INORGANIC CHEMISTRY1. INTRODUCTIONBy E. A. V . Ebsworth( University Chemical Laboratory, Cambridge)J. Lewis(The ‘victoria University of Manchester)THE general form of the Annual Reports is essentially the same as last year,except for the addition of a section on kinetics of inorganic reactions. Per-haps the most important development in the field of inorganic chemistryhas been the isolation of complexes of nitrogen with ruthenium andiridium, and the conversion of nitrogen into ammonia by transition-metalcomplexes.s This will obviously provide an impetus for considerable effortin this field of chemistry over the next few years.As noted last year, the rate of publication of Papers continues to in-crease, and hence the coverage of the literature in a report of this typebecomes more subjective.A number of review journals have appeared tohelp in the assimilation of this large flow of Papers, and it is to be hoped thatthese reviews will involve the comprehensive as well as the more generalreview articles. Among the new series which appeared this year areTramition Metal Chmistry, vol. 1--III,4 Structure and Bonding,S Organo-metallic Chemistry Reviews,6 and Co-ordination Chemistry Reviews.7 Anadditional communication journal, Inorganic and Nuclear Chemistry Letters,8the first number of which is dated October 1965, and the second volumeof Phillips and Williams’s book on ‘‘ Inorganic Chemistry ” have also beenpublished.A. D. Allen and C. V. Senoff, Chem. Comm., 1966, 621.a J. P. Collman and J. W.Kang, J . Amer. Chern. Xoc., 1966,88, 3459.M. E. Vol’pin and V. B. Shur, Nature, 1966, 209, 1236.Transition Metal Chemistry, ed. R. L. Carlin, Arnold, London, 1966.Structure and Bonding, Springer, New York, 1966.(I Organmetallic Chemistry Reviews, Elsevier, Amsterdam.Coordination Chemistry Reviews, ed. A. B. P. Lever, Elsevier, Amsterdam.a Inorganic and Nuclear Chemistry Letters, Pergamon Press, New York.O C. S. G. Phillips and R. J. P. Williams, “ Inorganic Chemistry,” vol. 11, ClarendonPress, Oxford, 19662. KINETICS AND MECHANISMS OF INORGANIC REACTIONSBy J. Burgess(Chemistry Department, Leicester University)As is usual in these Reports it is only possible to mention a proportion,here about a quarter, of the year's relevant references.In the process ofselection all references to two active fields which overlap organic chemistry,organo-silicon and -germanium chemistry, and oxidations of organic com-pounds by inorganic species, have been eliminated. The emphasis onreactions of transition-metal complexes in this Report reflects the continuedmajor interest in this aspect of inorganic kinetics. [Throughout this ReportL stands for any ligand, as specified in the text, X stands for a halogen atom((31, Br, I) unless otherwise stated, and AH$ and A$ represent enthalpiesand entropies of activation. References to the Russian literature quotepage numbers of the English translations.]Redox Reactions.-There has again been much work on inner-spherereductions of cobalt(m) Complexes by chromium(@. cis-[Co(en),(N,),]+ andcis-[Co(NHC,),(N,),]+ react by parallel paths involving a single or a doubleazide bridge.l For [Co(en>,(NCS)Xln+ (X = C1, NCS, NH,, OH,) chrom-ium@) attack can occur a t either nitrogen or sulphur to form the thiocyanatebridge., The importance of steric factors and ligand reducibility have beeninvestigated for reduction of thirty carboxylatopenta-amminecobalt(m)complexes ; for aromatic carboxylate ligands containing anitro group thereis evidence for chromium(n) attack a t the nitro group.3 The rate of ringclosure of [Cr( OH2),( O,C*CH,*CO,H)] ,+, containing unidentate malonate, tothe chelate [Cr( OH2),( O,C*CH,*CO,)] + is