, L., 196.Salger, F., 543.Sali6, G., 91.Saliman, P. M., 544.Salinger, R. M., 325.Sallach, R. A., 148.Salmon, J. E., 147.Salomon, M., 94.Salter, A. J., 58.Salthouse, J. A., 147.Salton, M., 498.Salton, M. R. J., 491.Salvadori, G., 290.Samejima, T., 458.Sammes, P. G., 421.Sammy, G., 280.Samokhvalov, G. I., 305.Samols, E., 478.Samplavskaya, K. K., 71.Samson, C., 576.Samuelson, O., 430, 533.Sanchez, M. G., 139.Sanchez Paradera, I., 319.Sanchez Paradera, J., 319.Sand, T., 145.Sandall, J. P. B., 220.Sandel, V. R., 238.Sander, C., 458.Sanders, F. K., 453.Sanders, J. V., 99, 100.Sanderson, A., 498.Sandhu, S.S., 180, 181,Sandorfy, C., 197, 203.Sandoval, A., 512.Sands, D. E., 580.Sandstrom, W., 287.Sanfeld, A., 82.Sanger, F., 510, 516.Sangiust, V., 555.182.Sangster, I., 432.Sanno, Y., 451.Sano, M., 448.Sano, T., 366, 367.Santavy, F., 396.Santhanakrishnan, T. S.,Santhanam, K. S. V., 556.Santoro, R. P., 576.Santos, P. L., 562.Santry, D. P., 196, 202.Sanzharovskii, A. T., 93.Sapp, P., 552.Sappok, R., 128.Sarabhai, A. G., 455.Sarbhai, K. P., 280.Sarcione, E. J., 464, 500.Sarel, S., 371.Sargent, F. P., 34.Sargent, R. N., 531.Sarry, B., 189.Sarycheva, I. K., 320.Sasada, T., 598.Sasakawa, S., 519.Sasaki, K., 344.Sasaki, Y., 410.Sasame, H. A., 466.Sass, R. L., 241, 327, 672,Sasse, W. H. F., 531.Sassoulas, R., 100.Sastry, K.V. L. N., 205.Sasvari, K., 575.Satake, K., 519.Satapathy, K. C., 149.Satarina, G. I., 550.Satchell, D. P. N., 168.Sato, K., 450.Sato, R., 461, 465.Sato, T., 426, 439, 449, 529.Sato, Y., 428.Sa,toh, C., 435.Satoh, D., 356, 428.Satoh, K., 477.Sattar, A., 288.Satyanarayana, S. R., 144.Sauer, J., 264.Sauer, J. C., 120.Sauers, C., 234.Sauers, R. R., 228, 257.Saunders, F. C., 334.Saunders, M., 224.Saunders, R. If., 434.Saunders, W. H., 253, 254.Sauvage, J. F., 107.Savage, B., 527.Savage, D. S., 345.Savchik, D. V., 87.Savina, L. A., 301.Savitri, T. S., 403.Savitsky, G. B., 206, 210.Savkina, I. G., 98.Sawicki, E., 530.Sawinski, J., 307.Sawistoweka, M. H., 269.Sawyer, B. C., 470.358.596658 INDEX OF AUTHORS’ NAMESSawyer, D.T., 95.Sawyer, W. M., 546.Saxby, J. D., 220.Sayigh, A. A. R., 322, 323.Sazhina, V. I., 127.Sazonova, V. A., 340.Sbarbati, N. E., 278.Sbrana, G., 219.Scanley, C. S., 135.Schaap, W. B., 554.Schachar, M. M., 549.Schachter, H., 517.Schach von Wittenau, M.,Schack, C. T., 124.Schaefer, F. C., 373.Schiifer, H., 69, 154, 155,Schaefer, H., 77.Schiifer, L., 187.Schaefer, M., 115.Schaefer, T., 201, 202, 208,Schiifer, W., 370, 378.Schaeffer, 13. B., 122.Schaeffer, It., 119, 120,124.Schafer, I. A., 483.Schafer, M. E., 336.Schaffer, H. M., 611.Schaffer, N. K., 516.Schaffer, R., 438.Schaffner, K., 249,422,423.Schaller, H., 451, 452.Schally, A. V., 522.Schaltegger, H., 337.Schank, K., 355.Schappell, F., 230.Schaschel, E., 124.Schatz, G., 453.Schemer, L.D., 59.Scheer, J. C., 255.Scheffold, R., 375.Schegoleva, T. A,, 301.Scheidl, F., 543.Scheiner, D., 549.Scheinmann, F., 283.Scheit, K. H., 451, 452.Schellenberg, K. A., 301.Schemyakin, M. M., 305.Schenk, P. W., 127, 140,Schepman, A. M., 517.Scheppele, S. E., 280.Scherer, 0. J., 141.Scheringer, C., 597.Scheuer, P. J., 344.Scheurbrandt, G., 452.Scheutzow, D., 338.Schick, H., 126.Schick, R., 132.Schierling, H. E., 559.Schiess, P. W., 285.Schiewe, G., 535.Schiff, H. I., 54.Schiff, J. A., 453.Schiffman, G., 497.345.157, 190.210, 346.144.Schildknecht, H., 345.Schill, G., 320, 355.Schiller, E. O., 530.Schiller, S., 504.Schilt, A.A., 536, 541.Schindel, H., 167.Schindler, F., 126, 130.Schliifer, H. L., 151.Schlatzer, R. K., 384.Schlegel, R., 124.Schlesinger, S. I., 107, 299.Schlessinger, R. H., 380,387, 400.Schleyer, P. von R., 210,216, 224, 227, 238, 286,351, 353.Schlogl, K., 340.Schlosser, M., 117, 253, 306,Schlotter, H.-A., 144.Schlunegger, H. U., 337.Schlyter, K., 72.Schmahl, N. G., 74.Schmeising, H. M., 78.Schmeisser, M., 130, 146.Schmerling, L., 329.Schmid, G., 89.Schmid, G. M., 87.Schmid, H., 111, 381, 402,Schmid, K., 465, 474, 491,Schmid, K. H., 129.Schmidbaur, H., 126, 127,Schmidpeter, A., 136, 139.Schmidt, A., 142.Schmidt, E., 370, 387.Schmidt, G. M. J., 265, 567,Schmidt, H., 81.Schmidt, H. W.H., 430.Schmidt, J. F., 141.Schmidt, M., 125, 131, 133,134, 141, 142, 143, 144,145, 146.311, 325.405, 578.492, 494, 502.128, 130.598.Schmidt, T., 343.Schmidt, U., 315.Schmidtke, H. H., 26.Schmieman, J. H., 540.Schmitt, J., 417.Schmitz, E., 256, 303, 372.Schmitz-Dumont, O., 127.Schmulbach, C. D., 147.Schmutz, H., 148.Schmutzier, R., 586.Schmutzler, R., 136, 138.Schnabel, E., 508, 509.Schneer-Erdey, A., 531.Schneider, B., 132.Schneider, D. F., 305.Schneider, G., 245, 451.Schneider, H., 118, 140.Schneider, H. J., 232.Schneider, K., 322.Schneider, P., 392.Schneider, W. G., 201.Schneider -Bernlohr, H.,Schneidman, K., 469.Schnepp, O., 60.Schnering, H. G., 575.Schnitt, G., 305.Schniirer, L.-B., 484.Schoder, C.E., 547.Schoellmann, G., 515, 516.Schoen, L. J., 19.Schoenborn, B. P., 609.Schoniger, W., 543.Schonowsky, H., 313.Schoepf, E., 475.Schoessler, M. A., 520.Schoffa, G., 38.Schofield, K., 274.Scholer, F., 371.Scholten, J. J. F., 100, 103,Scholz, C., 421.Scholz, H., 154, 155.Schomaker, V., 112, 184,Schotland, D. L., 480.Schriigle, W., 123.Schramm, C. H., 371.Schramm, G., 449, 453.Schrauzer, G. N., 172, 187.Schreiber, K., 408.Schreiber, P., 305.Schreiner, G., 129.Schrieber, K., 412.Schriempf, J. T., 176.Schriesheim, A., 255, 273,Schroder, E., 522.Schroder, G., 286, 304, 354,Schroeder, H., 121, 122.Schroeder, W. A., 519.Schrotter, H. W., 122.Schroth, W., 370, 392.Schubart, R., 394.Schubert, M., 494.Schubert, W.M., 258.Schuchardt, H., 94.Schudel, P., 318.Schiilke, U., 139.Schueller, K., 264.Schuetz, R. D., 108.Schug, J. C., 46, 47, 198.Schugar, H. J., 266.Schuit, G. C. A., 73.Schuldiner, S., 87, 88, 89.Schuler, R. H., 27, 46.Schulte-Elte, K. H., 349.Schulte-Frohlinde, D., 341.Schultz, B., 317.Schultz, H. P., 97.Schultz, J. F., 109.Schultz, M., 432.Schultz, P. J., 214.Schultz, R. G., 185.Schultze, D., 102.387.111.599.329.356INDEX OF AUTHORS’ NAMES 659Schultze, H. E., 491, 498.Schulz, H., 305.Schulz, M., 303.Schulz, W. W., 531.Schulze, J., 275.Schulzkiesow, H., 330.Schmacher, E., 115, 419.Schumann, D., 402, 405.Schumann, H., 132, 133,134, 142, 143, 144, 146.Schumb, W. C., 136.Schuster, D.I., 356.Schuster-Woldan, H., 182.Schwab, G., 544.Schwab, G.-M., 99,102,111.Schwab, P. A., 258, 372.Schwabe, K., 87.Schwabe, P., 134.Schwager, I., 270.Schwarberg, J. E., 534.Schwarcz, A., 259.Schwartz, E., 83.Schwartz, I. L., 520.Schwartz, N., 121.Schwartz, N. N., 122.Schwartz, R. N., 50.Schwarz, I. L., 520.Schwarz, J. C. P., 432.Schwarz, J. S. P., 391.Schwarz, V., 428, 476, 478.Schwarz, W., 238, 249.Schwarzhans, K.-E., 134.Schwarzmann, S., 573.Schwebke, G. L., 128.Schweet, R., 456.Schweiger, H. G., 456.Schweiger, M., 454.Schweiss, H., 97.Schweitzer, G. K., 529.Schweizer, E. E., 306, 374.Schweizer, M. P., 389, 456.Schweizer, P., 125.Schwendeman, R. H., 205.Schwenke, W., 87.Schwochau, K., 159.Schwochau, M., 315.Sciaky, R., 415.Scoggins, M.W., 544.Scoggins, R. B., 488.Scognamiglo, W., 466.Scollick, N. M., 275.Scopes, P. M., 458.Scott, A. I., 362, 363, 407,Scott, D. W., 63.Scott, F. L., 245, 251.Scott, J. E., 435.Scott, P. M., 341, 343.Scott, R. P. W., 533.Scott, W. T., 250.Scowen, E. F., 485, 489.Scriver, C. R., 483, 486.Sealy, A. J., 319.Searcy, A. W., 78.Searcy, I. W., 119.Searle, R., 326, 349.412.Searle, F., 430.Secci, M., 305.Sederholm, C. H., 209.Sedlak, J., 486.Seegmiller, J. E., 481, 488,Seel, F., 145, 538.Seelert, K., 310.Seelig, H. S., 103.Segal, G. &I., 412.Segal, H. L., 517.Segal, S., 477, 485.Segre, A., 215.Seidel, B., 264.Seidel, G., 468.Scidel, W., 135, 138.Seidl, G., 229.Seidl, H., 386.Seip, B., 130.Seip, R., 583.Sekeris, C. E., 470.Selby, B.D., 538, 544.Selig, H., 115, 125.Selivanova, N. M., 71.Selk, K., 153.Sellers, P., 64.Sellers, P. W., 66.Selva, A., 415.Selwitz, C. M., 306.Selwood, P. W., 99, 104.Seltzer, S., 266.Semenenko, K. N., 117.Semenov, I. N., 78.Semin, G. K., 597.Semke, L. K., 289, 439.Semlyen, J. A., 124.Senciall, I. R., 220.Senders, J. R., 326, 350.Senior, J. B., 147.Senise, P., 529.Senkowski, B. Z., 555.Senn, W. L., jun., 553.Seno, H., 547.Sensi, P., 428.Serfontain, W. J., 434.Sergeer, V. A., 382.Serjeant, E. P., 390.Serratosa, F., 316.Serre, J., 115.Serrone, D. M., 468.Serval, P., 289.Servis, K. L., 232.Seshadri, H. S., 499.Sethi, R.S., 554.Setlow, R. B., 446, 447.Settle, F. A., 116.Sevastianov, E. S., 84, 87.Severnyi, V. V., 130.Sewell, J. R., 547.Seyberlich, A., 315.Seyferth, D., 128, 271, 311,Se Yui-Yuan’, 345.Shaeffer, J., 456.Shafer, J. A., 293.Shaffer, E. W., 556.489.325.Shafran, R. N., 108.Shah, V. R., 365.Shahine, S. A. F., 528.Shain, I., 554.Shaker, M., 535.Shalek, P. D., 148.Shalitin, Y., 293.Shamir, J., 125.Shamma, M., 396, 402, 404.Shand, A. J., 343.Shang, C. T., 544.Shani, A., 338, 394.Shannon, J. S., 106, 377,Shapatina, E. N., 110.Shapiro, D., 441, 487.Shapiro, D. H., 412.Shapiro, E. L., 416.Shapiro, I., 525.Shapiro, J. S., 256.Shapiro, R., 389, 4.51.Shapiro, R. H., 412.Shapkin, P. S., 158.Sharan, B., 578.Sharifov, K.A,, 77.Sharma, B. D., 605, 612.Sharma, T., 563.Sharman, C. S., 196.Sharon, N., 434, 493, 498.Sharp, D. W. A., 138, 162,Shasha, B., 429, 442.Shasha, B. S., 432.Shashkova, E. M., 125, 301.Shashoua, V. E., 205.Shaulov, Yu. Kh., 66.Shaw, B. L., 165, 181, 185,Shaw, D. C., 516.Shaw, E., 447, 515, 516.Shaw, G., 389.Shaw, N., 497.Shaw, R. A., 124, 139.Shchegoleva, T. A., 125.Shcherbakova, Z. V., 89.Shchukarev, S. A., 68, 71,Sheehan, J. C., 297, 371,Sheehan, L., 481.Sheft, I., 115.Shefter, E., 599, 607.Sheldon, J. C., 192.Shelton, R. A. J., 147.Sheludyakov, V. D., 125.Shemschushima, E. A., 81.Shemyakin, M. M., 320,345.Shen, S., 539.Shen’ Khuai-Yui, 345.Shephard, F. E., 111.Shepherd, R.G., 387.Sheppard, N., 207,215,343.Sheppard, R. C., 459, 507.Sheppard, W. A., 323.Shergalis, W., 290.Sheridan, J., 209, 210.388, 389.175.190.73, 78.522660 INSherma, J., 532.Sherman, E., 552.Sherwin, K. A., 72.Shetlar, M. R., 499.Shevchuk, M. I., 305.Shevdunko, I. B., 41.Shibata, K., 426.Shibata, S., 127, 356, 592.Shields, L., 40.Shiengthong, D., 276.Shif, I., 434.Shigematsu, T., 529.Shigeta, Y., 585.Shim, K. S., 350.Shimanouchi, T., 207, 214.Shimaoka, N., 450.Shimidate, T., 449.Shimizu, B., 449.Shimizu, F., 502.Shimizu, Y., 286, 330.Shimojima, H., 535.Shimura, K., 482.Shindo, M., 133.Shine, H. J., 31, 281.Shine, R. J., 402.Shiner, V. J., 246, 247, 254.Shingleton, D. A., 335.Shingu, H., 203.Shipp, W., 453.Shiro, M., 410, 608.Shlyapintokh, V.Ya., 98.Shlygin, A. I., 96.Shmyera, G. O., 66.Shoeb, 2. E., 319.Sholiton, L. J., 470.Shone, R. L., 280.Shono, T., 213, 346.Shoolery, J. N., 214.Shoop, E. C., 405.Shooter, D., 104.Shoppee, C. W., 263, 427.Shore, P. A., 462.Shore, S. G., 118, 125.Shorland, F. B., 319.Short, E. L., 156.Short, G. D., 539.Shorter, J., 246, 297.Shortland, F. E., 229.Shostakovskii, M. F., 305,Shostakovskii, S. M., 310.Showalter, M., 229.Shreeve, J. M., 145.Shriver, D. F., 119, 127.Shteingarts, V. C., 333.Shull, H., 196.Shulman, R. G., 45.Shultice, R. W., 467.Shumilova, N. A., 94.Shumway, D. K., 301.Shupack, S. I., 166, 171,Shuster, L., 475.Shutov, Yu. M., 78.Shveikin, G.P., 66.Shvetsov, N. I., 139.310.172, 184.EX OF AUTHORS’ NAMESShvo, Y., 425.Sicher, J., 259, 303, 411.Sickfeld, J., 442.Sidbury, J. B., 479.Sidisunthorn, P., 342.Sidler, J. D., 270.Siebert, H., 535.Siebert, J. M., 552.Siebert, W., 125.Sieg, R. I?., 103.Siegbahn, K., 547.Siegel, S., 60, 107, 108, 150,Sieger, G. IT., 345.Siegert, M., 468.Siegmann, R. H., 311.Sieker, L. C., 517.Siekevitz, P., 500.Sigel, C . W., 357.Sigel, H., 172.Sigg, H. P., 360.Sih, C. J., 428.Sih, N. C., 250, 333.Sikes, W. L., 555.Silbert, J., 504.Silbert, L. S., 63.Sill&, L. G., 72.Silvander, B. G., 441.Silver, H. G., 205.Silver, L., 520.Silverman, G., 394.Silverman, H. P., 97.Silverman, J., 606.Silverman, M.S., 142.Silvers, S., 604.Silverstein, R. M., 305.Silverstone, H. J., 200.Silverton, J. V., 174, 584.Sim, G. A., 267, 335, 354,358, 361, 362, 363, 364,394, 602, 609, 610.Simkin, J. L., 493,499,500.Simmons, H. E., 346, 373.Simmons, R. F., 255.Simon, E., 328.Simon, G., 145.Simon, H., 253, 254.Simon, P., 414, 420.Simon, R. I<., 562.Simonetta, M., 195, 256.Simonis, A. >I., 460.Simpson, C. C., 128.Simpson, D., 275.Simpson, P. G., 580, 581.Simpson, IV. B., 131, 132,Sims, P., 462, 471.Sinfelt, J. H., 106, 110, 111.Singh, A. K., 582.Singh, A. N., 208.Singh, J., 74, 75.Singh, K. P., 301.Singh, P. P., 134.Singli, R. P., 540.Singu, K., 317.Sinke, G. C., 63.573.170.Sinn, R., 108.Sinsheher, R. L., 453.Sinyakova, S.I., 81.&ode, R., 97.Sipog, F., 411.Sipos, L., 562.Sirtl, E., 128.Sisido, K., 133, 303, 324.Sisler, H. H., 119, 126, 137.Sisti, A. J., 245, 307.Sitdykova, N. S., 117.Sittig, E., 52.Sixel, B., 483.Sisma, I?. L. J., 211, 25.5.Sjoberg, B., 379.Sjoerdsma, A., 489, 523.Sjostrand, B., 558.Sjzuki, M., 204.Skalrun, E. G., 93.Skattebd, L., 324.Skell, P. S., 43, 129, 254,262, 263, 317, 324, 348.Skelton, G. S., 382.Skinner, E. R., 499.Skinner, H. A,, 61, 62, 66,Sklarz, B., 425.Skom, J. H., 511.Skuratov, A. V., 78.Skuratov, S. M., 62, 64, 66,Sladky, F. 146.Slaidin, G. Ya., 94.Slater, R. C. L. M., 574.Slater, T. F., 470.Slaugh, L. H., 302.Slaughter, M., 570.SlavBk, J., 396.Slawksy, Z. I., 50.Sleeman, D.H., 24.Slessor, K. N., 432, 440.Slichter, C. P., 27.Sloan, A. D. B., 147.Sloan, M. F., 324.Sloane, N. H., 464.Slobodin, Y. M., 316.Slomp, G., 450, 553.Sloth, E. N., 116.Slough, W., 41.Slovtik, Z., 543.Slovokhotova, T. A., 110,Slusarchyk, W. A., 396.Sly, W. G., 611.Smales, A. A., 558.Small, A,, 329, 349.Small, G. J., 591.Small, R. J., 31.Small, R. W. H., 161, 571,Smalley, R. K., 309.Smeby, R. R., 524.Smellie, J. M., 489.Smellie, R. M. S., 453.Smick, R. L., 324.Smidsrod, O., 444.78, 132.72.111.579, 593INDEX OF AUTHORS’ NAMESSmillie, L. B., 517.Smirnova, E. K., 73.Smirnova, M. N., 548.Smirnov-Zamkov, J. V.,Smith, A. J., 255.Smith, B. C., 124, 139, 149.Smith, B. R., 233.Smith, B.V., 297.Smith, C. L., 128.Smith, C. R., 319.Smith, C. R., jun., 319.Smith, D., 76.Smith, D. C., 125.Smith, D. &I., 280.Smith, E., 402.Smith, E. L., 492, 493, 507,Smith, F., 439.Smith, G. F., 544.Smith, G. G., 255, 273.Smith, G. H., 510.Smith, G. P., 167.Smith, G. S., 576.Smith, G. V., 106, 107.Smith, G. W., 576, 595.Smith, H. A., 109.Smith, H. F., 122.Smith, H. J., 297.Smith, I. C. P., 29.Smith, I. W. M., 53.Smith, J. M., 104.Smith, J. N., 471.Smith, J. P., 167.Smith, J. T., 472.Smith, J. V., 578.Smith, E. A., 351.Smith, L. F., 510.Smith, L. H., 488, 490.Smith, M., 379.Smith, M. B., 290, 324.Smith, &l. C., 374.Smith, M. L., 254.Smith, N. K., 63.Smith, P., 578.Smith, P. B., 249.Smith, P.J., 216, 252.Smith, R. A., 256, 453.Smith, R. D., 346.Smith, S., 242, 243.Smith, S. G., 224, 290.Smith, S. J., 360, 400.Smith, T. D., 127.Smith, W. B., 97, 229.Smith, W. T., jun., 534.Smithen, C. E., 370, 374,Smith-Sonneborn, J., 453.Smoes, S., 78.Smoler, I., 93.Smolinsky, G., 44, 45, 200.Smolkova, E., 564.Smrekar, O., 155.Smrt, J., 451, 452.Smyth, D. G., 611,513,516,256.519.376.565.Snatzke, G., 366, 407, 411,412, 418, 426.Snedden, W., 430.Sneeden, R. P. A., 188.Sneen, R. A., 233, 311,421.Snelders, H. A. M., 535.Snell, R. L., 281.Sniegoski, L. T., 289, 290.Snodgrass, G. J. A., 478.Snoeck, J., 486.Snow, 31. R., 166, 586.Snyder, C. H., 306.Snyder, E. I., 216, 351.Snyder, L. C., 45, 200.Snyderman, S.E., 483.Sobell, H. M., 457, 605,Sobelman, I. I., 59.Sober, E. K., 481.Sobol, V. V., 94.Soderberg, R. H., 162.Soedomo, G., 442.Sogani, N. C., 537.Sohar, P., 381.Sokal, J. E., 500.Sokalski, Z . , 108.Sokolov, N. D., 26.Sokolovsky, M., 495, 513.Sokolow-ski, J., 436.Solderberg, R. H., 585.Sole, M. J., 135.Sollich, W. A., 104.Solodovnik, V. D., 320.Soloman, P. W., 533.Solomon, I. J., 143.Solomon, I. T., 119.Solomon, W. C., 264.Solon, E., 90.Solymosi, F., 102.Soman, R., 361.Somiya, T., 564.Son, C. D., 484.Ssndergaard, G., 478.Sondheimer, F., 218, 276,301, 338, 339, 355, 394,415, 424, 425.Sonnenbichler, J., 454.Sonnet, P. E., 257.Sonntag, F. I., 265, 567.sorm, F., 281, 321, 357,359, 360, 413, 426, 427,451, 507, 517.Sorokin, V.P., 118.Sosnina, I. E., 62.Soszynska, E., 306.Soto, A. R., 306.Soundararajan, S., 168,212,218, 220.South, A., 477.South, D. S., 282.Sovers, O., 56.Sowa, W., 443.Soyster, H. E., 404.Spaner, S., 430.Sparatore, F., 319.Spark, A. A., 318.600.661Sparks, R., 607.Spassov, S., 207.Spauszus, S., 557.Speakman, J. C., 612.Specer, H., 399.Specht, H., 540.Speckamp, W. N., 220.Specker, H., 535.Speier, J. L., 259.Spenadel, L., 103.Spencer, E. Y., 369.Spencer, J. F., 319.Spencer, J. F. T., 440.Spenser, I. D., 370, 397.Speros, D. M., 72.Speziale, A. J., 290.Spiegelberg, H., 438.Spiegelman, S., 453.Spielman, J. R., 119.Spillman, J. A., 136.Spinar, L. H., 581.Spiro, M.J., 493, 501.Spiro, R. G., 491, 493, 490,Spiteller, G., 396, 402, 410.Spiteller-Friedman, M., 402.Spittler, T. M., 116.Spolter, L., 504.Sprague, J. W., 136.Sprague, M. J., 146.Sprake, C. H. S., 63.Sprickett, R. G. W., 371.Spring, F. S., 450.Springall, H. D., 61, 62.Spurlock, L. A., 233.Spumy, J., 89.Spyrides, G. J., 455.Srinivasan, R., 347, 352,Srinivasan, S., 90, 94.Srivastava, G., 123.Srivastava, G. P., 208.Sroka, W., 508.Srzdnicki, J., 87.Staab, H. A., 31, 322, 339.Staab, R. A., 550.Stacey, G. W., 380.Stacey, M., 333, 437, 492.Stachurski, Z., 93.Stackelberg, M., 613.Stadler, H. P., 599.Staehelin, M., 454,Stiillberg-S tenhagen, S.,Stafford, F. E., 78.Stafford, J. D., 110.Stahlmann, C., 483.Stalder, G., 481.Stamires, D.K., 41, 103.Stamm, W., 140.Stammler, M., 134.Stamper, J. G., 10.Stanek, J., 429.Stanishevskii, L. S., 305.Stanko, V. I., 121.Stanley, T. W., 530.501.355.319, 560662 INDEX OF AUTHORS’ NAMESStansby, M. E., 319.Stansfield, F., 280.Stanton, D. W., 363.Stapelfeldt, H. E., 539, 540.Stark, G. R., 510, 512, 513.Stark, J. R., 440.Stark, K., 184.Starkovsky, N. A,, 385.Starling, W. W., 419.Staron, N., 475.Starr, M. P., 381.Starrat, A. N., 360, 367.Star$, J., 556, 557.Staudinger, H. J., 464.Staudinger, V. H., 462.Stauffacher, D., 402, 426,Staveley, L. A. K., 73.Stear, A. N., 184.Steele, D. R., 108.Steele, J. A., 419.Steele, W. C., 64, 69.Stefaniak, L., 212, 215.Stefanovid, M., 304, 422.Steffan, G., 259.Stegeman, G., 70.Steger, E., 140.Stehling, F.C., 285.Steigbigel, N. H., 472.Steigman, G. A., 574.Steigner, E., 538.Stein, A., 338.Stein, L., 149.Stein, W. H., 481, 510, 511,512, 513, 516, 523.Steinberg, H., 118.Steinberger, N., 31, 217.Steinchen-Sanfeld, A., 62.Steiner, H., 285.Steiner, K., 343.Steinfelder, K., 412.Steinfink, H., 572.Steinhoff, G. W., 336, 378.Steinitz, K., 479.Steinmans, H., 432.Steinwand, 9. J., 272.Stembridge, C. H., 561.Stemmermann, M. G., 480.Stenhagen, E., 319, 559,Stenlake, J. B., 360, 400.Stephen, J. F., 330.Stephen, M. J., 36.Stephens, F. B., 93.Stephens, P. J., 189.Stephens, R., 333.Stephens, R. D., 313.Stephenson, G. F., 376.Stephenson, N. C., 164,165,Stephenson, T.A., 156,166.Sterling, C., 611.Stern, M. H., 318.Stern, R. L., 329.St,ernbach, L. H., 394.Sternhell, S., 367.Sternlicht, H., 45, 200.560.586.Sterr, G., 589.Steudel, R., 144.Stevens, C. L., 436, 437,Stevens, I. D. R., 347.Stevens, J. D., 456.Stevens, L. G., 74.Stevens, M. P., 553.Stevens, R. K., 321.Stevens, W., 308.Stevenson, D. P., 23.Stevenson, F. K., 495.Stevenson, R., 345, 420,Stewart, B. B., 134.Stewart, C. A., 265.Stewart, F. H. C., 219, 370.Stewart, G. H., 533.Stewart, J. M., 522.Stewart, R. D., 124.Stewart, R. F., 606.Stiddard, M. H. B., 180,Stiles, M., 328, 352.Stille, J. K., 257, 258, 372.Stillinger, F. H., 82.Stimmler, L., 478.Stinson, S. C., 257.Stock, J. T., 541.Stock, L.M., 274, 308.Stockdale, F., 503.Stocking, C. R., 452.Stockwell, P. B., 177.Stodola, F. H., 308.Stogryn, E. L., 371.Stogsdill, R. M., 588.Stoicheff, B. P., 210.Stojanac, Z., 268, 379.Stokely, P. F., 120.Stolle, K., 397.Stolow, R. D., 214.Stomberg, R., 583, 584.Stone, A. J., 46, 199.Stone, C. W., 531.Stone, E. W., 30, 31, 38.Stone, F. G. A., 69, 114,Stone, G. R., 299.Stone, T. J., 29, 336, 341.Stork, G., 307, 314, 350,Storlie, J. C., 189.Stornebrink, P. J., 543,563.Story, P. R., 228.Storz, J., 453.Stothers, J. B., 217, 360,Stout, C. A., 391.Stout, G., 367.Stout, G. H., 610, 612.Stout, R., 307.Stout, V. J., 367.Stout, V. R., 610.Stowe, M. E., 347.Stowell, J. C., 372.450.447, 611.181, 182, 190, 191.Stoffyn, P., 544.125, 188.368, 379.426.Strachan, P., 267, 335.Strachan, R.G., 414.Strlihle, J., 158.Striiuli, U. D., 470.Strain, H. H., 275.Strashsim, A., 546.Strating, J., 249, 324.Straub, W. A., 661.Strauch, B. S., 297.Straughan, B. P., 123.Strauss, H. L., 29, 30.Strausz, 0. P., 60.Streamer, C. W., 484.Strehlow, H., 82.Streib, W. E., 581.Streibl, M., 321.Steith, J., 329, 348, 372.Streitwieser, A., 195, 203,232, 233, 245, 270, 276.Strel’tsov, 0. A., 110.Streng, A. G., 39.Stretton, A. D. W., 455.Stretton, J. L., 53.Strickland, R. D., 532.Strobach, D. R., 441.Strohl, J. H., 534, 554,563.Strohmeier, W., 180.Strom, E. T., 31, 215, 413.Strominger, J. L., 436, 498,Stroud, D. B. E., 432.Struchkov, Yu.T., 597,598.Strumeyer, D. H., 516.Struve, W., 505.Stuart, A. P., 286.Stuart, K. L., 400.Stuart, M. C., 68.Stubbs, W. H., 180, 187.Stuber, H., 477.Studier, M. H., 116, 557.Stumm, W., 98.Stump, E. C., jun., 143.Sturgeon, R. J., 491.Sturm, E., 337.Stutzman, L. A., 464.Su, G., 290.Suami, T., 441.SuArez, T. H., 278.Subba Rao, G. S. R., 416.Subrahmanyam, G., 348.Subramanian, P. M., 252.SuchQ, M., 357, 360.Sucrow, W., 315.Suddens, A. J., 146.Sudheendranath, C. S., 541.Sudmeier, J. L., 553.Sudo, K., 363.Suetaka, W., 213.Suga, K., 306.Sugahara, H., 331.Sugasawa, T., 409.Sugihara, J. M., 249.Sugimoto, K., 436.Sugimoto, N., 410.Sugisawa, H., 443.504, 505.Sugimoto, s. I., 39INDEX OF AUTHORS' NAMES 663Sugita, J., 304.Suhalolnik, R.J., 450.Suhrmann, R., 100.Sujishi, S., 131.Suld, G., 286.Sullivan, C. E., 251.Sullivan, H. R., 465.Sullivan, J. O., 17.Sullivan, M., 488.Sulston, J. E:, 452.Summers, T. J., 175.Summerson, W. H., 516.Surnner, G. G., 591.Sumimoto, M., 364, 369.Sundaralingam, M., 596.Sundkvist, G. J., 546.Sundstrom, G., 307.Sunner, S., 64, 65, 72.Supp, G. R., 542.Surash, J. J., 98.Surtees, J. R., 126.Suryanarayana, S. TT., 534.Surzur, J.-M., 262.Suschitzky, H., 309, 381.Susz, B. P., 153.Sutcliffe, E. Y., 280.Sutcliffe, K. W., 478.Sutcliffe, L. H., 168.Sutherland, M. D., 344.Sutherland, J. K., 359.Sutherland, J. W., 536.Sutherland, S. A,, 362, 363.Sutin, N., 178.Sutton, D., 170.Sutton, L.E., 385.Sutton, P. W., 567.Suzuki, H., 425, 443.Suzuki, J., 554, 555.Suzuki, K., 509.Suzuki, M., 550, 551.Suzuki, N., 529.Suzuki, R., 311.Suzuki, S., 344, 436, 450.Svadkosikaya, G. E., 97.Svec, H. J., 69.Svennerholm, L., 486.Sverdlov, C. R., 213.Sveshnikova, E. B., 60.Svoboda, M., 259, 303.Swain, C. G., 242.Swain, H. A., jun., 63.Swain, R., 451.Swaminathan, S., 581.Swanson, A. L., 432.Swanson, J. A., 74.Swaroop, B., 151.Swartz, H. A., 557.Sweeley, C. C., 430.Sweeney, C. C., 160.Sweeny, J., 404.Sweet, T. R., 530.Swensen, W. E., 305.Swift, H. E., 126.Swift, T. J., 178.Swindbourne, E. S., 256.Swindells, R., 151.Swinkels, D. A. J., 86.Syhora, K., 428.Symes, T. G., 220.Symons, M.C. R., 28, 2933, 35, 39, 40, 177, 183.Syrkin, Ya. K., 305.Szabo, A.-G., 405.Szabb, 2. G., 102.Szar, J. C., 163.Szarek, W. A., 409, 436.Szer, W., 456.Szivek, J., 547.Szmant, H. H., 290.Szorenyi, B., 518.Szymanski, H. A,, 204.Szymanski, J. W., 121.Taagepera, M. R., 255.Taber, A. M., 101, 299.Taborsky, R. G., 528.Tabuchi, H., 286.Tabushi, I., 310.Tabushi, M., 529.Tacussel, J., 93.Tada, K., 461, 482, 483.Tada, M., 359.Tadanier, J., 234.Taddei, F., 211, 270.Taft, D. D., 307.Taft, R. W., 202, 240, 258.Tagaki, W., 270.Taguchi, H., 101.Taha, F. I. M., 160.Taha, I. A. I., 233.Taha, M. I., 442.Tahara, A., 304.Taimsalu, P., 206.Taka,gi, J., 535.Takagi, K., 310.Takagi, T., 302.Takahashi, H., 214, 220.Takahashi, I., 447.Takahashi, K., 507.Takahashi, M., 315, 363.Takahashi, S., 205, 494.Takahashi, T., 208, 366.Takashashi, Y., 439.Takaki, G.T., 178.Takano, T., 598.Takano, Y., 351, 368.Takasugi, M., 425.Takaya, T., 308.Takeda, K., 401.Takeda, R., 374.Takeda, Y., 318.Takei, W. J., 605.Takemori, I., 426.Takemoto, T., 357.Takeshita, T., 253.Takeshita, Y., 357.Takeuchi, S., 450.Takeuchi, T., 542, 550, 551,Takimoto, H. H., 342.Takitani, S., 530.Talakin, D. G., 64.556, 560.Talapatra, S. K., 404, 405.Talat,y, E. R., 413.Talipov, Sh. T., 537.Tallan, H. H., 523.Tallec, A,, 302.Tallent, W. H., 357.Taller, R. A., 212.Talmadge, D. W., 511.Talrose, V. L., 560.Talvik, A., 297.Tam, S. W., 334.Tamamushi, R., 89.Tamaru, K., 110.Tamm, C., 360, 426.Tamm, I., 453.Tamorria, C.R., 345.Tamura, Y., 410.Tamura, Z., 530.Tanabe, K., 413, 418, 430.Tanabe, &I., 425.Tanahashi, Y., 366.Tanaka, J., 197.Tanaka, K., 496.Tanaka, M., 507, 536.Tanaka, N., 89, 450.Tanaka, O., 419.Tanaka, S., 545.Tanaka, T., 133, 410, 428.Tanaka, Y., 369.Tandon, K. N., 538.Tandon, S. G., 528.Tanford, C., 430.Tani, H., 399.Tanida, H., 230, 351, 368.Tanida, H. H., 275.Taniyama, I., 108.Tankey, H., 290.Tanner, D. D., 231, 266.Tao, E. V. P., 257.Tao Chzhen-e, 345.Tarasevich, M. R., 94.Tartakovsky, V. A., 300.Tarver, H., 510.Tarver, M. L., 553.Tasumi, M., 207.Tataru, E., 103.Tate, D. P., 186.Tateno, J., 40.Tatevskii, V. M., 18, 207.Tatlow, J.C., 97, 333.Tattershall, B. W., 135.Taub, D., 303.Taube, H., 155, 178.Tavale, S. S., 594.Tavger, B. A., 26.Taylor, A., 377.Taylor, D. A. H., 365.Taylor, D. M., 558.Taylor, D. McK., 576.Taylor, E. C., 245, 377,Taylor, F. B., 126.Taylor, H., 99.Taylor, M. J., 218.Taylor, N. I?., 438.Taylor, P. M., 440.389664 INDEX OF AUTHORS’ NAMESTaylor, P. R., 452.Taylor, R., 255, 275.Taylor, R. C., 180.Taylor, W. C., 304, 335.Taylor, 17.’. F., 110.Taylor, W. I., 396, 402,Tebbe, F., 122.Tebbe, T., 119, 120.Tebben, J. H., 108.Tecotzky, TI., 148.Tedesco, T. A., 477.Tedoradze, G., 91.Teerlink. W. J., 249.Tefler, A., 546.Teichmann, B., 299.Tejima, S., 430, 437.Telder, A., 276.Teller, E., 50.Temkin, M.I., 90, 110.Temp6, J., 218.Tempel, E., 323.Tempest, W., 49.Temple, C., jun., 390.Templeton, D. H., 116, 127,149, 171, 571, 572, 576,677, 579, 580.Templeton, J. F., 370.Templeton, L. K., 580.Temussi, P. A., 594.Teneh, A. J., 38.Tener, G. M., 452.Tennant, G., 245, 295, 370,Tenningkeit, J., 451.Teotino, U., 466.Tephly, T. It., 466.Tepperman, H. M., 468.Teranishi, H., 256.Teranishi, R., 559.Terao, S., 407, 426.Terent’ev, P. B., 302.Terepka, A. R., 532.ter Maten, G., 200.Ternay, A. L., jun., 392.Ternbah, M., 408.Terry, R., 68.Tesi, G., 139.Tesler, A., 504.Tessier, J., 426.Testa, E., 250.Tevebaugh, A. D., 124.Thaler, W. A., 268.Thaller, V., 33 1.Thayer, J. S., 128, 135.Theander, O., 430,431,439,Theilacker, W., 378.Their, S., 485.Theml, P., 91.Thesing, J., 378.Thetford, R., 451.Thibault, R.J., 206.Thiele, K.