much slower than the rate of reduc-tion of [Co(NH,),( 02C*CH2*C02H)]2+ by chromium(n) .4 This evidence,together with rate constants and product distribution from analogous reduc-tions of malonate half-ester c~mplexes,~ refutes the earlier postulate ofchromium(@ attack a t the remote oxygen atom of the malonate ligand.The transition state now suggested contains chromium bonded to oxygenatoms from both carboxyl groups of the bridging malonate.The nature ofintermediates in the chromium( 11) reduction of nicotinamido- and isonicotin-amido-penta-amminecobalt(m) casts further doubt on the general applica-bility of the remote attack hypothesis.6 Reaction rates of chromium(I1) withcis- and truns-[Co(en),(OH2),]3+ and [Co(en),(OH2)(NH,)33f indicate a transeffect, though this is much less marked than for reduction by iron(=).'Electron exchange in the chromium(lr)-[Cr( OH2),(NH,)I3+ reactionoccurs by an inner-sphere mechanism.8 The detection of transient iron(m)* A.Haim, J. Amer. Chem. SOC., 1966, 88, 2324.a A. Haim and N. Sutin, J . Arner. Chem. Soc., 1966, 88,434.E. S. Gould, J . Amer. Chem. SOC., 1966, 88, 2983.D. €I. Huchital and H. Taube, Inorg. Chem., 1965, 4, 1660.D. H. Huchital and H. Taube, J . Amer. Chem. Soc., 1965, 87, 5371.6 F. R. Nordmeyer and H. Taube, J. Amer. Chem. SOC., 1966, 88, 4295.7 R. D. Cannon and J. E. Earley, J . Amer. Chem.Soc., 1965,87,5264; 1966,88,1872. * J. H. Espenson and D. W. Carlyle, Inorg. Chem., 1966, 5,586BURGESS : KINETICS O F INORGANIC REACTIONS 131complexes by fast reaction techniques in the reaction of iron(=) with severalcobalt@) complexes confirms that these are also inner-sphere reaction^.^Transition-state chromium-oxygen-vanadium bridging has now been demon-stratedl0 and may be compared with earlier reports of Cr-O-Cr and V-0-Vbridging.V-0-U bridging occurs in the vanadium(m)-uranium(vr) re-action.llThe use of the “oxygen isotopic fractionation factor,” f, the ratio ofrates, d In lS0/d In l*O, has been discussed as a means for differentiatingbetween inner-sphere and outer-sphere oxidations. For inner-sphere oxida-tions, e.g. [Co(NH3),( OH)]2+-chromium(rr), where Co-0 bond stretching isimportant in the formation of the transition state, f is significantly largerthan for outer-sphere oxidations, e.g. [CO(NH~),(OH)]~+-[RU(~H,),]~+.Vanadium(r1) and europium(rr) reductions have f values similar to those for[Ru(NH,),]~+ reductions, suggesting that these cations, unlike chromium(n),reduce penta-amminecobalt(m) complexes by an outer-sphere mechanism.12However, there is evidence for chlorine bridging in the europium(rr)-chromium (m) system.l3There have been several studies of outer-sphere redox reactions. Ratesand activation parameters have been determined by the temperature- jumptechnique for the hexachloroiridate(n)-hexabromoiridate(m) forward andreverse reactions.l4 Electron transfer rates in the manganate-perruthenatesystem have been reported ; in the ruthenate-perruthenate system rateswere too fast to follow. These results were compared with rnanganate-permanganate electron exchange data in the light of Marcus’s theories.15l[ron(m) oxidation of [Ta6CIl,] 2+ to [Ta,C1,2]4+ proceeds by two one-electrontransfers.16 Electron transfer in the system iron(=)-iron(m) in complexeswith 1,lO-phenanthroline (unsubstituted and methyl derivatives) is too fastto measure even from n.m.r. line-broadening.l7 Rates of oxidation ofruthenium@) complexes of substituted 1 ,lo-phenanthrolines by cerium(rv)are consistent with Marcus’s equations for outer-sphere oxidations.l*Activation energies and frequency factors for oxidation of the same com-plexes by thallium(~n),~~ and of iron(@ Complexes of