-H., 188, 189.Thielemann, H., 144.Thies, C., 133.403,484.388.440.Thilo, E., 139, 141.Thirsk, H. R., 92, 98.Thoai, N., 303.Thom, E., 389.Thom, K. F., 143, 146.Thoma, J. A., 512.Thomas, A., 40, 117.Thomas, A. F., 216.Thomas, C. C., 460.Thomas, D. D., 44.Thomas, D. H., 99, 100.Thomas, D. H. H., 481.Thomas, F. G., 152.Thomas, G., 389.Thomas, G. H. S., 444.Thomas, H. J., 448.Thomas, J. D. R., 115, 532.Thomas, J. R., 29.Thomas, K., 492.Thomas, R. J., 275.Thomas, W. A., 219.Thomas, W. L., 529.Thomlinson, S., 480.Thompson, A., 137, 155.Thompson, C. J., 485.Thompson, D. D., 485.Thompson, E.0. P., 507.Thompson, G. A,, 419.Thompson, J. L., 443.Thompson, M., 534.Thompson, M. C., 165, 173.Thompson, M. J., 388. .Thompson, N. S., 289, 439.Thompson, R. C., 146.Thompson, W., 497.Thompson, W. R., 380.Thomson, A. E. R., 471.Thomson, C., 27, 42.Thomson, J. B., 345.Thomson, R. H., 343.Thonon, C. H., 108.Thorh, S., 65.Thorn, R. J., 78.Thornton, D. A., 181.Thornton, E. R., 221, 234,Thronsden, H. P., 338, 353,Thurman, J. C., 309.Thurmann-Moe, T., 613.Thurston, P. E., 347.Thweatt, J. G., 341.Ticha, M., 430.Tiel??, M., 411.Tieckelmann, H., 283, 384.Tiefenthaler, H., 381.Tiers, G. V. D., 206.Tilak, M., 509.Tildon, J. T., 297.Tillack, J., 157.Tille, D., 188.Tilley, J. N., 323.Timberlake, C. F., 161.Timell, T., 444.Timell, T.E., 289.Timmermans, J., 486.247, 268.423, 601.Timms, P. L., 119, 123.Tin, M., 550.Tin-Lok, C., 280.Tinsley, I. J., 469.Tipper, D., 498.Tirouflet, J., 340.Tishchenko, I. G., 305.Tisiornia, E., 319.Tissler, M., 387.Tobe, 31. L., 128, 148, 178.Tobey, S. W., 241.Tobias, M. A., 248.Tobias, R. S., 152, 155,Tobiason, F. L., 205.Tobin, M. V., 110.Tobiseh, J., 576.Tobler, E., 263.Toechi, G., 244.Toda, T., 368.Todd, Lord (A. R.), 341,Todd, G., 532.Todd, P. F., 29, 30, 31, 33.Toelrelt, W. G., 329.Tiiigyessy, J., 557, 563.Tiimoshozi, I., 316.Toeniskoetter, R. H., 124.Toennies, J. P., 52.Topert, M., 144.Toft, P., 365.Tolrita, K., 494, 502.Tokuhiro, T., 289.Tolruyama, K., 230, 437.Tolg, G., 543, 544.Tolgyesi, W.S., 238.Tolkachev, V. A., 41.Tollin, G., 31, 166.Tomasek, V., 507.Tomasi, TV., 97.Tomasz, M., 350, 367, 379.Tometsko, A., 509.Tomich, E. G., 468.Tomiie, Y., 608.Tomilov, A. P., 97, 302.Tomita, K., 457.Tomita, K.-I., 605, 606.Tomita, M., 401, 407, 426.Tomita, Y., 448.Tomkins, G. M., 469.Tomkins, I. B., 158.Tomlinson, &I. L., 173.Tomlinson, R. V., 452.Tomoeda, M., 363, 414.Tomoskozi, I., 249.Toner, J. J., 466.Toney, M. K., 261.Tong, G. L., 449.Tong, L. K. J., 280.Toogood, J. B., 425.Topper, Y. J., 477.Torgov, I. V., 412.Tori, K., 351, 368.Torii, M., 443.Toribara, T. Y., 552.Torimitsu, S., 302.Tornheim, J., 497.343, 392, 447, 457IKDEX OF AUTHORS’ NAXES 665Torper, G., 129.Torre, H.D., 531.Torssell, K., 125.Tbth, T., 531.Totter, J. R., 463.Tournoux, M., 134.Tourtellotte, C. D., 481.Touster, O., 469.Townley, E. R., 421.Townley, R. R. W., 478.Towns, R., 602.Townsend, L. B., 447.Townsend, 31. G., 200.Toyama, Y., 319.Toyne, K. J., 297.Tracey, H. J., 507.Tracy, H. J., 459, 523.Traetteherg, M., 130, 209,Trager, W. F., 214.Trambouze, Y., 100.Trams, E. G., 487.Travis, D. N., 13.Trapelis, V. J., 286, 304,306, 383, 394.Traylor, T. G., 257.Traynham, J. G., 246, 249.Trefonas, L. Bf., 602.Treibs, W., 338.Treichel, P. M., 114, 188.TrBmillon, B., 81.Tremmr, N. R., 414, 450.Trent, D. E., 160.Trepka, R. D., 269.Treshchova, E. G., 219.Trevalion, P. A., 40.Trevillyan, A.E., 310, 333.Trevorrow, L. E., 150.Trippett, S., 313.Trober, A., 66.TrojBnek, J., 406.Troll, W., 472.Trosciaaiec, H. J., 122.Trost, €3. M., 309.Trotter, J., 141, 582, 591,Trotz, S. I., 121.Trozzolo, A. M., 42, 43, 44,Truce, W. E., 323.Trueblood, K., 607.Truman, D. E. S., 453.Truong-Ho, M., 426.Truter, M. R., 189, 586,592, 602, 604.Tryon, M., 552.Tsang, S. M., 273;.Tsau, 31. U., 484.Tschesche, R., 366, 398,407, 422, 426, 427, 428.Tsfasman, S. B., 81.Tsitovich, D. D., 380.Ts’o, P. 0. P., 389, 447,Tsolis, A. K., 324.TSOU, C. L., 509.215, 583.592, 597, 599, 608.200.456, 458.Tsubomura, H., 24.Tsuchihashi, G.-I., 242.Tsuchiya, K., 213.Tsuchiya, T., 560.Tsuda, K., 401, 417, 419,Tsuda, Y., 366, 367, 398,Tsugita, A., 497.Tsuji, J., 317, 331.Tsuji, T., 230, 351, 368.Tsukamoto, A., 301.Tsukamoto, H., 441, 468,Tsutsui, T., 363.Tsutsumi, K., 546.Tsuzuki, Y., 430.Tubyanskaya, V.S., 66.Tuck, D. J., 127.Tucker, L. C. N., 437.Tucker, M. A., 178.Tucker, R. G., 447.Tucker, S. W., 246.Tuckley, E. S. G., 24.Tummler, R., 412.Tufts, L. E., 549.Tulinsky, A., 604.Tullen, P., 357.Tulloch, A, P., 319.Tullock, C. W., 145.Tunnicliff, D. D., 547.Tuppy, H., 453, 519.Turbert, H., 471.Turina, S., 530.Turlrevich, J., 41.Turnbull, A. G., 161.Turnbull, J. P., 359.Turner, A. B., 342, 381.Turner, A. F., 388.Turner, D. A., 557.Turner, E. E., 335.Turner, H. S., 124.Turner, J. C., 400.Turner, J. O., 240.Turner, M.A., 256.Turner, R. B., 62, 241, 327.Turner, R. W., 187, 587.Turner, W. N., 436, 438.Turnham, D. S., 555.Turova, N. Ya., 117.Turribn, C., 63.Tur’yan, Yu. I., 94.Tute, M. S., 387.Tuttle, T. R., 29, 35, 200.Tweit, R. C., 428.Tyerman, W. J. R., 56.Tyler, F. H., 488.Tyler, J. K., 210, 212.Tyman, J, H. P., 100.Tyor, M. P., 485.Tyree, S. Y., jun., 134, 151,153, 158, 159.Tyrell, J., 24.Tyssee, D. A., 143.Tyubenev, A. K., 117.Tyulin, V. I., 207.428.410.492.Tyurin, Yu. M., 89.Tyurkin, Yu. M., 101.Tza Chuan-sin, 89.Tzschach, A., 140, 141.Ubbelohde, A. R., 53, 127.Ubrych, M., 520.Uchida, T., 507.Uda, H., 249, 369.Uebel, J. J., 216, 219, 244.Ueda, K., 450.Ueda, T., 387.Uenishi, R. K., 143.Ueno, Y., 308.Uflyand, N.Yu., 89.Ugelstad, J., 273.Ugi, I., 370.Ugo, R., 190.Uhle, F. C., 237.Uhlig, E., 163, 172.Ukita, T., 448.Ukshe, E. A., 83, 98.Ulbricht, T. L. V., 446, 448,449, 450, 456, 468.Ulery, H. E., 258.Ullrich, V., 462, 464.Ulrich, H., 322, 323.Vlrich, J. A., 486.Ulrich, M., 428.Clshafer, P. R., 403.Tilstrup, J., 127.Ememoto, K., 34.Umezawa, R., 3.58.Umezawa, H., 450.Undenfriend, S., 462.Underwood, A. L., 541.Underwood, G. R., 378.Unrau, A. M., 443.Untch, K. G., 216, 464.Urbanski, T., 212, 215.Urbas, B., 444.Urbigkit, J. R., 555.Urch, D. S., 119, 126.Urnes, P., 458.Uroda, J. C., 310, 414.Urquizza, R., 416.Urry, G., 32, 129, 130.Urry, G. W., 250.Urscheler, H.-R., 320.Uschold, R., 271.Usher, D.A., 383.Uthe, J. F., 276.Utley, J. H. P., 276, 331.Utzinger, E. C., 423.Uyeo, S., 363, 407, 426.Uzan, R., 275.Uzarewocz, A., 301.Uzlova, L. A., 306.Vacca, A., 73.Vaciago, A., 604.Vacik, J., 532.Vaidya, W. AT,., 21.Vnjgaad, V., 539, 540.Vala, M. T., 197.Valange, P., 326, 350666 INDEX OF AUTHORS’ NAMESValberg, L. S., 547.Valenta, Z., 399, 408, 409.Valentine, G. H., 480.Valicenti, J. A., 306.Valkanas, G., 250.Vallance-Owen, J., 510.Vallarho, L. M., 163, 175.Vallee, L. M., 53.Valverde-Lopez, S., 408.van Armners, M., 319, 384.Van Artsdalen, E. R., 76.van Auken, T. V., 356.van Bac, N., 312.van Creveld, S., 479, 480.Vandeman, P. R., 484.van der Hende, J. H., 579.Van den Hurk, J. W. G.,189.van den Gen, A., 419.van der Hoeven, M.G., 321.van der Kerk, G. J. M.,132, 134, 189, 344, 395.Van der Waals, J. H., 42,200.Vanderzee, C. E., 74.van Dorp, D. A., 304.van Dyke, C. H., 130.Vane, F. M., 217.Van Es, A., 308.Vangedaal, S. 360, 426.Van Hook, 0. W., 105.Vanhorn, E., 472.Van Katwijk, J., 204.van Leusen, A. M., 324.van Leuven, H. C. E., 543.van Ligten, J. W. L., 528.van Loon, J. C., 532.van Meersscho, M., 603.van Meter, J. P., 327, 380.Van Mews, N., 544.van Montfoort, A., 103.Vannerberg, N.-G., 569.van Nordstrand, R. A.,van Overstraeten, A., 302.van Rooyen, M. H. M.,Van Rysselberghe, P., 90.Van Sickle, D. E., 266.van Tamelen, E. E., 403,van Velthuyzen, H., 528.van Velzen, J. C., 334.van Voorst, J.D. W., 200.van Wazer, J. R., 113.v. Ardenne, M., 412.Varimbi, J., 161.Varma, R., 128, 129, 212.Varshavskii, S. L., 302.Varshney, K. G., 528.Varushchenko, R. M., 68.Vasiliev, Yu. B., 95.Vasil‘lcova, 1. V., 73, 158.Vad’kova, L. V., 68.Vasilyev, Yu. B., 89.Vaaina, I. V., 345.Vaska, L., 179, 190.103, 547.319.450.Vassanelli, P., 467,468,470.Vasta, B. M., 96.Vatakencherry, P. A., 234,Vaterlaus, B. P., 438.Vaughan, J., 249, 275, 331.Vaughan, J. D., 274.Vaughan, J. M., 443, 444.Vaughan, L. G., 128, 271,Vaughan, M. H., jun., 452.Vaughan, P., 595.Vaughan, P. A., 601.Vaughan, V. L., 274.Vaughan, W. R., 259.Vaughn, J. G., 482.Vaulx, R. L., 392.Vaver, V. A., 320.Vavrzhichka, S., 85.Vdovin, V. N., 373.Veber, D.F., 378.VeEefa, M., 281.Veda, T., 104.Veenboer, J. Th., 147.Veenstra, H. W., 482.Veeravagu, P., 254.Veibel, S., 544.Veiga, J. S., 30.Veksler, V. I., 435.Venanzi, L. M., 170, 174.Venkataraghavan, R., 212,Venlcatasubramanian, N. ,Ventura, J. J., 133.Venugopalan, M., 430.Verbit, L., 246.Vercellotti, J. R., 440, 444.Verdone, J. A., 272.Veretil’nyi, A. Ya., 98.Verhaegen, G., 78.Verma, A. R., 570.Verma, R. D., 21.Vermilyea, D. A., 98.Verschoor, G. C., 606.Veselovskii, V. I., 94, 98.Veself, V., 537.Vesnina, B. L., 118.Vest, R. D., 373.Vetter, H. J., 118, 138,Vetter, K. J., 81.Vetter, W., 368, 412.Vezey, E. E., 17.Vickers, G. D., 121, 139.Vickers, T. J., 548, 550.Viehe, H. G., 309, 314, 326,Viellard, H., 249.Vielstich, W., 94.Vietzke, H., 140.Vigevani, A., 430.Vignau, H., 426.Vigneron-Voortman, 294.Viguera, J.M., 319.Villaescusa, F. W., 380.369.325.219.303.141.329, 350.Villotti, R., 330, 418.Vinal, R. S., 163.Vinarova, L. T., 537.Vincent, J. S., 42.Vincow, G., 41.Vineyard, B. D., 259.Vink, H., 531.Violanda, A. T., 554.Violante, E. J., 564.Virupashka, T. K., 510.Visakorpi, J., 478.Visscher, W., 94.Visser, H. K. A., 482,Viste, S., 160.Viswanathan, N., 403.Vithayathil, P. J., 512,513.Vliegenthart, J. G., 134.Vokkl, W., 88.Volter, J., 108.Voet, D., 458.Vogel, C., 122.Vogel, E., 338, 339, 361,352, 353, 354, 394.Voithenleitner, F., 241, 337.Voitkevich, S. A., 97.Vojnovich, C., 442.Volfin, P., 509.Volk, B.W., 488.Volkov, Yu. P., 345.Vollbracht, L., 276.Vol’nov, I. I., 115.Volodina, Z. V., 434.Volod’ Kin, A. A., 330.Vol’pin, M. E., 131.Volz, H., 240, 241.Volz de Lecea, M. J., 240.von Bulow, B. G., 324.von Buttlar, H., 94.von Daehne, W., 426.von der Mond, T., 100.von der Sluys-von derVlugt, M. J., 241.Von Dippe, P., 470.von Euw, J., 428.von Gierke, E., 479.von Gizycki, U., 341.von Mutzenbecher, G., 421.von Stackelberg, M., 81, 93,von Sydow, E., 368.von Wartburg, A., 357.Vorbriiggen, H., 396.Vorob’ev, A. F., 72.Vorobyev, V. I., 455.Voronkova, V. V., 531.Vorozhtsov, N. N., 333,*336.Vorozhtsov, N. H., ~un.,Vosos, P. H., 573.v. Philipsborn, W., 402.Vreugdenhil, A. D., 325.Vrieze, K., 191.Vrij, J., 467.VrkoE, J., 359.Vroelant, C., 203.Vyas, V.A., 254.94.333INDEX OF AUTHORS’ NAMES 667Wachmeister, C. A., 441.Wacker, O., 492.Wada, F., 461.Wada, M., 133.Wada, T., 356.Wada,. Y., 137, 212, 482,Waddell, W. J., 474.Waddington, T. C., 147.Wade, K., 122.Wadsley, A. D., 576.Wadso, I., 64, 72, 74.Wadsworth, W. S., jun.,Wiichter, J., 249.Waegell, B., 367.WiigerIe, R. R., 141, 144.Wagner, F., 370.Wagner, G., 448.Wagner, H., 128, 391.Wagner, K., 66.Wagner, R. I., 124.Wagner, W. F., 534.Wahl, G. H., 328.Waiblinger, H., 255.Waight, E. S., 250.Wades, P. C., 187.Waisman, H. A., 482.Waisvisz, J. M., 321.Wakabayashi, T., 409, 529.Wakao, N., 104.Wakefield, B. J., 118, 280,335, 383.Waki, H., 532.Walborsky, H.M., 266,270.Waldbillig, J. O., 272.Waldmann, S., 130.Walitzi, E. M., 577.Walker, A., 132.Walker, G., 593.Walker, J., 123.Walker, J. A., 533.Walker, R. W., 450.Walker, S., 126.Wall, J. S., 260.Wall, L. A., 333.Wallace, B. J., 488.Wallace, R. M., 183.Wallace, T. J., 255, 323.Wallace, W. E., 569.Wallenfels, K., 440.Waller, J. G., 143.Walling, C., 260, 261, 266,Walhann, J. C., 572.Wallwork, S. C., 170, 614.Walrafen, G. A., 144.Walrafen, G. E., 131.Walser, A., 407.Walsh, A. D., 8, 9. 13, 16.483.323.323.. ~ . ~ 18, 52, 23, 26.Walsh, J. H.. 534.Walsh, K. A , 296, 507.Walter, A. J., 150.Walter, W., 211.Walters, G. K., 59.YWalther, A., 408.Walton, F. A., 152.Walton, E., 450.Walton, H.F., 532.Walton, R. A., 151.Walzcyk, J., 549, 556.Wampler, D. L., 671.Wan, J. K. S., 264.Wang, C. C., 581.Wang, F. E., 580.Wang, J. C., 74, 175.Wang, K. Z., 509.Wang, S. S., 248.Wannagat, U., 124, 129,130, 155, 161.Wanelick, H. W., 341.Warawara, E. J., 411.Ward, A. D., 364.Ward, B., 328, 335.Ward, C. H., 205.Ward, C. R., 205.Ward, D. N., 519.Ward, G. A., 136.Ward, R. L., 33, 34.Wardell, J. L., 168.Waring, A. J., 350, 385,456.Warkenstein, J., 270.Warne, R. J., 124.Warneck, P., 17.Warner, J., 455.Warner, R. C., 453.Warner, T. B., 87, 88.Warnhoff, E. W., 359, 366.Warren, C. D., 433.Warren, C. G., 148.Warren, L., 487.Warren, S. G., 312, 323.Warsop, P. A., 16, 18, 22,Wasada, N., 560.Washburn, W.H., 219.Wasilewski, J. C., 561.Wason, S. K., 125.Wasserman, E., 42, 43, 44,Wasserman, H. H., 376.Wasserman, J., 559.Watabe, T., 468.Watanabe, A., 207.Watanabe, H., 215, 412.Watanabe, K., 11, 17, 25,Watanabe, M., 356.Watanabe, S., 306.Watanabe, T., 589.Watanabe, Y., 401.Waterbury, G. R., 545.Waters, J. H., 171, 172.Waters, T. N., 150, 162,Waters, W. A., 29, 336,341.Watkins, J. C., 343.Watkias, w. M., 441.Watling, R. C., 189,592.Watson, A. M., 111.Watson, E. S., 660.23, 25.45, 200.450.588, 589.Watson, G. J., 474.Watson, J. K. G., 24.Watson, J. P., 336.Watson, J. T., 559.Watson, T. R., 374.Watts, D. W., 178.Watts, J. E. M., 489.Watts, R. W. E., 485, 489,Watts, W. E., 224,227,238,Watts-Tobin, R.J., 83, 85.Wawrzyczek, W., 536.Weaver, J. R., 547.Weaver, W. M., 245.Webb, J. R., 544.Webb, J. S., 321.Webb, L. E., 586, 604.Webb, M., 484.Webber, G. M., 330, 417.Webber, J. M., 438, 444.Weber, A., 215.Weber, J., 86, 88, 93, 96,Weber, J. P., 196.Weber, J. Q., 136.Webster, D. E., 101, 102,129, 274, 276.Webster, G. R., 397.Webster, M., 130.Webster, R. K., 558.Wechter, W. J., 415.Weddige, H., 297.Wedemeyer, K. F., 322.Wedler, G., 100.Weedon, B. C. L., 97, 318.W e e d , R. O., 319.Wege, D., 236.Wegemund, B., 423.Wehl, J., 309.Wehrli, H., 422, 423.Wei, L., 588.Weichmann, H., 137.Weidel, W., 491, 498.Weidemeier, H., 77, 78.Weidenbach, G., 103.Weidler, A. M., 273.Weigel, H., 429, 430, 433,Weiher, J.F., 172.Weil, J. H., 41.Weimann, G., 451.Weirnrtr, R. D., 255.Weinbaum, G., 450.Weinberg, A. N., 477.Weinberg, K., 423.Weiner, R. F., 37.Weingarten, H., 280.Weininger, S. J., 234, 268.Weinstein, B., 425.W0instein, I. B., 456.Weis, W., 378.Weisbach, J. A., 400, 404,Weisburger, E. K., 472,473.Weisburger, J. H., 472,473.490.286, 353.416, 467.437, 441.405668We&, A., 320.We&, E., 116, 117,184, 412, 431, 692.Weiss, J., 144.Weiss, J. F., 166.Weiss, K. H., 345.Weiss, R., 573.Weiss, U., 410.Weissberger, E., 162.Weissmann, B., 497.INDEX OF AUTHORS' NAMES18,Weissmann; c.; 453.Weissman, S. I., 32, 200.Weisz, P. B., 103, 111.Weitkamp, H., 213, 643.Welford, G. A., 557.Welford, M., 365.Welkie, G.W., 453.Weller, P. F., 60.Wellman, K. M., 411.Wells, J. N., 290.Wells, P. B., 106, 108.Wells, R. J., 369.Wells, W. W., 430, 477.Weltin, E., 196.Welton, J. P., 487.Wempen, I., 448.Wendisch, D., 351.Wendlandt, W. W., 156,167, 560, 561.Wendler, N. L., 303.Wenkert, E., 329,362,400.Wenschuh, E., 151.Wenschuh, W., 161.Wenthe, A. M., 297.Wentworth, R. A. D., 154.Wenzel, A. W., 548.Wenziger, G. R., 410.Werdlandt, H. G., 143.Werk, E. E., jun., 470.Werkema, M. S., 600.Werner, D., 145.Werner, R. P. M., 179.Werner Zorbach, W., 437.Werries, E., 497.Werth, R. G., 225.West, B. O., 137.West, C. D., 548.West, L., 498.West, R., 128, 135, 241.West, T. S., 530, 550, 551.Westall, D. G., 480.Westall, R.G., 480, 482,Westenberg, A. A., 45.Westfelt, L., 359.Westheimer, F. H., 383,Westland, A. D., 166.Westman, T. L., 215,Westphalen, T., 418.Weterings, C. A. M., 108.Weth, E., 286.Wetlesen, C. U., 554.Wetter, G., 140.Wetter, W., 396.Wettstein, A., 421.483, 490.457.Wexler, S., 335.Wexler, W., 304.Wexter, A. S., 552.Weygand, F., 306.Whalen, D. M., 116, 324.Whalley, E., 218, 288.Whalley, W. B., 391.Wheat, R., 434.Wheatley, P. J., 137, 142338, 353, 582, 592, 601.Wheeler, 0. H., 290, 297.Whelan, W. J., 440, 442.Wheland, Q. W., 195, 203.Whiffen, D. H., 37, 38, 40199, 202.Whipple, E. B., 257.Whistler, R. L., 429, 436437, 438, 442.Whitaker, R. D., 147.White, A. B., 69.White, A. H., 177.White, A. M., 274.White, D.A., 330.White, D. E., 363.White, D. R., 51, 55.White, E. H., 329, 387.White, E. P., 377, 398.White, H. F., 210, 553.White, H. S., 286.White, J., 434.White, J. D., 360.White, J. G., 675.White, R. W., 369.White, W. H., 516.White, W. N., 286.Whitehurst, D. D., 258,372Whiteley, T. E., 437.Whitfield, G. H., 308, 317Whitham, G. H., 232, 35tWhiting, G. C., 431.Whiting, M. C., 321, 347Whitney, E. D., 147.Whittaker, D., 229.Whyman, P. E., 595.Wiberg, E., 133.Wiberg, K. B., 221, 348.Wiberg, N., 129.Wiberley, S. E., 204.Wickberg, B., 400.Wicke, E., 94.Wickramasinghe, J. A. F232, 415.Wickstrom, A., 443.Widmer, E., 343.Widom, B., 51.Wieber, M., 144.Wiechert, R., 415.Wieczorek, J. S., 384, 417Wieland, P., 421.Wiemann, J., 302, 303.Wierzchowski, P., 531.Wiesboeck, R.A., 122.Wiesner, K., 369, 408, 40'415.425.423.Wiezorek, J. J., 330.Wiggle, R. R., 146.Wightman, M., 559.Wightman, R. H., 304.Wijenberg, 5. B. G., 543,Wijers, H. E., 317.Wijga, P. W. O., 552.Wijnen, M. D., 540.Wilcox, C. F., 237, 249.Wild, A., 140.Wild, G. A., 682.Wild, S. B., 152.Wildervmck, J. C., 158.Wildman, S. C., 453.Wildman, W. C., 397, 399,Wiley, J., 221.Wilford, J. B., 188.Wilhelm, J., 146.Wilkins, C., 249.Wilkins, C. J., 142.Wilkins, C. K., jun., 386.Wilkins, C. T., 146.Wilkins, D. H., 534.Wilkinson, A. J., 185.Wilkinson, G., 156, 160,162, 163, 166, 167, 174,176, 177, 182, 186, 190,191, 313, 339, 591.663.402.Wilkinson, P.G., 8.Will, F. G., 88, 89.Willeboordse, F., 545, 562.Willemsens, L. C., 134.Willemsen, I,. L. M., 543,Willett, R. D., 167, 688.Willey, G. R., 129.Willhalm, B., 216.Williams, A., 296.Williams, C. H., jun., 460.Williams, C. S., 175.Williams, D., 51.Williams, D. E., 694.Williams, D. G., 289, 439.Williams, D. H., 212, 214,368, 396, 411, 412.Williams, D. J., 402.Williams, D. T., 438.Williams, G. H., 334, 335.Williams, G. J., 56.Williams, H. E., 479, 480.Williams, H. J., 573.Williams, H. P., 151.Williams, I. A., 423.Williams, J., 120.Williams, J. K., 219.Williams, J. M., 521.Williams, J. P., 542.Williams, K., 470.Williams, L. F., 181.Williams, N. R., 204, 429,Williams, P. C., 543.Williams, P. P., 146, 578.Wille, H.-W., 151.563.438INDEX OF AUTHORS’ NAMES 669Williams, R., 60, 171, 172,Williams, R. L., 120.Williams, R. P., 321.Williams, R. T., 460, 463.Williams, T., 542, 544.Williams, W. D., 360.Williamson, D. G., 24.Williamson, D. M., 416.Williamson, K. L., 213.Williamson, M. J., 274.Williamson, S. M., 70, 116,Willis, R. G., 314, 328.Wilmers, M. J., 478.Wilner, D., 225.Wilputte-Steinert, L., 256.Wilson, A., 614.Wilson, A. D., 563.Wilson, A. T., 321.Wilson, B. W., 158.Wilson, C. L., 528,529, 552,Wilson, D. V., 389.Wilson, E. G., 19, 26.Wilson, E. O., 71.Wilson, F., 547.Wilson, G. E., 345.Wilson, G. E., jun., 394.Wilson, I. W., 495.Wilson, J. L., 103.Wilson, J. M., 368,396,412,Wilson, J. S., 399.Wilson, K. V., 336.Wilson, L., 550.Wilson, P. D., 147.Wilson, R., 34.Wilson, R. E., 548.Wilson, S. A., 596.Wilson, V., 490.Wilson, V. K., 480.Wilzbach, K. E., 328, 419.Wimmer, I., 229.Windaus, A., 418.Winefordner, J. D., 548,Winkler, H. J. S., 356.Winkler, J. A., 303.Winsel, A. W., 101.Winstein, S., 203, 216, 227,230, 241, 242, 243, 244,252, 257, 327, 352.340.577.Wilmet-Devos, B., 276.553.430.550.Winter, E., 180.Winter, G., 152.Winter, T. G., 52.Winterbottom, J. M., 106.Wintersteiner, O., 419, 425.Winder, R. J., 499, 501,Wirth, T. H., 169, 276.Wise, S. S., 67.Wise, W. B., 218.Wise, W. M., 542.Wisotsky, M. J., 241.502.Witmowski, M., 212, 215.Witherell, D. R., 257.Withey, R. J., 249.Witkop, B., 495.Witkowski, R. E., 206.Witschard, G., 305, 306.Witteman, W. J., 52.Wittig, G., 306, 336, 337.Wittman, G., 163.Wittmann, H. G., 456.Wittmann, R., 451.Witwit, A. S., 553.Witz, J., 458.Wohl, R. A., 213.Wojnarowski, T., 311.Wold, A., 157.Wold, J. K., 444.Wolf, A. P., 258.Wolf, C. F., 321.Wolf, H., 412.Wolf, H. C., 60.Wolf, H. P., 477, 478.Wolf, K., 370, 390.Wolf, L., 286.Wolf, R., 388.Wolf, w., 599.Wolfe, S., 436.Wolfenden, R., 454.WOW, I. A., 319.Wolff, R. E., 357.Wolford, R. K., 289.Wolfrom, M. L., 429, 430,434, 435, 436, 437, 439,440, 441, 442, 444.Wolfsberg, &I., 290.Wollgiehn, R., 452.Wollish, E. G., 555.Wollnik, U., 268.Wollrab, V., 321.Wolovsliy, R., 339.Won-Bong Bang, 581.Wong, C. M., 409.Wong, D., 469.Wong, E. W. C., 224.Wong, M., 77.Wong, P., 477.Wong, R. Y. K., 432.Wong, S. H., 461.WonGin Ng, 477.Woo, L., 462.Wood, A. J., 554.Wood, C. S., 330, 382.Wood, D. E., 200.Wood, D. L., 437.Wood, H. B., 439.Wood, H. C. S., 237, 381.Wood, J. D. L. H., 559.Wood, 5. L., 174, 205, 206,472.Wood, J. S., 159, 162, 165,169, 179, 586, 588.Wood, N. F., 306, 309.Wood, P. B., 163, 178.Woodhead, J. L., 149.Woodhouse, E. J., 127.Woodhouse, R. L., 72.Woodroffe, G. L., 554.Woodruff, H. B., 374.Woodruff, R. J., 153.Woods, H. P., 18.Woodward, H., 543.Woodward, R. B., 227, 327,354, 388, 608.Woody, N. C., 483.Woolley, D. W., 522.Work, E., 498.Workman, R. J., 462.Woronkow, M. G., 130.Wortman, B., 504.Wotiz, J. H., 62.Wrathall, J. W., 173.Wray, K. L., 52.Wray, W. L., 52.Wright, B. G., 251.Wright, C. M., 136.Wright, G. J., 275, 331.Wright, I. G., 403.Wright, J. C., 120.Wrhbel, J. T., 410.Wroblova, H., 86, 95, 96.Wu, T. K., 201.Wu, V. Y., 570.Wuensch, B. J., 575.Wufson, N. S., 430.Wuketick, St., 490.Wulfman, C. E., 26.Wulfson, N. S., 412.Wunsch, E., 522.Wyatt, C. S., 472.Wybenga, F. T., 546.Wybregt, S. H., 478.Wyllie, S. G., 361.Wynne-Jones, W. F. K., 97.WU, Y.-C., 492, 494.Xin-Ten Ting, 310.Xuong, N. D., 302.Yager, W. A,, 42, 43, 44,Yagil, G., 135.Yakhontov, L. N., 305.Yakobson, G. G., 333.Yakovleva, E. V., 94.Yakubovich, A. Ya., 139.Yakubovich, V. S., 139.Ya Kul’ba, F., 127.Yalow, R. S., 511.Yamada, Y., 359, 558.Yamagami, M., 161.Yamagishi, S., 558.Yamaguchi, S., 401.Yamaki, H., 450.Yamamoto, A., 407, 441,Yamamoto, T., 319.Yamamura, S., 410.Yamano, T., 461.Yamao, M., 545.Yamasaki, M., 397.Yamashima, I., 491.200.492670 INDEX OF AUTHORS’ NAMESYamaahiro, D., 519.Yamoaka, N., 440.Yanai, M., 363.Yanatovskii, M. Ts., 305.Yankeelov, J. A., 512.Yang, J. T., 458.Yang, S. T., 511.Yannoni, N. F., 606.Yarborough, V. A., 553.Yariv, S., 528.Yasnoka, N., 608.Yassi, J., 407, 426.Yasuda, K., 133.Yasui, B., 410.Yasumori, I., 107.Yasunobu, K. T., 507.Yates, D. J. C., 106, 110.Yates, K. M., 480.Yates, P., 356, 405.Yates, R. E., 69.Yeager, E., 94.Yeowell, D. A., 397, 403.Yhland, M., 31, 34.Yiannois, C. N., 304.Yii, A. P., 241.Ying-Hsiuch Chen, F., 376.Yingst, R. E., 184.Yip, R. W., 352, 390.Yoder, C. H., 130.Yoe, J. H., 552.Yoffe, A. D., 135.Yoke, J. T., 166.Yonehara, H., 450.Yonemitsu, O., 403.Yonemoto, T., 202.Yonezawa, T., 203.Yoshida, H., 530.Yoshida, K., 286.Yoshida, T., 307,482,483.Yoshikoshi, A., 361, 362.Yoshimori, T., 556.Yoshikura, M., 315.Yoshimi, N., 545.Yoshimma, H., 468.Yoshimura, J., 439.Yoshino, T., 325.Yoshioka, M., 215, 412.Yosioka, I., 319.Young, A. E., 238,239,270.Young, A. R., 126.Young, A. R., jun.. 143.Young, B. C., 256.Young, D. A., 127.Young, D. M., 512.Young, D. W., 362, 363.Young, F., 498.Young, I. M., 384.Young, J. E., 168.Young, L., 81, 471.Young, M. A., 124.Youssefyeh, R., 416.Youssefyeh, R. D., 308,415.Yu, C., 448.Yu, T. F., 488.Yu Da-jiun, 577.Yu, A. P., 327.Yung, N., 448.Yuntsen, H., 450.Yunmov, S. Yu., 401.Yur’ev, Yu. A., 219.Zabel, R., 508.Zabicky, J., 294.Zabin, B. A., 155.Zabkiewicz, J. A., 314, 328.Zacharewicz, W., 301.Zachariasen, W. H., 579.Zachau, H. G., 454.Zafiriou, O., 387.Zagorevskii, V. A., 300,392.Zahn, H., 508, 509.Zaorzky, V. I., 341.Zahradnik, R., 280.Zahrobsky, R. F., 606.Zaidi, S. S. H., 546.Zaidlewicz, M., 301.Zaikin, I. D., 66.Zaikin, V. G., 412.Zaitseva, N. D., 158.Zakharkin, L. I., 121, 127,Zakutskii, V. I., 93.Zalar, F. V., 351.Zalesskaya, T. E., 307.Zalkin, A., 116, 127, 149,171, 571, 572, 576, 577,579, 580.301, 302.Zalkind, Ts. I., 98.Zalkow, J. H., 379.Zalkow, L. H., 249, 263,Zaman, A., 407, 426.Zamecnik, P. C., 448.Zamochnick, S. B., 549.Zandstra, P. J., 213.Zanker, F., 326, 349.Zannoni, V. G., 481.Zanon, I., 16.Zarembski, P., 490.Zaretskii, V. I., 412.Zarfas, D. E., 480.Zatko, D. A,, 636.Zauer, K., 381.Zhvada, J., 259, 303.Zavgorodduii, V. S., 132.Zawidski, J., 87.Zborilova, L., 146.Zderic, J. A., 440.Zeeh, B., 415.Zeeman, P. B., 547.Zeffer, H., 410.426.Zecher, w., 387.Zehavi, U., 434.Zeigel, R. F., 501.Zeilenga, G. R., 115.Zeiss, H., 188, 338, 353,Zeleznick, L., 447.Zelikoff, M., 12.ZelniEek, E., 479.Zelnik, R., 364.Zeman, A., 557.Zemlicka, J., 451, 452.Zergenyi, J., 249.Zerner, B., 296.Zettemtron, R., 484.Zevenhuizen, L. P. T. M.,Zharkova, L. A., 66.Zhdanov, Yu. A., 305, 439.Zhelankin, V. I., 66.Zhmakin, G. G., 87.Zhuge, A. L., 519.Zhukova, I. F., 108.Zhungietu, G. I., 439.Ziauddin, 388.Ziebold, T. O., 546.Zief, M., 371.Zieger, H. E., 333.Ziegler, D. M., 465.Ziegler, E., 388.Ziegler, L. K., 481.Zienty, F. B., 259.Zil’berman, A. N., 303.Zil’berman, E. N., 308.Zimmer, H., 268.Zimmer, W., 66.Zimmer-Galler, R., 139.Zimmerman, H. E., 203,Zimmerman, H. K., 435,Zimmerman, S. E., 253.Zinder, N. D., 508.Zingales, F., 190.Zingaro, R. A., 142, 146.Zinov’ev, A. A., 146.Zinser, D., 334.Zirakzadeh, M., 605.Zirner, J., 352.Zobacova, A., 436.Zoll, E. C., 394.Zolotarev, B. M., 430.Zorbach, W. W., 448.Zuckerman, J. J., 128, 130.Zuman, P., 80, 297.Zwahenburg, B., 249, 250,Zweifel, G., 229, 258, 300.Zwietering, P., 100, 111.Zwitkowits, P., 343.ZQka, J., 640.Zylber, J., 364.601.442.330, 342, 353.436.324

ISSN:0365-6217    

DOI:10.1039/AR9646100617

出版商:RSC    

年代:1964

数据来源: RSC

摘要:

I N D E X OF SUBJECTSAbsorption,. ultraviolet ; ee UltravioletAcarones, isomeric, Acenaphthene, -bromo--chloro-, Acenaphthene- ,-diol dinitrate, Acetaldehyde, energy transfer, 0Acetanilide, metabolic hydroxylation,. Acetylene as bridging group in complexes,t-butyl-, trimerisation,. fluoro-t-butyl-, oligomerisation,. 0internuclear distances, 0, 0Acetylenes, addition to, , 0, conversion into benzenes, diaryl-, dihydroboration,. hydrogenation,. 0oxidation,. polymerisation,. reduction,. removal of traces of, 0absorptionAcetylenic complexes, Acetylenyl radicals, Acetylide complexes, Acetylides, , Acid, allenic CIS, 0Acid anhydrides, stable, 0Acids, acetylenic, a-alkylalkanoic, ir spectra, 0carboxylic, heats of ionisation andneutralisation,.organic, nmr spectra, 0OXY-, PO~YOXY-, simple, unsaturated, cyclodimerisation of, Acoric acid, Actinides, Actinomycin complex with deoxyguanineActivation analysis, Activity, optical, due to boron,. Acyclic compounds, crystallography, Acyl-enzyme intermediates, Acyloin condensation,. 0Adamantanyl hexafluoroantimonat e , Addition,. electrophilic, to olehs, nucleophilic, to double bonds, of radicals, 0to aromatic compounds, to olefins, ’-deoxy-, ’-deoxy-’-homocitnxllylamino-, residues, Adenine, -methyl-, 0Adenosine, ’-amino-‘-deoxy-, ’-deoxy-, 0p- Adenosine- ‘- -uridine- -phosphoricacid, 0Adenylic acid polymers, Adianene, Adiantoxide, Adsorption,. entropies of, heats of, kinetics of, of ions at electrodes, of molecules at electrodes, of organic compounds, on solid metals, Aeruginosin By Affinine, 0Agropyrene, Ailanthone, Ajmaline, Alanes, Alcohol dehydrogenases, Alcohols, conversion into aldehydes, 0Aldehydes, preparation,.0, 0-Aldehydes, steroidal, Aldoses, oxidation of, Alicyclic compounds, Aliphatic compounds, Alka-lY-diynes, rearrangement to ben-“ Alkali carbonyls,” Alkali-metal organic compounds, acetylenediolates, Alkali metals, Alkaloids, Alkenes, cyclodimerisation,. Alkoxyl, determin in organic compounds,Alkylesters, primary, eliminationfrom, Alkylation of nucleic acid bases, N-Alkylation of amino-sugars, Alkylbenzenes, hydrogenation,. 0 Alkynylamines, , Allene, addition of HBr, , dimerisetion,.Allenes, addition of HBr, asymmetric synthesis, biogenesis, ,%substituted, solvolysis of, Allohimachalol, Alloxan,. 0, Ally complexes, Allylic complexes, derivatives, 0hydrates, ir spectra, 0reaction mechanisms, physical properties, 0zenes, reaction with ice, 0nmr spectra, 0preparative, 0D-Allose, ethers of carbohydrates, radical, INDEX O F SUBJECTS0,-Aluminazarophenanthrene, -methyl-Aluminium compounds, Amaryllidaceae alkaloids, , 0Amaryllidine, 0Amicetin,. 0Amicetose, Amide bonds in carbohydrate-proteinAmides, reaction mechanisms for, p-Amidobenzoates, carbohydrate, Amines, aromatic, metabolism of, intertiary, preparation by Ritter reaction,.Amino-acid metabolism, disorders of, 0transport, diseases of, Amino-residues, blocked terminal, Amino-sugars, Aminopyrine, metabolic demethylation,.Aminyl, electronic spectrum, 0Ammonia, decomposition,.00-phenyl-, hea-ts of formation,. complexes, relation to cancer, 0electronic spectrum, relaxation,. synthesis, catalytic, 0“ Amozonolysis,” 0Amylopectin,. Amylose, Anabasine, Analysers, automatic, Analysis, differential thermal, electrochemical, elemental, of organic compounds, gravimetric, mass spectrometric, qualitative inorganic, quantitative organic, radiochemical, reaction-rate methods, spectroscopic, teaching of, thermal, 0Anatobine, Anderson’s disease, Andirobin,. a-Androstane-Sj, a, a-triol, Androsterone, Angiotensin , Angolensic acid, methyl ester, , Angustmycin A and C, 0Anhydro -sugars, Anions, aromatic, nitrogen-containing, 0complex, halogen-containing, -co-ordinate, free-radical, Annofoline, 0Annothe, 0[ ]Annulene, hexadehydro-, 0[]Annulene trisulphide, , Annulenes, , , , , 0Anthracene, fluorescence, 0neutron-diffraction study, photo-oxides, Anthracene-trinitrobenzene complex, Antimony compounds, , , Aphins, , Aphyllidine, ( -)-enantiornery Apiose, Apocrotonosine, 00Apoglaziovine, 00Aporphines, 00Apocyanaceae alkaloids, Apparacine, 0Arborescin,.Arctiopicrin,. 0Arene cations in inorganic complexes, Arginine, 0hgininosuccinicaciduria, 0Arbtolactone, 0Aromatic compounds, -hydroxy-, inorganic complexes of, non-benzenoid compounds, rings, physical properties, Arsenic acid, heat of ionisation,.Arsenic compounds, 0, , Arsine, relaxation,. Artabsin,. Arthropods, secretions from, Aryl radicals, Arylamines, metabolism in relation toArynes, Ascophyllan,. L-Ascorbic acid, 0Aspidosperma dasymrpon alkaloids, 0Associations, long-distance, Astatine, Asymmetric synthesis (butadiene andAtisine, , 0Atoms in flames, ~-AzabicycIo[,,] nonane, Azepines, , Azetidine--carboxylic acid, a-Azido-ketones, decomposition,. Azine radical anions, 0Azines, Aziridine, ,-dimethyl-, nitrosation,. Aziridines, 0, Aziridones, Azirine, Azoles, 0-Azoniabicyclo[ ,l,O]hexane bromide,,-diethyl-,-diphenyl-, 0cis - - Azonialbic y clo [ , ,00~ tane iodide,,-dimethyl-, 0trans- -Azoniabicyclo[ 0,l ,O]tridecaneiodide, ,-dhethyl-, 0Azulenes, , Azurin,.0Bacteria, cell-walls of, , 0Barbiturate, ammonium, (0Barenes, complexes, 0, 0, cancer, dimenthyl fumarate), Azaferrocene,” ring fused to a large ring, 0hydrogen exchange, ‘‘ Barrelene,” , 0, Barton reaction,. Bases, heats of ionisation and neutralis-Benzaldehyde, o-nitro-, Benzaldoxime, p-chloro-N-methyl-, Benzamide-hydrogen tri-iodide complex,Benzene dathrates, ation,. in nucleic acids, derivatives, esr, Exchange of hydrogen with deuter-hexasubstituted, 0ium and tritium, 0, 0epoxide, hydrogenation,. 0neutron-dZfraction study, pentabromofluoro - , pentachlorofluoro- , triplet state, 0, 00Benzene-l,-diazo-oxide, photolysis, Benzenes, biogenesis of, 0Benzenesulphenate, methyl o-nitro-, Benzidine rearrangement, Benzimidazoles, ,-Benziodoxol--one, I-hydroxy, ,Benzocycloalkenyl derivatives, solvolysis,Benzocyclopropene derivative, , Benzo[,-a; ’,’-bldithiphen,.,,,,,,,-octafluoro-l,,a,a,,,a,b-octahydro-, Benzo[b]furans, Benzoic acid, o-iodoso-, anhydride, ’-dibromo-, Benzonorcaradiene isomers, Benzopyrene, addition to nucleic acidBenzoquinone-cyclo-octene adduct, Benzotriazoles, Benzothiazole--sulphonamide as carbonicBenzotrifluoride, halogenation of, Benzoyl ion,. pentamethyl-, 0Benzyl halides, o-substituted, reactivities,Benzylidene radical, Benzyne, , Beryllium compounds, , heats of formation,.Beyerol, Biacetyl, phosphorescence, 0Bicyclic systems, carbonium ions in,. Bicyclobutanes, Bicyclo[, ,O]heptene derivatives, Bicycle[ ,, llnonanes, 0Bicyclo[,,l]nonan--ol, Bicyclo[,,l]non--yl esters, acetolysis,Bicyclo[,,l]octa-,-diene, Bicyclo[,,]octatriene, , 0, Bicyclo-octenes, Bicy clo[ ,,]octen- - yl derivatives, Bicyclo[,,l]oct--en--yl esters, solvoly-pyrimidines, anhydrase inhibitor, sis, Bicyclo[,,l]oct--yl esters, acetolysis,Bicycle[ ,l ,l]pentane, Bifurcated bond, 0Binary compounds, crystallography, Biogenesis of alkaloids, of allenes, of nucleotide sugaxs, of plasma proteins, site of, of terpenes, Biogenetic conversions of polyacetylenes,Biological reactions, cdorimetry of, Biphenyls, ,’ :,’-bridged, Bipyrazinyl complexes, Bipyrroles, , Bismuth compounds, Bithienyls, Black-beetles, secretions from, Blasticidin S, 0Bluebell seeds, glucomannan in,. Bond energies, determination by calori-metry, a-Bonds, metal-ligand, 0Bonds, three-centre, a-Bonds in organometallic compounds ofBoranes, , 0isomeric, 0Borates, “ Borides ” as catalysts, 0Borine complexes, Borinyl, electronic spectrum, Borohydride reduction of sugar tosyl-Borohydrides, alkali, reduction by, 00Boron compound, optically active, compounds, heats of combustion,.derivatives, 0hydrides, , anions from, 0silicide, 0displacement of nitro-substituent, 0lengths, isotope effect, transition elements, hydrazones, heats of formation,.‘‘ Boron trifluoride dihydrate,” Boron-carbon compounds, 0, Boron-nitrogen bond, nature of, Boron-oxygen compounds, , Boron-phosphorus compounds, Boron-sulphur compounds, Bradykinin analogues, inhibition,. structure, Brominat ions, Bromides, Bromine compounds, oxidation of carbohydrates, Bromodichloromethane-diethyl etherBromotrichloromethane, addition to alk-Bullvalene, , derivatives, compounds, complex, enes, 0 Burnamine, 0Butadiene anion,. complex, Butenes, addition of iodine, Buxenine-G, , 0Cacalol, Cacalone, “ Cacodyl disulphide,” , Cadmium compounds, Caesium ozonide, Calorimeters, , , Calorimetry, secondary standard for, Calpurnine, a-Campholenyl ester, acetolysis, Cancer, Cannabinol, A-,-trans-tetrahydro-, Cantharanthine, Capillene, Capillin,.Carabrone, Carbamide, N-bromo-, use for oxidations,Carbanions, crystallographic structure,Carbazoles, Carbene, Carbenes, 00, 0, Carbides, Carbodi-imide, dicyclohexyl, Carbodi-imides, N-sulphonyl-, Carbohydrate esters, ethers, orthoester, Carbohydrate-polypeptide bonds, Carbohydrate-polypeptide polymers, Carbohydrates, amino - derivatives, anhydro-derivatives, branched, characterisation,. , 0, higher, thio-, unsaturated, Carbon,. surface oxides, , complexes, -co-ordinate, dioxide, absorbent for, electronic spectrum, , dioxide, relaxation,. inversion of, dibromo-, dichloro-, dihalogeno-, deoxy-, disulphide, electronic spectrum, monoxide, relaxation,., , , monoxide-binding pigment, Carbon-hydrogen,. deter-, Carbon-hydrogen-oxygen compounds,heats of combustion,. Carbon-sulphur bond-dissociationenergies, Carbonic anhydrase, inhibitor of, Carbonitrides, 0Carbonium ions, ions, non-classical, theory, 0stable, , Carbonyl chloride, electronic spectrum, complexes, -groups, polar interactions between,. ir stretching frequencies, , Carbonyl-,-dimethylbuta- ,li-diene-osmium, crystal structure, Carbonyls, metal, 0Cmboranes, 0, 0Carboxylic acids, reactions, 0Carboxypeptidase, 0Cardenolides, biogenesis, Car-ben-e-one, -methyl-, irradiation of,Carminic acid, Carnosol, p-Carotene and its derivatives, , Carotenoids, Carrobiose, a-Caryophylene alcohol, Caryophyllenes, Cassine, Casticin,.Catalysis, dual-function,. by metals, Catalysts, “ borides,” 0crystallite size of, 0, 0evaporated metal films, morphology, platinum black, 0platinum in molecular sieve, 0platinum on alumina, 0preparation,. Raney metals, 00silver films, supported metals, 0unsupported metals, 0acid derivatives, preparation,. 0Catechins, Catenane, Cell division,. Cellulose of green coffee beam, Celluloses, Centrosema seeds, polysaccharide in,. Cephaeline, Cephalosporin C, Cervicarcin,. Charge transfer, ligand-metal, v-w Charge-transfer complexes, Chemical shifts in nmr, calculation of,Chemiluminescence, Chimonanthine, 0Chloranil, Chloride ions, ligand field strength, Chlorides, heats of formation,.Chlorination,. heats of, Chlorine compounds, , Chlorobactene, Chlorobora-heterocycles, 0Chloroboranea, reaction with dienes, 0Chlorosulphene, Chlorotrifluoroethylene, dimerisation,. walls of bacteria, , 00 Chloroxanthin,. Chloryl, electronic spectrum, Cholestane, a,a-methylene-, Cholesterol, biosynthesis, Chondroitin,. -sulphate, Chromans, Chromatin,. Chromatography, adsorption,. column,. of carbohydrates, partition,. thin-layer, 0Chromium complexes, , compounds, , Chromose A, Chromyl chloride, oxidation by, 0Chronopo tentiometry , Chymotrypsin,. active centre, inactivation,. reaction mechanism for, a-Chymotrypsin,.n-Chymotrypsin,. Chymotrypsinogen,. 0activation of, Chymotrypsinogen A, structure, Cimicidine, 0Cimicine, 0Cinnamic acids, substituted, Cinnolines, Circular dichroism of steroids, a- and P-methyl-, solvolysis ofbenzoates, gas, of nucleic acids and their derivatives,Citrinin,. Citrullinuria, 0Claisen rearrangement, , , Clathrate hydrate of tri-n-butyl-Clathrates, Cleavamine, 0methiodide, dihydro-, 0Clovoboranes, 0Cobalt complexes, , , Cochineal, colouring matter of, Cockroach, American,. sex attractant of,Codeine, Codeinone, 0Codizlnt fragile, mannan in,. Coenzyme-& ,,, Coffee beans, green,. cellulose of, Colchicine, Columbin,. Combustion,. heats of, sulphonium fluoride, compounds, , , , , 0of organofluorine compounds, standardsfor, Complex formation,.heats of, Complexes, T--T charge transfer, containing three different metals, halogen-containing, inorganic, 0Y*molecular, crystallography of, square-planar, with - or &membered rings, Compressibility of tramition states, Computer, use in amlysis, , Conessidine, 0Configuration,. absolute, determhtion of,0in relation to metabolism, of inorganic complexes, Conformations of piperidine derivatives,of steroids, Conkurchine, 0Conodur amine , 0 Conodurine, 0Co-ordination compounds, crystallography,Copaene, Cope rearrangement, Copper compounds, , , Copper(r) nitrate, anhydrous, two forms,nitrate, gmeous, 0Copper(rr) complex, Copper-catalysed substitution,.0Cordycepin,. 0Correlation chart for pmr chemicalCorrin,. tetradehydro-, nickel complexes,tram-Corrin,. pentamethyl-, Corynantheic acid, dihydro-, 0Corynebacteriwn irRidiosum, blue dyeCotton effect, , 00shifts, 0from, for cyclic ketones, for nucleic acid bases, Coulometry, controlled potential, Coumalin,. ,-dimethyl-, dimers, Coumarans, Coumarin,. photodimerisation,. Coumarins, Coupling constant, absolute sign,. 