the same ligands byperoxodisulphate, *O show linear correlation over a wide range of values.The question of one- or two-electron transfers in redox reactions involvingthallium has been discussed in several other papers. In the silver(n-thallium(1) reaction in nitric acid, two one-electron steps are indicated ;21similarly, results of vanadium( m)-thallium( III) experiments rule out simul-A.Haim and N. Sutin, J . Amer. Chem. SOC., 1966, 88, 5343.T. W. Newton and F. B. Baker, J . Phys. C‘hem., 1966, 70, 1943.lo J. H. Espenson, Inorg. Chem., 1965, 4, 1533.l3 H. Diebler, I?. H. Dodel, and H. Taube, Inorg. Clzern., 1966, 5, 1685.l3 A. Adin and A. G. Sykcs, J . Chem. SOC. (A), 1966, 1230.l5 E. V. Luoma and C. H. Brubacker, Inorg. Chena., 1966, 5, 1618, 1637.l6 J. H. Espenson and R. E. McCarley, J . Amer. Chern. Xoc., 1966, 88, 1053.l7 D. W. Larsen and A. C. Wahl, J. Chem. Phys., 1965, 43, 3765.l8 J. D.Miller and R. H. Prince, J . Chem. SOC. (A), 1966, 1370.J. D. Miller and R. H. Prince, J . Chem. SOC. (A), 1966, 1048.8 o J. Burgess and R. H. Frince, J . Chem. SOC. (A), 1966, 1772.21 R. ‘VV. Dundon and J. W. Gryder, Inorg. Chern., 1863, 5,986.P. Hurwitz and K. Kustin, Trans. Paraday SOC., 1966, 62, 427132 INORGANIC CHEMISTRYtaneous two-electron transfer.22 However, kinetics of the vanadium(@-t U u r n ( m ) reaction, and relative rates of reaction of vanadium(rr) andvanadium(rn) with thallium(m), suggest two-electron transfer in thiscase.23The importance of ion-pairing in redox reactions has been illustrated forreaction of ferrocyanide with peroxodisulphate, where variation of rate withpotassium ion concentration indicates that [KFe( CN),]3- and [KS,O,]- arethe reacting species.24Substitution Reactions of Complexes.-The temperature- jump methodhas proved valuable for studying kinetics of formation of complexes.Iron(rr) reacts with nitric oxide a t approximately the same rate as withlJ0-phenanthroline or 2,2’-bipyridyl.25 In formation of a-alanine com-plexes of nickel(=) and cobalt(@ the rate-determining step is the loss of awater molecule, but the kinetics of formation of the manganese(n) complexwith B-alanine are consistent with rate-controlling ring closure.a6 Tempera-ture-jump 27 and pressure-jump 28 studies of the reaction of nickel(=) withmalonate give similar results; the rate-determining step is the loss of waterfrom the nickel cation followed by reaction with malonate or hydrogenmalonate ion.This mechanism is the same as for the cobalt(@-malonatereaction.29 Temperature- jump studies of the reaction of magnesium(n)with oxine also indicate parallel reactions of the metal ion with ligand andwith protonated ligand.30The equilibrium Co3+ + C1- + CoC12+ in hydrochloric acid has beeninvestigated by the stopped-flow method.s1 The forward reaction is inter-esting as a rare example of a reaction of aquated cobalt(m). Formation ofthe mono-acetylacetone (acac) complex of iron(m) in acid solution 32 occurs,as in the malonate and oxine examples above, by parallel reactions of acacand acac.€€+ with FeSf or with Fe(OH)2+. But kinetics of reaction ofcopper(=) with acetylacetone indicate reaction only with the unprotonatedligand.s3 Rates of formation of terpyridyl complexes of first-row transitionmetals are similar to rates of formation of the respective 1,lO-phenanthroline,2,2’- bipyridyl, and pyridine complexes, which implies that attachment ofthe first nitrogen is the kinetically important stage for each of these ligands.The stability constants of the monoterpyridyl complexes are dictated byrates of dissociation rather than of formation.34 Replacement of watermolecules by diethylenetriamine (as dien.H+) or nitrilotriacetate (N’I’AS-)z 2 N.A. Daugherty, J. Amer. Chem. SOC., 1965, 87, 5026.2s F. B. Baker, w. D. Brewer, and T. W. Newton, Inorg. Chem., 1966, 5, 1294.84 R. W. Chlebek and M. W. Lister, Cunud. J. Chem., 1966, 44, 437.25 K. Kusth, I. A. Taub, and E.Weinstock, Inorg. Chem., 1966, 5, 1079.26 K. Kusth, R. F. Pasternak, and E. M. Weinstock, J . Amer. Chem. SOC., 1966,27 F. P. Cavasino, J . Phys. Chem., 1965, 69, 4380.28 H. Hoffman and J. Stuehr, J . Phys. Chem., 1966, 70, 955.2 8 F. p. Cavasho, RiceTCa S C ~ . , 1965, 8A, 1120.50 D. N. Hague and M. Eigen, Trans. Paraday soc., 1966, 62, 1236.31 T. J. Conocchioli, G. H. Nancollas, and N. Sutin, Inorg. Chem., 1966, 5, 1.82 W. K. Ong and R. H. Prince, J . Chem. SOC. (A), 1966, 458.33 R. c. &rile, M. Cefola, P. 8. Gentile, and A. V. Celiano, J . Phys. Chem., 1966,a4 R. H. Holyer, C. D. Hubbard, S . F. A. Kettle, and R. G. Wilkins, InoTg. Chem.,88, 4610.70, 1358.1966, 5, 622BURGESS : KINETICS O F INORGANIC REACTIONS 133in [Ni(0H2),L]2+ (L = substituted 1,lO-phenanthroline) occurs a t rateswhose logarithms correlate with Hammett Q constants for the respectivesubstituents.This shows effective transmission of substituent effects acrossboth ligand molecule and metal atom to the reaction site. The differencein electrostatic interaction accounts for the very much faster reaction of[Ni(OH2),L]2+ with NTA3- than with dien. H+.35The unwrapping of a multidentate ligand from one metal ion and itstransfer to another has been studied for copper(n)-EDTA reacting withnickel(=) and zinc(=) tetraethylenepentamine complexes,36 with zinc(=) inthe presence of hydroxide, acetate, and azide ions,S7 and for cobalt(n)-EDTAwith nickel@) .38 Dissociation of complexes of EDTA derivatives has alsobeen studied, €or instance mercury(rr)-trans- 1,2-diaminocyclohexanetetra-acetate in acid solution;3Q also cobalt@)-EDTA and cobalt(m)-hydroxy-ethylethylenediaminetriacetate in acid solution 4O and in the presence ofthaUium(m).41 The mechanism of EDTA exchange in solutions of itscalcium complex involves several paths, the relative importance of whichdepends strongly on pH.d2 Ligand exchange reactions for tetra-ligandcomplexes of zirconium, hafnium, and thorium with acetylacetone andtrifluoroacetylacetone have been investigated by n.m .r.spectros~opy.~~The dependence of racemisation rates of [Cr( 02C-C02)3]3- on the natureof the complementary alkali metal cation in solution suggests an inter-mediate in which an oxalate is bonded by only one oxygen to the chromium.44Hydrolysis rates of [Ni(aca~),],~~ and of [VO(acac),] and [ B e ( a c a ~ ) ~ ] , ~ ~ atvarying acid concentration, imply that protonation of unidentate acetyl-acetone molecules is an important factor in the mechanism, but kinetics ofaquation and lSO exchange for [Cr(acac),] show no evidence for a significantcontribution from protonation of unidentate ligand molecules.47There is still much work on reactions of complexes of the penta-amrninecobalt(n1) type.Gay and Lalor 48 were not able to distinguishbetween 8,lC.B and SN2P mechanisms for hydroxide reaction with[Co(NH3),(NCS)]2+ or [Cr(NH,),(NCS)J2+, but Banerjea and das Gupta 4Qfavour the &2IP mechanism for base hydrolysis of the former. For re-actions of [Co(en),LX]"+ (L = OH, NO2, Cl, or an amine; en = ethylene-diamine or one of its substituted derivatives) kinetics of reactions undervarious conditions, deuterium isotope effects, and steric effects all indicate85 R.K. Steinhaus and D. W. Margerum, J. Amy. Chern. SOC., 1966, 88, 441.36 D. W. Margerum and J. D. Carr, J . Amer. Chem. SOC., 1966, 88, 1639, 1645.37 D. W. Margerum, B. A. Zabin, and D. L. Janes, Inorg. Chem., 1966, 5, 250.38 