0reactions, electrolytic, “ Covalent return,.” definition,. Crinamine, -hydroxy-, 0Croconate, diammonium, 00Crotonosine, 00Cryostat for magnetic-susceptibility“ Cryptic acid,” Crystal-field stabilisation energy, Crystallite diameter of metal catalysts,0, 0Crystallography , Cubane, , 00derivatives, octaphenyl- (reputed), , , 0Cucurbitacin-A, ‘‘ Cupressene,” Cyanates, alkyl, Cyano-complexes, Cyanogen azide, Cyanogen fluoride, “ Cyanozolysis,” 0measurements, Cyanuric acid, 0Cycloadditions, , Cycloalkane- , -diones, Cycloalkenes, hydrogenation,.0Cycloalkynes, reduction,. Cyclobuta[b ]naphthalene, Cyclobutane- ,-dione, tetramethyl-,photolysk, Cyclobutanes, Cyclobutene, ,-dimethyl-,-dimethyl-ene-, Cyclobutenedione derivatives, , 0,, Cyclobutenium cation,. -chloro- ,,,-te traphen yl , pentachlorostannate, -chloro-,,,-tetraphenyl-, ,-dipolar, reduction,. Cyclocamphanone, irradiation of, Cyclodecane, ,-dibromo-, 0Cyclodecapentaene, ,g-methylene, cis- Cyclodecene, Cyclodecylamine hydrochloride, 0Cyclododecatriene derivative, Cycloheptatriene conformers, Cycloheptatrienyl complexes, Cyclohexa-l,-diene-l,-dicarboxylate, di-methyl ,-dihydroxy-, Cyclohexane, manufacture, 0ring inversion,.rings, conformation,. Cyclohexane-,-dione, 0Cyclohexanone, Z-bromo- and ,g-dibromo-,,,-tetramethyl-, 0Cyclo( hexa-m-phenylene), [,,- aH,]Cyclohexene, addition of HBr,Cyclohexanealdehyde, polymerisation,. 0Cyclohex--enones, photochemical re-Cycloheximide, Cyclohexyl esters, solvolysis, Cyclomicrophyllines-A, -B, and -C, 0Cyclonona- ,,-triene, , C yclo-oc ta- , -diem, pho tolysis, Cyclo-octane, conformation,. Cyclo-octatetraene, addition of dienophiles, anion,. 0oc taphenyl- , arrangement, 0radicals, 0Cyclo-octa-l,,,-tetraene, tetramethyl-,Cyclo-octa- ,,-triene, photoisomers, Cyclo-octa- ,,-triene, Cyclo-octene, trans-, configuration,.trans-, resolution,. Cyclo - oc t ene-benzoquinone adduct, Cyclo-oct--enone, Cycle-octyl esters, solvolysis, actions, Cyclopentadienyl, Cyclopentadienyl-metal complexes, n-Cyclopentadienyl-n-pyrrolyliron,. toluene-p-sulphonates, -methyl-, re-T- Cyclopentadienylhexakis( trifluoro-methyl) benzenerhodium , Cyclopentadienylidene radical, trans-Cyclopentane-,-diamine, absoluteconfiguration,. Cyclopentene, - bromo -, solvolysis, Cyclopent--enyl esters, acetolysis, -Cyclopent-‘-enylethyl esters, acetolysis,, -Cyclopent-’-enylpropyl ester, solvo-lysis, Cyclophanes, Cyclopropabenzene derivative, , Cyclopropane, deuterated, Cyclopropanes, Cyclopropenes, Cyclopropyl ring in a bicyclic system,Cyclosilanes, Cystathioninuria, Cystinosis, Cystinuria, Cytidine, Z’-deoxy-Ci-hydroxy-, Cytochrome of Pseudomonas, 0Cytochrome C, 0Cytolipin-H, Cytomycin,.0Cytosine, 0participation in deamination,. N-Dealkylation,. metabolic, Doca-,g-dienyl esters, solvolysis, ,Decalins, conformers, %Decalylamine, deamination,. Decomposition,. thermal, heats of, Degradation of carbohydrates, Dehydroannulenes, Dehydrocamphor, Dehydrogenase for glyceraldehyde -phosphate, Dehydrogenases for alcohol, Dehydrogenation,. catalytic, of hydro-carbons, Dehydro-otobain,. Demethylation,. metabolic, , Dendrobine, 0Deoxyribonucleic acid, 0Deoxy-sugars, Deserpideine, 0Desosamine, Deuterium exchange by steroids, “ Dewar-anthracene,” “ Dewar-benzene,” derivatives, , Dextrans, acetolysis, Dextrins, Schardinger, Diacetylenes, aromatisation,.Diamino - sugars, Diaminopregnane alkaloids, 0Diarsine complexes, Diarylmethyl chlorides, solvolysis, Diazepinones, ,-Diazetidone, ,,,-tetraphenyl-, Diaziridone, oxide, eIectronic spectrum, Diazocines, Diazomethane adducts, Diazonium compounds, aromatic, Dibenzocyclo-octatetraene, rearrange-Dibenzodiazocines, Dibenzoylmethane , ,’-dichloro-, Diborane, reduction by, 00Dicarbonium ions, 0Di-p-chlorophenyl hydrogen phosphate,Dichroism, circular ; see Circular dichroismDicinnamyl disulphide, Diels-Alder reaction,., , photochemically induced, Dienes, addition of ,l-dichloro-,-difluoroethylene, Dienone-phenol rearrangement, 0, ,Diethyl ether-bromodichloromethanecomplex, Differential thermal analysis, , 0Diffuse layer at electrodes, Difluoroaminyl, electronic spectrum, Digifolein,. Diginin,. Digiprolactone, Digipurpurogenins, Digitoxigenin,. , Dihept--enoyl peroxide, decomposition,.Dihydroindoline-codeinone, 0Di-imide, 0Diketohexose, ,-~-threo-, fl-Diketones, cyclic, Dilituric acid, 0Dimer formation in DNA, Dimethanolaconinone hydriodide trihy-, :,-DimethanonaphthaIeney octahy-Dimethyl maleate, isomerisation,. Dimothylphenylsulphoniiim perchlorate,nz-Dinitrobenzene anion,. Dinucleoside phosphates, Diolefins, hydrogenation of, 0,,-Dioxaborinium cations, ,-Dioxan,.trans-,-dibromo-, 0o-Diphenoquinones, Diphenylmethyl esters, p-chloro-, solvoly-Diphenylmethylene radical, Diphosphine complexes, Diphosphorus tetrachloride complexes,Diploptene, Di- (-’-pyridylethyl) sulphide as ligand,Disaccharide intolerance, hereditary, Disaccharides, Diseases, metabolic inherited, ,-Diselenone-iodoform addition corn-ment, drate, dro-, sulphoxjde, 0trans-,-dichloro - , 0sis, 0pound, ,Disilicides, 0Dispersion,. optical rotatory ; gee OpticalDispiro[ ,,,]- ,,,- tetraoxohexa-Distillation for analytical separations, Disulphur monoxide, Diterpenes, ,-Dithiacyclodeca-,S-diyne, , -Di thie tan,. dic yanome thylene - , ,-Dithiin,.Divicine, Dolabradiene, Double bonds, participation in reactionmechanism, , , Double layer a t electrodes, Drug metabolism, 0Drugs: AY-, DPEA, Lilly , SKFA, rotatory dispersiondecane, 0Durene, -nitro-, halogenation,. Eburicoic acid, Echitamine halides, tram-Effect in octahedral complexes, Eicosaborane-, 0Electric discharges in inorganic com-pounds, “ Electrocatalysis,” Electrochemical analysis, Electrode, oxygen,. , double layer, 0reactions, 0kinetics, multi-step, 0photo-effects, technique for study of, theory, Electrodes, metal, adsorption on,. platinum, Electrodeposition,. use in analysis, Electrolysis, use for analytical separations,Electrolytic reduction of organic com-Electron paramagnetic resonance, inpounds, 0electrochemistry, probe, use in analysis, spectroscopy, use in analysis, spin resonance, of steroids, spectra, line shapes and widths, theory, transfer in inorganic complexes, intramolecular, trapped in ice, Electrons, trapped, 0Electrophoresis, Eliminations, olefin-forming, various organic, Emetine, Emission spectroscopy, use in analysis, Emulsion,.Enantiomers arrangement in crystals,, Energy exchange, electronic, Energy transfer, molecular, electronic-electronic, electronic-translation,. rotation-translation,. vibration-electronic, vibration-rotation,. vibration-translation,. 0vibration-vibration , Energy-level diagram for octahedral com-Enmein,. , 0Enthalpimetry, direct injection,.Enzymes, oxidising, 0Enzymic transfer of monosaccharideresidues, 0Eperuic acid, Episulphides, Epoxidation,. Epoxides, Equilenin derivatives, Equilin,. Erysotrine, 0Erythrina alkaloids, 0Erythrocentaurin,. Erythroidines, 0Ester bonds in carbohydra,te-protein com-plexes, Esters, nmr spectra, 0preparation,. 0reaction mechanisms for, 0, , Ethers, ir spectra, 0E thylammonium , trimethyl-, -deuteriumisotope effect on elimination from,Ethylammonium N-ethyldithiocarbamatefor group separation in analysis, Ethylene, tetramethyl-, epoxidation,. Ethylenes, substituted, nmr spectra,spectra, 0Eucarvone, photolysis, Europium complex, Evaporated metal films as cat,alysts, Exchange reactions, isotopic, 0, 0Excitons, triplot, , 00Explosion,.heats of, Fatty acids, natural, Fernenes, Ferredoxin,. 0Ferrocene, alkylation,. 0Ferrocenes, 0Filicene, epoxide, Filipin,. Fischer-Tropsch syntheses, 0Flame calorimetry, photometry, Flavans, Flavonoids, Fluorene, Z-acetamido- , metabolism of, Fluorenone ketyl, -Fluorenyl toluene -p - sulphomte, ,, -Fluorenylidene radical, Fluorescence snectroscotm atomic, plexes, trinitro-, acetolysis, Fluorides, Fluorination,. electrolytic, heats of, Fluorine, determn,. compounds, , Fluorine-containing free radicals, ligands, Fluorocarbon derivatives of metals, -Fluoroeurine, 0Fly-over ” ligand in an inorganic com-plex, , Forbes disease, Formaldehyde, electronic spectrum, Formic acid, decomposition,.0Fomyl, electronic spectrum, 0Fractionation of proteins, Fragmentation reactions, Free radicals in gas phase, in inorganic crystals, in liquid phase, in organic crystals, in solids, fluorine-containing, in zero magnetic field, migration,. oxyanion,. randomly oriented, in solids, 0Friedo-hydrocarbons, Fructose intolerance, hereditary, Fructosuria, essential, D-Fucosamine, L-Fucose in a trisaccharide, Fucoxanthin,. Fuel cells, , Fulvene, Functional groups, determn in organicFungapavine, 0 Funtuline, 0Furans derivatives, , Furan-,-dicarboxylic acid, Furan-,,,-tetrol, tetrahydro-, 0Furanose ring, nitrogen-containing, Furazan,.Furopelargones A and By Fusarubin,. Fusidic acid, Galactan,. Galactosaemia, Galanthamine, 0, 0Gallium compounds, Galvanic analysis, , Gargoylism, Garryine, ,0Gastrin,. 0, Gaucher’s disease, Genetic code, , Genetic effects on metabolism, Genistein,. -methyl-, Gentiobiose, , -analogue, 0Germanate, chloride, catalysts for, 0compounds, Germanides, 0Germanium compounds, Glands, submaxillary, Glaucarubin,. , 0Glaucophdc acid, diethyl-, 0Glaziovine, 00y-Globulins, y-Glucan in mangoes, Glucan in Pinw mugo Turva pollen,. Glucan in Polyperus giganticus, a-Glucan in Polypmus giganticus, Glucans, , , , D - Glucitol, photo - oxidation,. Glucomannan in bluebell seeds, in sugar maple, in white spruce pulp, a-D-Glucopyranosyl-(l-t l’)-D-glyCerOl, -deoxy--sulpho-, 0Glucosamine, metabolism, 0~-Gluc~samine derivatives, Glucose, polymerisation,.E - and p-Glucose, Glucosylamines, N-aryl, Glutethimide, N-hydroxymethyl-, N-acetyl-, 0metabolism, N-methyl-, metabolism of, Glyceraldehyde -phosphate dehydrogen-Glycine ahain in mucopeptides, 0Glycogen,. enzymic determination,. Glycogenesis, Glycopeptides from ovalbumin,. , Glycoproteins, biosynthesis, Glycosaminoglycans, , 0Glycosides, , Glycosidic bonds in carbohydrate-poly-peptide polymers, Glycosyl halides, solvolysis, Glycosylamines, hydrolysis, Glyotoxin,. Gmelinol, Gold, atomic weight, compounds, , Gougerotin,. 0Gout in relation to hyperurbemitt, Gouy-Chapman theory, Graphite compounds, Gratiogenin,. Grayanotoxins, Grifolin,.0Grignard reactions, 0Griseofulvin,. 0Group separation in analysis, Groups, functional, determn in organicGuanine, -methyl-, 0, Guianolides, D -Gulosamine, Gums, plant, Haemanthidine, 0Hafnium compounds, ase, storage diseases, reagents, structure, compounds, Halfordine, 0Halides, 0Halogen compounds, , organic, physical properties, 0Halogen-containing complex anions, Halogen,. determn,. , Halogenation of nucleic acid bases, Halogenobenzenes, reactions with nucleo-philes, Hamamelose, Haplocine, 0Haptoglobin,. 00Hardwickiic acid, Hartnup disease, Harunganin,. Hasubanonine, 0 Heats of chlorination,. of combustion of boron compounds, of carbon-hydrogen-oxygen com-of hydrocarbons, of organohalogen compounds, of organometallic compounds, of organosulphur compounds, of phosphorus compounds, of silicon compounds, pounds, of complex formation,.of explosion,. of fluorination,. of formation of aluminium compounds,of beryllium compounds, of boron compounds, of chlorides, of metal oxides, of selenides, of sulphides, of tellurides, of hydrogenation,. , , 0of hydrolysis, of ionisation,. of neutralisntion,. of reduction,. 0of thermal decomposit,ion,. of acids and bases, Helanin,. 0Ilelenalin,. Helium, electronic energy exchange, Hemicelluloses, Heparin,. 0, , Hepta-,-dieneY reaction with hepta-Reptafluoro- -iodopropane, reaction withHeptuloses, Heteratisine, 0, 0Heterocycles, 0crystallography, 0inorganic, - and -membered, 0 -membered, -membered, -membered, oxygen,.0sulphur, tin,. fluoro- -iodopropane, hepta- , -diem, 0 Heterocyclic compounds, small rings,physicd properties of, ‘‘ Hexa-acrylonitrile,” , Hexadecacarbonylhexarhodium, 0Hexafluorantimonates of organic cations,Hex- -ene, -deuterio-, stereospecific addi-[L-*H]Hex-l-ene, addition of zHBr, Nex--eny, cyclisation,. Hexosaminidase, ,-N-acetyl-, Hexose, -thio-, Hibaene, Himachalol, Himbosine, 0Hindrance to rotation in carbohydrates,Histidinaemia, Histidine, 0residues in chymotrypsin,. Homoconjugation,. stabilising carboniumions, Homocycles, crystallography, Homocyclic compounds, -, -, and -membered, physical properties of,-membered, physical properties of,with large rings, physical propertiesof, Homocystinuria, Homoribose, Huacra pona palm seeds, reserve poly-Hudson rules of isorotation for nucleosides,Huckel theory, , tion of aHBr, -phenyl-, esters, solvolysis, saccharide in,.for annulenes, for esr, for electronic spectra, for norbornadienyl, Humulene, , 0Hyaluronic acid, Hyaluronic acid-protein complex, Hydrates of salts, Hydrazine, for reduction of double bonds,reduction by, , 0Hydrazinolysis of esters, Hydrazo-compounds, aromatic, Hydrazone complexes, Hydrazyl radicals, Hydride ion,. position in spectrochemicalHydrides of metals, Hydrido-complexes, Hydroboronation,.00of hexofuranoside, of steroid monoenes, stereochemistry, , 00, 0series, 0Hydrocarbon radical-carbonium ion,. Hydrocarbons, alternant, pairing theoremfor, 0catalytic dehydrogenation,. Fischer-Tropsch synthesis, 0heats of combustion,. physical properties, 0re-forming of, saturated, molecular-orbital theory, Hydrogen atoms in flames, bond, bifurcated, , 0bonds in inorganic complexes, chloride, relaxation,. determn,. , exchange, , fluoride, carbohydrate reactions in,. isotope separation factors, , ,-rnigration during solvolysis, overvoltage, sulphide, electronic spectrum, tri-iodide-benzamide complex, para-Hydrogen conversion,. catalysis of,Hydrogen-deuterium isotope exchange,Hydrogenation,. catalytic, heat of, , , 0of mono-oleh, 0, 0Hydrogenolysis, 0“ Hydrol,” Hydrolysis, heats of, of glycosylamines, Hydroxykynureninuria, 0Hydroxyl, determn in organic compounds,Hydroxylamine, 0-methyl-, Hydroxylamines, formation of meta-bolism of amines, Hydroxylation,.metabolic, of steroids, Hydroxymethylation,. metabolic, Hy osc yamine, Hyperconjugation,. effect in esr, in -protein couplings, Hyperglycinaemia, H yperglycinuria, Hyperlysinaemia, Hyperoxaluria, primary, Hyperprolinaemia, Hyperuricaemia in relation to gout, Hypervalinaemia, Hyptolide, Ibogaine, Ice, reaction with alkali metals, 0Ichthynone, Idiocy, amaurotic family, D-Idose derivatives, Imidazoles, ImidazoC,l -i]purine, -’-chloroethyl- ,s-Imino-sugar, Iminoxy-radicals, Inclusion compound, channel type, withIndazoles, 0, 0, 0radical, NN-dialkyl-, Illudin-s, as catalysts, , , dihydro-gH-, 0perhydrotriphenylene, INDEX OFH-Indene, Indenylidene radical, Indium compounds, Indole alkaloids, 0Indoles, Indole-trinitrobenzene complex, Indolium perchlorate, ,l-dimethyl-, Indolizines, Indol--ylacetic acid, Inducers, biphasic action,.Indyne, , Infrared spectra of steroids, use in analysis of polyatomic species,Inhibition of drug metabolism by mor-Inhibitors, biphasic action,. Inner layer a t electrodes, , Instruments for er study, Insulin,. conformations, 0phine, of cholesterol biosynthesis, immunoassay, 0inhibition of action of, 0modifications, 0structure, 0synthesis, 0polar, between carbonyl groups, Interactions, molecular, Iodides, Iodine, addition to butenes, compounds, , heptafluoride, titrations, Malachite Green as indicatorfor, Iodine-starch complex, Iodine-tetrahydroselenophen complex,Iodination of -nitropropane, Iodoform-,-diselenane addition com-pound, Ion association,. solvent effects, exchange, use for carbohydrates, 0pairing for anions of nitrobenzenes, carbonium, dinegative triplet, 00free radical, Ions, adsorption a t electrodes, stable, , Ionisation of acids and bases, heats of, Ionophoresis of carbohydrates, 0Ircheline, 0Iridium complexes, compounds, , Iridoids, , Iridomyrecin,.0, Iron compounds, 0, y-Irradiation of carbohydrates, Irradiation (uv) of nucleic acid bases,I$obenzofuran,. Isochromam, Isocyanates, alkyl, Isocyanato-complexes, Isocytosine, 0Isoindoles, SUBJECTS Isojervine, Isolongifolene, -0 -somaltosyl-D -glucose, Isomaltotriose, Isoniazid, metabolism, ‘ ‘ Isopanose , ” Isoprosenolic acid, Isoquinoline alkaloids, Isoquinolines, Isoquinuclidine, “ Isoracemisation,.” Isothebaine, 00Isothiazolones, , Isothiocyanates, reaction with -amino-Isotope effect on bond lengths, sugars, boron,. on iodination,. solvent, exchange, 0hydrogen-deuterium, Isotopes, use in analysis, Isotutin,. a-bromo-, 0Isovenenatine, 0Jacozine, Jamine , 0cis-Jasmone, Javanacin,.Kaurane derivative, Kaurene, Kermesic acid, a-Kessyl alcohol, Kessyl glycol, Keto-groups, introduction into carbo-hydrates, Ketones, conversion into oleks, 0preparation,. 0reaction mechanisms, -Ketonoanolide, Kinetics of adsorption,. Kojibiose, Krabbe disease, Krypton compounds, Kurchiline, 0Kurcholessine, 0Lactone rule (Hudson-Klyne), Lactones, macrocyclic unsaturated, Lagosin,. Laminaribiose, 0Laminwin,. Lampterol, Langmuir isotherm, modified, Lanthanides, Laurifoline chloride, 00LCAO approximation,. Lead compounds, Leprotene, Leucodystrophy, globoid cell, Lewis acids, effect on Diels-Alder reac-tions, Lichenin,. Lifschitz metal complexes, of electrode reactions, INDEX O F SUBJEOTSLigands, tetradentate, 0Ligand-field strength of chloride ions, strength of sulphur, theory, theory of octahedral complexes, Lignans from “ lignum vitae,” N-Lignoceroyl-l-sphingosyl-lactoside, ,Limit dextrinosis, Limonins, Line-shapes in 0sr spectra, widths in sr spectra, Lipid storage diseases, Lipids, metabolic peroxidation,.Lipochondrodystrophy, Liquid scintillation counting, Lithium, alkyl derivatives, toluene-p-sulphonate, aluminium hydride, reduction by, halides, reactivities with methylpolyiodide, Liver diseases, Lobinaline, Lochnericine, 0Lochnerinine, 0Loliolide, Lonchocarpic acid, Longifolene , a-Longipinene, Luminol, light-production from, , Lupeol, Lyconnotine, 0Lycopodium alkaloids, 0sLysine vasopressin,.complex with copper,L-L ysine, ( DL- - amino - -carbox y -ethyl)-, McArdle’s disease, 0Macrolides, Macronine, 0Macusine-A, -B, and -C, 0Magnesium compounds, , Magnetic susceptibility, cryostat forMaleic anhydride, addition of thiols, Maleonitriledithiolate complexes, Maltobiuronic acid, 0Maltosamine, 0Manganese compounds, , Mangoes, glucan of, Mannan in Codium fragile, Mannich reaction,. 0D-Mannofuranosides, Maple-syrup urine disease, Mass spectrometry of alkaloids, of carbohydrates, 0of steroids, of terpenes, use in analysis, measurement of, C-Mavacurine, 0Melamines, Melanins, Melinonine-A, 0Mercapto-amine complexes, Mercepturic acids, formation during meta-bolism, 0Mercury compounds, , Metabolism, acceleration of, exchange, relaxation,. genetic effects on,.inhibition of, of amino-acids, diseases affecting, 0of drugs, 0of glucosamine, 0of purines, diseases affecting, of pyrimidines, diseases affecting, of sugars, disorders of, stimulation of, hydrides, oxides, oxidation by, 0oxides, sulphides, selenides, telluridesand chlorides: heats of formation,. Metal-amine solutions, Metal-metal bonds in complexes, 0, Metals, adsorption on,. Metal atoms, heats of formation,. reduction by, 0as catalysts, carbonyls of, 0-co-ordinated, , 0determn by X-ray fluorescence spectro-scopy, in organic compounds, fluorocarbon derivatives, unsupported, as catalysts, 0Metallocenes, 0Metaphanine, 0Me taplexigenin,.Meteorites, alkanes in,. Methacrylic acid, reaction with hydroxylradicals, Methane, relaxation,. Methicillin,. -Methylcyclohexyl hydratropate, pyroly-sis, Methylene, electronic spectrum, , Mevalonic acid phosphates, Michael condensation,. to give a resorcinol,Microscopy, use in analysis, Mitoridine, 0Mossbauer effect, Molecular addition compounds, calori-metry of, Molecular-orbital theory for esr, 0for inorganic complexes, , , for organic compounds, for transition-metal complexes, Molecules, adsorption a t electrodes, non-hydride triatomic, electronic spec-polyatomic, electronic spectra, AB,, electronic spectra, AH,, electronic spectra, AH,, electronic spectra, HAB, electronic spectra, 0containing electrons, spectra, containing electrons, spectra, containing electrons, spectra, 0containing electrons, spectra, containing electrons, spectra, 0tra, containing electrons, spectra, containing < electrons, spectra, containing electrons, spectra, Containing electrons, spectra, containing electrons, spectra, containing electrons, spectra, containing electrons, spectra, containing electrons, spectra, Mollisin,. Molybdenum compounds, , ’-Mononucleotides, ’-O-methyl ethers,Mono-olefins, hydrogenation,.0, 0Monosaccharides, Monoterpenes, Monspessulanine, Morphine, alkaloids, inhibition of drug metabolism, Mucin,. , 0Mucopeptides, , 0glycine in,. 0Mucopolysaccharides, in animal tissues, Multiple reflection cells, Muscular function,.diseases affecting, 0Mycocerosic acid, 0Mycinose, Myoinositol, 0Myrcene, cyclisation,. 0Naphthacene, ,-dichloro- ,-di-Naphthalene derivatives, synthesis of, 0phenyl-, ,-dichloro-, ,-dinitro-, fluorescence, 0triplet state, Naphthalene- -carboxamide, I -ethyl-,,-tetrahydro--oxo-, metabolismof, Kaphthaquinone, ,-dihydroxy-, anion,.’,’-Naphthocyclobutadiene, or-Naphthol, Narcissamine, 0a-Karcotine, Neighbouring-group displacement inNeochymotrypsinogens, Neoguanosine, Neoisothujyl esters, acetolysis, Neon,. relaxation,. Neothiobinupharidine, 0Neothu j yl esters , ace to ysis , Neptunium compounds, Neryl diphenyl phosphate, solvolysis, Nessler reagents, Neurotoxin from puffer fish, Neutron diffraction study of benzene, Nickel complexes, , Nicotine, Niemann-Picks disease, carbohydrate reactions, participation,. compounds, , alkaloids, Nimbin,.Niobium compounds, Nitramine rearrangement, Nitranilate, ammonium, 00Nitrate complexes, 0Nitrations, Nitrato-complexes, 0, Nitrenes, , 00, Nitric oxide, relaxation,. , , , Nitroalkane ions, alkylation,. 0Nitrobenzene, anion,. radical from, Nitrogen atoms in flames, compounds (inorganic type), determn,. determn in helium, dioxide, electronic spectrum, energy transfer, , , excitation,. 0fluorides, groups in organic compounds, physicalNitrogen-containing aromatic anions, 0Nitro-group, displacement of, 0Nitronic esters, aliphatic, Nitrophenol anions, p-Nitrophenyl azide, Nitrosophenols, Nitrosyl complexes, Nobiline, 0Noble metals, identification,.Noble-gas compounds, Non-pairing approach (Linnett) to valencytheory, Nopinyl esters, Noradrenaline, effect on metabolism, Norbornane-,-cis-ezo-diol, -phenyl-,conversion into -endo-phenylnorbor-nan--one, Norbornanes, ,-dihalogeno-, elminationfrom , Norbornadiene, , , Norbornadien- - yl cation,. Norbornadienyl derivatives, sovolysis, ,Norbornene, , properties, 0spectra, addition of aHBr, spectra, sis, Norborn--en--ylmethyl esters, acetolg-Norbornyl derivatives, deamination,. ~-Norcholest - -en- - ylmethyl es ters, sol --Norergosta-,,-trien- P-yl acetate,A-Norsteroids, , 0, Nortricyclanone , phot olysis, 0Nortricyclene, ring-opening, , Noviose, Novobiocin,. Nuclear magnetic resonance of carbo-solvolysis, ion,.0volysis, ,-dibromo-l%methyl-, Ihydrates, 0of nucleic acid derivatives, Nuclear magnetic resonance of steroids,theory, 0use in analysis, , Nucleic acids, , , 0bases in,. Nucleophiles, ambient, 0Nucleosides, ’,’-dideoxy-, 0’-O-methyl-, synthesis, triphosphates, Nucleotide sugars, biosynthesis, Nucleotides, pyridine, metabolism of, 0Obscurinervidine, 0Obscurinervine, 0Ochoteneimine, 00Ochropamine, 0Ochropine, 0Octaborane-, Octa-,-diene, cyclisation,. 0 cta-,- diene - ,-dicarboxylic acid, , -Octotillol, (Estradiol, -bromo-, (Estrone, Olefin complexes, Olefins, addition of enamines, dihydroxy-, 0exchange in inorganic complexes, additions to, , catalytic oxidation,.hydrogenation,. 0, 0, 0isomerisation,. 0, preparation,. 0, 0racemisation,. 0, 0Oligoadenylic acids, , Oligosaccharides, Optical rotatory dispersion of carbo-hydrates, 0of nucleic acids and their deriva-tives, of steroids, power, theory, Order-disorder in inorganic compounds,Organic compounds, adsorption,. electrolytic oxidation,. Organoalkali-metal reagents, Organofluorine compounds, thermo-ohemistry of, Organohalogen compounds, heats of com-bustion,. Organometallic compounds, heats of com-bustion,. reactions of, 0Organosulphur compounds, heats of com-bustion,. Organozinc reagents, Ormomnine, Orotate, rubidium -fluoro-, 0Orotic aciduria, Osazones, 0Osmium compounds, Ovalbumin,. glycopeptides from, Overvoltage, hydrogen,.oxygen,. Oxadiazoles, Oxalates, Oxalic acid, dideuterio-, Oxazoles, Oxepins, Oxidases, mixed-function,. 0Oxidation by enzymes, 0catalytic, of olefins, chemiluminescent , electrolytic, of monosaccharides, of NADPH, 0of organic compounds, 0heats of formation,. Oxides, N-Oxides, formation in demethylation,.Oxhes, complexes of, Oxyacetylene flame, use in analysis, ?xy-acids, z, Oxy-Cope rearrangement, Oxygen atoms in flames, compounds, inorganic, determn,. , , , electrode, , energy transfer, exchange by esters, 0heterocycles, 0overvoltage, relaxation,., singlet molecular, oxidation by, 0uptake in enzyme reactions, 0Oxygen-carrier, iridium complex, Oxygenyl compounds, Oxytocin,. modifications and structure,Ozone solvate, Paeodorin,. Palladium compounds, , , complexes, Panose, Papain,. 0Paper chromatography, Paviser-Parr-Pople method in quantumParomose, Parthenolide, 0Participation in reactions by double bonds,, Penicillin-penillonic acid rearrangement,Penicillenic acid h e r , Pentalenyl dianion,. n-Pentane, Pentatetraenes, Pent -- enyl derivatives, solvol ysis , Pentoses, -amino- -deoxy- , Pent-a-yne, -chloro--methy, solvolysis,Peptides, 0Peracids, oxidation by, 0Perfluoro-compounds, aromatic, theory, by neighbouring groups, INDEX OB’ SUBJECTS Perfluoro-organic ligands in inorganiccomplexes, Perhydrotriphenylene inclusion com-pound, Perhydroxyl radical, Periplogenh, Perivine, 0Perkinamine hydrochloride, 0Peroxidation,. metabolic, Peroxocarbonates, Perxenate ion,.Perylene, Petaline, , 00Pfaundler-Hurler syndrome, Phages, , protein in,. 0Phenanthrene, fluorescence in,. 0Phenanthridines, Phenethylammonium, trimethyl-,deuterium exchange, Phenol, Phenol-dienone rearrangement, 0Phenols, oxidation of, Phenonium ions, , Phenoxide ions, position of charge, 0Phenyl azide adducts, -Phenylallyl esters, exchange of acylgroups, Phenylboronates, carbohydrate, Phenylketonuria, Phenylosotriazoles, Phomazarin,. Phosgene, electronic spectrum, Phosphates, Phosphine complexes, 0, 0, Phosphinyl, electronic spectrum, 0Photo-effects in electrochemistry, Phosphoketolase reaction,.Phospole -oxide, I-ethoxy-, Phosphonitriles, Phosphorimetry, 0Phosphorus acids and salts, heats of combustion,. radicals, of carbohydrates, derivatives, , relaxation,. compounds, , peroxides, 0tricyanide, organic, 0Phosphorus-nitrogen compounds, Photochemical replacement reactions, in-Photo-oxidation of carbohydrates, Photo-reactions of steroids, Phthalocyanin,. use in analysis, Phthienoic esters, 0Physalaemin,. 