T. R. Bhat, D. Radhamma, and J. Shankar, Inorg. Chem., 1966, 5, 1132.38 D. 1;. Janes and D. W. Margerum, Inorg. Chem., 1966, 5, 1135.40 S. P. Tanner and W. C. E. Higginson, J. Chem. SOC. (A), 1966, 537.41 S. P. Tanner and W. C. E. Higginson, J. Chem. SOC. ( A ) , 1966, 59.42 R. J. Kula and G. H. Reed, Analyt. Chem., 1966, 38, 697.43 A.C. Adams and E. M. Larsen, Inorg. Chem., 1966, 5, 228, 814; T. J. Pinnavaia44 J. A. Kernohan, A. L. Odell, R. W. Olliff, and F. B. Seaton, Nutwe, 1966, 209,4 5 R. G. Pearson and J. W. Moore, Inorg. Chem., 1966, 5, 1523.R. G. Pearson and J. W. Moore, Inorg. Chem., 1966, 5, 1528.4 7 J. Agett and A. L. Odell, J. Chem. SOC. (A), 1966, 1820.46 D. L. Gay and G. C. Lalor, J. Chern. SOC. (A), 1966, 1179.4Q D. Banerjea and T. P. das Gupta, J. InoTg. Nuclear Chem., 1966, 28. 1667.and R. C. Fay, ibid., p. 233.906134 INORGANIC CHEMISTRY&11P or &21P mechanisms, never XNlCB.50 Ion-pairing has a markedeffect on the rate of aquation of [Cr(NH,),Cll2+ in the presence of sulphate,nitrate, or several organic anions; faster rates in the presence of these ionsare ascribed to enhanced reactivity of ion-~airs.5~ Kinetics and products ofbase hydrolysis of [CO(NH,),X]~+ (X = C1, Br, I, NO,) in solutions contain-ing added ions, e.g., NCS-, SO4,-, can be explained much morereadily by an SNICB than by an 5,2 but kinetics of cyanideexchange with [Co(en),(SO,)(CN)] seem inconsistent with an SNlcB mech-a n i ~ r n .~ ~ Kinetic studies of this type in non-aqueous solvents are yieldingresults but it is still too early to draw definite conclusion^.^^Both cis- and trans-[Co( en),(NO,) (NCS)] + and [Co(en),(NO,) (NH9)I2 +, inacid solution, aquate by an SN1C.A mechanism rather than the SN2CAmechanism more usually found for cobalt(m), rhodium(rn), and iridium(m)complexes of this type.55 Several other examples of the importance ofprotonation of nitro groups in acid aquation have been reported, for the[Co(NR,),(NO,)] +, [ Co( NH,),(NO,),] +, and [Co ( en),(NO,),] + cations.56Reactions of [ Co (NH,) (OH,)] + and [Co (en) , (OH,) ,] + with cyanat e havebeen studied by tracer experiments. The product carbamato-complex isformed from the former without breaking the cobalt-oxygen bond, and inthe [Co(en),(CO,)]+ from the latter the carbonato ligand contains one oxygenatom from the water originally on the cobalt, one from the cyanate, andone from the solvent.67Rates of halogen exchange for [Rh(NH3),XI2+ and [:Ir(NH3)5X]2+ arein the same order as rates for the analogous halogenopenta-amminecobalt(m)complexes 58 and parallel ligand-field strengths, but reaction rates of[Rh(NH3),XI2+ with hydroxide are in the opposite order.59 A significanttrans effect, both on rates and on actimtion energies, has been reportedfor trans-[Rh(en),X,]+ reacting with various X-.Results imply a widevariation in the importance of Rh . . . OH2 bonding in the transition statesfor different pairs of halogens as X and Reaction of [Rh(OH,)J3+with chloride involves the initial rate-determining loss of one water molecule ;the marked inverse dependence of rate on pH is due to the greater reactivityof [Rh(OH2),(0E)]2+ than of the hexa-squo ion.61Further examples of square-planar complexes which exhibit kineticbehaviour characteristic of octahedral complexes have been reported. InSo S. C . Chan and F.Leh, J . Chem. SOC. (A), 1966, 126, 129, 134, 138; S. C. man,ibid., pp. 142, 1124, 1310.61 J. B. Walker and C. B. Monk, J . Chem. SOC. ( A ) , 1966, 1372.62 D. A. Buckingham, I. I. Olsen, and A. M. Sargeson, J . Amer. Chem. SOC., 1966,53 E. Campi, C. Paradisi, G. Schiavon, and M. L. Tobe, Chem. Comm., 1966, 682.64 E.g., B. Bosnich, J. Ferguson, and M. L. Tobe, J. Chem. SOC. ( A ) , 1966, 1636.55 R. V. Bradley, E. 0. Greaves, and P. J. Staples, J . Chem. SOC. ( A ) , 1966, 986.68 G. C. Lalor, J . Chem. SOC. ( A ) , 1966, 1; D. G. Lambed and J. G. Meson, J. Amer.Chem. SOC., 1966, 88, 1633, 1637; U. D. Gomwalk and A. McAuley, J . Chem. SOC. (A),1966, 1692, 1694.5 7 A. M. Sargeson and €3. Taube, Inorg. Chem., 1966, 5, 1094.68 G. B. Scmidt, 2.phys. Chem. (Frankfurt), 1966, 50, 222.59 0. W. Bushnell, G. C. Lalor, and E. A. Moelqm-Hughes, J . Chem. SOC. ( A ) ,60 H. L. Bott, E. J. Bounsall, and A. J. Poci, J . Chem. Soc. ( A ) , 1966, 1275.61 K. Swaminathan and G. M. Harrsi, J . Amer. Chem. SOC., 1966, 88, 4411.88,5443.1966, 719BURGESS : KINETICS O F INORGANIC REACTIONS 135palladium(=) complexes of N-alkyltriamines bulky alkyl groups lead to such“pseudo-octahedral ” behaviour. Hydroxide ion catalysis has been demon-strated for these complexes and explained by a CB mechanism; this is thefist example of hydroxide catalysis in a square-planar system.62 Pseudo-octahedral behaviour is also found 63 in reactions of the gold(m) complex[AU(l?h4dien-H)X](PF6), where Et,dien-H represents the anion formed byremoval of a proton from tetraethyldiethylenetriamine, but the species[Au(dien)ClI2+, which lacks the sterically-interfering ethyl groups, exhibitsnormal square-planar kinetic behaviour.The normal rate law also appliesto reactions of [AuC13L] (L = heterocyclic nitrogen base) with chloride,azide, and nitrite,64 and to the reverse reaction of [AuClJ- with L.65 The[AuCl,L] reactions exhibit marked nucleophilic discrimination, and second-order rate constants depend greatly on the nature of the substrate andentering group. Rate constants for reaction with chloride are linearly relatedto the basicity of the leaving group. Rate constants for reaction of[Pt(bipy)Cl,] ~ t h aliphatic amines and pyridines are linearly related to thebasicity of tbe entering group,66 though basicity plays a smaller role in deter-mining reactivity in platinum(@ than in gold@) complexes.Rate con-stants, and so,me AH$ and AS$ values, have been reported for many reactionsof [PtL,X,] (L = nitrogen or phosphorus base). Complexes where L = PEt,have proved especially useful as they shorn high nucleophilic discrimination.Results are discussed in terms of ligand polarisabilities and solvationeffects.67 Although the rate law for hydroxide reaction with trans-pt( H2N*CH,~CH2*OB),C1,] takes the form normal for square-planar species,direct attack of hydroxide at platinum seems less likely than an anchimericassistance mechanism.6g Isomerisationrates for [Pd(NCS)L] + + [Pd(SCN)L]+[L = (Et,N*CH,*CH,),NH], and reaction rates for both isomers with brom-ide, indicate that this isomerisation is inter- rather than intra-molecular.6*The trans effect in palladium@) complexes has been studied for carbonmonoxide reaction with [PdX,IZ- (X = halide, NO,, NCS, CN). Theseand earlier resnlts lead to the same trans effect series as established forplatinum(@ Kinetics of cleavage of halogen-bridged platinum( n) com-plexes by amines have been compared with those of amine attack on normalunbridged platinum(n) complexes.71Ca,rbonyls.