0, Phytolaccogenin,. , 0Picraphylline, 0Picrosalvin,. Picryl chloride as nucleotide condensingagent, Pimaricin,. Piperidines, Piptanthine, Plant gums, Plasma emission spectrometer, Platinum black as catalyst, 0complexes, , compounds, , electrodes, in molecular sieves t~ catalyst, 0Platinum-alumina catalysts, 0Pleiocarpamine, 0Pleuromucoid, Point-dipole model for 0sr of aromaticmolecules, 0Polarography , instruments for, dc, Polyacetylenes, Polyatomic molecules, electronic spectra,Polygallic acid, Polymers, analysis of, Poly(methy methacrylate), as host forPolyoxy-acids, Polypeptides, blocked terminal amino-residues in,.Polypeptide-carbohydrate polymers, Polysaccharides, Polyuronides, PompB’s disease, 0Porphines, 0in complexes, Porphyrins, , Potassium, relaxation,. Potentiation of neuromuscular blockingPressure, effect on reaction rates, , effect on phenylation of t-butylbenzene,study of triplet states, spectrum after irradiation,.agents, “ Prismane ” derivative, , , Progesterone, -hydroxy-, metabolicPrometaphanine, 0Pronuciferine, 00Propane, -nitro-, iodination of, Propylamine, ,,-trideuterio-, deamina-tion,. Propyne, addition of HBr, , Protactinium compounds, Proteins, 0hydroxylation,. blocked terminal amino-residues in,. synthesis, Protein-hyaluronic acid complex, Proton magnetic resonance, 0ptonations, Pseudoaromatic,” definition,. Pseudocapacitance, Pseudocellobiuronic acid, 0“ Pseudoindene,” Pseudo-octahedral complex, definit,ion,.Pseudopolymerisation,. Psicofuranine, 0Pteridines, 0Pulcherrimine, Pulcherriminic mid, Purines, , 0diseases affecting metabolism of, Puromycin,.inhibition of protein synthesisby, Purpeline, 0Pyoluteorin,. Pyracene, reduction to give anion,. Pyrans, 0Pyrazoles, 0Pyrazolino- steroids, Pyrazolium iodide, ,-dimethyl-, 0Pyridazines, Pyridine alkaloids, nucleotides, metabolism, 0N-oxides, ring, conversion into benzene ring, Pyridines, dihydro-, from pyrrolenines, a-Pyridone, l-methyl-, 0photoisomers, ,-Pyridyne, Pyrimidine, hexahydro -- thio- , 0Pyrimidines, , 0Pyrolysis of norbornadiene, e-Pyrone, photoisomers, Pyrones, 0Pyrrole alkaloids, Py-rroles, , Pyrrolenine-pyridine rearrangement, Pyrrolylpyrroles, , Pyrylium salts, 0Pinw mugo Turrar pollen,. glucan andheteropolysaccharide in,. Polyporus giganticw, galactan in,.polysaccharides in,. Psezcdomom, polyuronide in,. Quadricycloheptyl derivatives, solvolysis,Quantum theory, organic, Quantum-chemical theory for esr, “ Quasiaromatic,” definition,. Quassins, biogenesis, 0Quebrachamine, 0Quinoline alkaloids, complexes, N-oxides, Quinolines, , Quinomethanes, Quinones, Quinoxaline N-oxides, diseases affecting metabolism of, photochemistry, triplet state, Racemisation,. intramolecular, Radical ions, stable, transfer, intramolecular, among steroids,Radicals, addition of, 0conformations of, odd alternant, , steady-state concentration,. transient, in liquid phase, trapped, See also Free radicalsRadiochemical amlysis, Raney cobalt, reduction by, 0use in analysis, metals as catalysts, 00nickel, reduction by, 0Rare-earth ions, energy transfer, 0Raujemidine, 0Reaction mechanisms, for inorganic complexes, rates, use for analysis, Reactions, named: see under the name,eg, Wittig, Cope“ topochemical,” Reactivity indices, 0Rearrangement, Claisen,. Cope, of aliphatic compounds, of aromatic compounds, , of benzidines, of 0- to N-glucosides in nucleosides, p;f nitramines, oxy-Cope,” Reconstruction of DNA, Reductase, NADPH-cytochrome c, 0Reduction,.electrolytic, , 0heats of, 0of organic compounds, Reformatsky reaction,. stereochemistry of,Re-forming of petroleum, Refractories, analysis of, Relaxation,. rotational, techniques in electrode-reaction study,vibrational, Renierapupurin,. Renieratene, Replacement reactiom of octahedral com-Reserpine, 0Reticuline, 00Retro-Diels-Alder reaction,., Rhenium compounds, Rhodium complexes, Rhodopin,. Ribonuclease, carboxymethylation,. plexes, photochemical, inorganic, 0compounds, , , 0S-dinitrophenyl-, partial structure, subtilisin pieces, Ribonucleese-B, Ribose p-bromophenylhydrazone, 0Rimuene, Robustic acid, Rocks, analysis of, , , , Rosane, Rosenonolactone, Rosololactone, Rotation,. hindered, in carbohydrates,Rotational barriers, 0, Ruthenium and its compounds, 0, tetroxide, oxidation by, S a l h , Salicylamide, Salts, hydrates of, Samaderins B and C, Sarcostin,. Scandenin,. Scandium, Schardinger dextrins, Schiff bases, transamination,.Scintillation counting, liquid, Securinine, 0, 0Seed oils, 0, Selection rules for vibrational exchange,Selectivity index, in analysis, Selenides, heats of formation,. Selenium, relaxation,. compounds, , , Selenocinnamates, aryl, hydrolysis of, Semiquinone anions, radicals, Senegenic acid, Senegenin,. Separation,. electrolytic, factor for hydrogen isotopes, , for analysis, methods, Seredamine, 0Serratenediol, , Sesquiterpenes, , 0Seven-co-ordinated metals, , 0Sex difference in metabolism, Shionone, Silane, relaxation,. Silicates, Silicides, 0Silicon carbide, 0compounds, , , 0cyclic compounds, 0Silver compounds, , films as catalysts, powder, use in analysis, Silyl ethers of carbohydrates, Silylene, electronic spectrum, Simarolide, , 0Skatole-trinitrobenzene complex, ct-Smegamycolic acid, 0Smiles rearrangement, Sodium, fluorescence, quenching after excitation,.reaction with ice, , Solasodine, 0Solvent effects on ion association,. extraction,. use in analysis, , Sophorose, Spectra, electronic, of inorganic complexes,of organic molecules, , of polyatomic molecules, far-infrared, of complexes, of organic molecules, 0infrared; see Infrared spectramass; see Mrtss spectraSpectrocolorimetry, Spectrofluorimetry, Spectrograms, multicolumn,. Spectrometry, atomic fluorescence, Spectrophotometry, infrared, Spectroscopy, atomic absorption,. 0ultraviolet, visible, electron,.use in analysis, emission,. use in analysis, use in analysis, X-ray fluorescence, Spermine phosphate, Spin density, calculation of, Sph-spin coupling in terpene field, Spinochrome-M and -B, Spiro [ ,]pentene, Split-p-orbital approach (Dewar) tovalence theory, Splittings, hyperfine, in esr, Sporidesmin,. Spot tests, Stabilisation energy, crystal field, Stachene, Starch, amylomaize, fractionation of, Starch-iodine complex, Stepharine, 00Stereospecificity of metabolism, Steroid alkaloids, 0, , Steroids, in ring systems, -aldehydes, cyano-, 0epoxy-, , -keto-Ad-, -keto-~-nor-, metabolic hydroxylation,. monounsaturated, hydroboronation,.a-nor-, 0B-nor-, pyrazolino-, reactions of rings A and B in,.reactions of ring c in,. reactions of ring D in,. 0syntheses of, with benzenoid c ring, , Stibine complexes, 0Still, centrifugal molecular, Strain energies in ring systems, pseudo-Strophanthidin,. Strygosine, Styrenes, hydration,. Styryl chloride, c&?- and tram-, modes ofSubstitution,. catalysis by copper, 0electrophilic aliphatic, electrophilic, aromatic, , nucleophilic, , , , 0, prediction of aromatic, 0Subtilisin,. 0Sucrose, enzymic oxidation,. Sugar maple, glucomannan in,. Sugar metabolism, disorders of, Sugars, nucleotide, biosynthesis, Sulphadiazine, metabolism, Sulphadimidine, metabolism, Sulphanes, Sulphenes, reaction,. Sulphidea, Sulphines, Sulphonic acid, aromatic, naturally occur-ring, , 0Sulphonium salts, elimination from, Sulphoxides, solvolysis, Sulphoxylic acid, Sulphur acids, allotropes, compounds (inorganic type), , ,determn in organic compounds, dioxide, electronic spectrum, donors in complexes, heterocycles, ligand field strength, ligands, monoxide, relaxation,.heats of formation,. Sulphur-fluorine compounds, Sulphuric acid, heat of formation,. Supported metal catalysts, 0Swietenine, , 0Synthesis, stereospecific, of nucleosides,Syphilobin-A and -F, Syringe reactions, Sternphylium radicinum, antifungal meta-bolite from, Taka-amylase A, Takadiastase ribonuclease, 0Talopyranoside, methyl ,-dideoxy-, -imino-,-O-isopropylidene-a-~-, Tantalum compounds, Tauranin,.0Taurine, Tay-Sacks disease, Technetium compounds, Teichoic acids, 0, , 0Tellurides, Tellurium compounds, , , Tenuazonic acid, Terpene alkaloids, 0Terpenes, model for biosynthesis, physical methods for study of, Terpinen--0, Tetra-n-alkylammonium salts as reactionmedia, ,a,,a-Tetra-azapentalene, ,-di-bromo-,-dimethyl-, 0,a, ,a-Tetra- azapentalene- ,-&car-boxylic acid, ,-dimethyl-, 0Tetraborane carbonyl, Te tracyanoquinodime thane complexes,Tetracyclines, Tetracycloxides, Tetrafluorophosphorus radical, Tetrahydroselenophen-iodine complex,Tetramethylenediammonium chloride,Tetraoxygen,. -co-ordinate, heat of formation,. Tetrazoles, Tetrodoxin,. , , 0Tetroses, ,-di-O-methyl-, Thallium compounds, Thalmelatine, 00THAM, secondary standard for calori-metry, -Thenoio acid, Theophylline, -glycoside, -phenyl-, Thermal analysis, 0Thermochemistry, Thermogravimetry, , 0Thiachromans, Thiachromenes, Thiadiazoles, Thian -oxide, -ChlOrO-, solvolysis, Thianthrene ,0-dioxides, Thiapyrans, Thiaselenacyclopentane spiran,.,,,-Thiatriazole, -ethO~y-, decom-position,. Thiazepines, ,-Thiazines, ,-Thiazin--one, - hydroxy-, Thiazolidine ring, non-planar, 0Thiazolidinedione, -phenyl-, 0Thiete sulphones, Thiobinupharidine, 0Thiocarbonyl chloride, electronic spec-Thiocyanato-complexes, Thioesters, -Thio-~-~-glucopyside, methyl -S-Thioketones, Thiol radicals, ,-Thioles, Thiols, addition to maleic anhydride, Thionyl radicals, Thiophens, Thiophosgene, electronic spectrum, Thiosemkarbazones of carbohydrates, 0Thorium compounds, Thujones, Thujopsene, 0Thujyl alcohols, Thyroglobuline, Thyrotropin,.Tin complexes, , , 0compounds, , heterocycles, Titanium complexes, 0compounds, Titration,. acid-base, amperometric, 0complexometric, conductometric, 0constant-current potentiometric, ,coulometric, differential electrolytic potentiometric,instrumental, nephelometric, trum, p-D-glycopyranosyl-, 0Thio-sugars, , INDEX OFphotometric, potentiometric, precipitation,. , radiometric, , redos, thermometric, turbidimetric, visual, Toluene isomers, , Tomentogenin,. Topochemistry, , Toxol, Toyocamycin,. , 0Transamination,. Transferases, glycosaminoglycan sulpho-,Transition element, 0sialyl, 0metals, complexes, 0, , , ,, , 0ions, spectra, oxidation state, peroxy-compounds, Tremetone, ‘‘ Triafulvenes,” Triarylmethyl cations, 0Triazines, Triazoles, Tribenzotriptycene, triplet state, Tri-n-butylsulphonium fluoride, clathratehydrate, Trichodermin,.0Trichodermol derivative, fungicidal, 0Trichothecin,. 0Ikicyanomethanide ion,. Tricyclodecanyl esters, acetolysis, Tricycle[ ,, ,0 °]deca-,, S-triene, Tricyclohexanes, 0Tricyclohexanones, Tricyclo[,,0,0a~]pentane derivative,, Tri(cyclopropy)methyl benzoate, solvoly-sis, Trifiuoromethyl, effect of substitution formethyl on crystallography, Trimethylamine oxide, Trimethylammonio -group, m -p - direc t ingin nitration,. Trimethylene thiourea, 0Trindane, 0,,-Trinitrobenzene and its derivatives,reactions, , spectra, ,,-Trinitrobenzene anion,. complexes, Trioxan,. 0,,-tricyclohexyl-, 0Triphenylcyclopropenium perchlorate,Triphenylmethane, acidity, 0Triplet excitom, , 00Triptycene, 0Fquinacene, , states, triplet state, Trishomocyclopropenyl ” cation,. SUBJEUTS Triterpenes, Tritium spectra, 0Trityl [carbolayZ-lsO]benzoate, l0-equili-bration,. Trityl cation,. 0, y -Tr opolone, Tropones, Truxillic acids, , Trypsin,. pancreatic, inhibitor of, 0Trypsinogen,. 0Tryptophan,. metabolism in relation tocancer, Tubercidin,. 0Tubercle bacilli, acids from, 0Tuberocidin,. Tubulosine, 00Tungsten complexes, LTunnelling, Twist form of steroids, Tyrosinosis, Uleine, 0Ultraviolet absorption of steroids, Umbilical cord, human,. Undeca-l,-diyne, hydration,. Uracil, -methyl-, 0, Uranium compounds, , Uraniuni (vI), determn,. extraction for analysis, Urea, tetramethyl-, aa medium for alkyla-tions, 0Urethane, -halogeno-N-phenyl-, cyclisa-tion,. Uric acid, -riboside, Ustilagic acid, Valence-bond approach for esr, Valence theory, organic, Vallesamine, 0, 0Vanadates, Vanadium complexes, compounds, Vasopressin,. complex with copper, dimer, Veatchine, 0Venenatine, 0Veratramine, Vemcarol, 0Verticillol, Vinblastine, 0Vindoline, Vindolinine, Vinyl radical, , Violanthrone, Violuric acid, 0Viomycin,. Viosamine, Virgiline, Voacamidine, 0Voacamine, 0Voacarine, 0Vobesine, 0, 0Voltammetry, compounds, use in analysis, 0 Vinca r0m alkaloids, 0Vomnga bis-indole alkaloids, 0Wagner-Meerwein rearrangement, Water, electronic spectrum, structure of, White birch sap, polysaccharide in,. spruce pulp, glucomannan in,. Widdrol, 0Wittig reaction,. 0Worn-Kishner reduction,. 0Xanthinuria, Xanthophanic acid, 0Xenon compounds, difiuoride, electronic spectrum, tetrafluoride, electronic spectrum, Xylam, o-Xylene anion,. X-Ray absorption-edge spectrometry, usecrystallography of nucleoside anologues,diffraction analysis, fluorescence, use in analysis, in anaIysis, a-Ylangene, Yohinibine, 0Zeatin,. Zinc compounds, ,Zirconium compounds, Printed in Great Britain by Butler & Tanner Ltd, Frome and Londo

ISSN:0365-6217    

DOI:10.1039/AR9646100671

出版商:RSC    

年代:1964

数据来源: RSC