-Kinetics of carbon monoxide exchange, and of triphenyl-phosphine reaction, with nickel carbonyl are fist-order in carbonyl and zero-order in CO or PPh,, and the reactions occur a t similar rates in toluene62 W. H. Baddley and F.Basolo, J. Amer. Chem. SOC., 1966, 88, 2944.63 C. F. Weick and F. Basolo, Inorg. Chem., 1966, 5, 576.64 L. Cattalini and M. L. Tobe, Inorg. Chem., 1966, 5, 1145.65 L. Cattalini, M. Nicolini, and A. Orio, Inorg. Chem., 1966, 5, 1674.66 L. Cattalini, A. Orio, and A. Doni, Inorg. Chem., 1966, 5, 1517.6 7 G. Faraone, U. BeUuco, V. Ricevuto, and R. Ettorre, J . Inorg. Nuclear Chem.,1966, 28, 863; U. Belluco, A. Orio, and M. Martelli, Inorg. Chenz., 1966, 5, 1370, andreferences therein.68 F. Basolo and K. H. Stephen, Inorg. Nuclear Chem. Letters, 1966, 2, 23.F. Basolo, W. H. Baddley, end K. J. Weidenbaum, J . Amer. Chem. SOC., 1966.7 O A. B. Fasman, G. G. Kutyukov, and D. V. Sokol’skii, Russ. J . Inorg. Chem.,7l R. G. Pearson and M. M. Muir, J .Amer. Chem. SOC., 1966, 88, 2163.88, 1576.1965, 10, 727136 INORGANIC CHEMISTRYat 0"c. It was therefore assumed that these reactions had a common rate-determining step, the loss of a molecule of CO from the carbonyl. Enthlpiesand entropies of activation €or the two reactions have now been shown todiffer greatly, implying more complicated mechanisms.72 Results have alsobeen published for similar reactions of Hg[Co(CO),], and related c0mpounds.7~Werner and Prinz v4 found reactions of molybdenum hexacarbonyl withbenzene derivatives, amines, and phosphines to be first-order in carbonyland zero-order in base, although rates did depend on the nature of theentering base. Angelici and Graham,75 working a t higher base concentra-tions, showed that the full rate-law was: rate = E,[Mo(CO),]+E,[Mo(CO),][base]. The second-order term represents Sx2 attack by the base, butwhether at molybdenum or carbon is not known.In compoundsMo(CO),L, (L = toluene, p-xylene, mesitylene) replacement of L by PCl,,PPhCl,, or P(n-C4Hg)3 follows simple second-order kinetics.76Reaction of Co(CO),(NO) with phosphines, arsines, or nitrogen bases itJsecond-order, in contrast to analogous reactions of isoelectronic Ni(Co),.'?There is a similar difference in kinetic behaviour between reactions of theisoelectronic compounds Co(CO),(NO)L and Ni( CO),L [L = Asph,, P(OR),,Decomposition of cobalt hydrogen carbonyl is a simpl~ second-orderrea~tion.'~ Replacement of carbon monoxide in n-cyclopentadienylrhodiumdicarbonyl by phosphine, phosphites, and isonitriles is also second-order.mAddition of water, oxygen, or methyl iodide to trans-[Ir(CO)(PPh,),X] isagain second-order ; the activation parameters give some clues to the naturesof the transition states.81Typical Elements.-Decompositions of nonaborane-15 and octaborane-12are first-order.82 Reactions of the type PhBC1, plus 2,4-dinifronaphthyl-amine show second-order kinetics and are thought to occur by an SN2mechanism.83 The mechanism of decomposition 84 of BH,,PF, and similaradducts is similar to that of BIE,,CO, that is BH,,L + BH, + L followedby BH, + BH,,L ---f B2H6 + L.Alkaline hydrolysis of BF,,ONMe,, ~ E Iof BF,,amine adducts, is first-order, independent of hydroxide concentra-tion ;a5 alkaline hydrolysis of SO,,NEt, is second-order, which is consistentwith nucleophilic attack by OH- a t sulphur.86 Kinetics of hydroxidereaction with difluoramine, HNF,, are also second-order ; the mechanismL.R. Kangas, R. F. Heck, P. M. Henry, S. Breitschaft, E. M. Thorsteinson, and78 S. Breitschaft and B. Basolo, J . Amer. Chem. SOC., 1966, 88, 2702.7 4 H. Werner and R. Prinz, J . Organometallic Chem., 1966, 5, 79; H. Werner, ibid.,75 R. J. Angelici and J. R. Graham, J. Amer. Chem. SOC., 1966, 88, 3658.76 F. Zingales, A. Chiesa, and F. Basolo, J . Amer. Chem. SOC., 1966, 88, 2707.77 R. J. Mawby, D. Morris, E. M. Thorsteinson, and F. Basolo, Inorg. Chem., 1966,5, 27; E. M. Thorsteinson and F. Basolo, J. Amer. Chem. SOC., 1966, 88, 3929.78 E. M. Thorsteinson and F.Basolo, Imrg. Chem., 1966, 5, 1691.7s K. H. Brandes and H. B. Jonassen, 2. anorg. Chem., 1966, 343, 215.H. G. Schuster-Woldan and F. Basolo, J . Amer. Chem. SOC., 1966, 88, 1657.81 P. B. Chock and J. Halpern, J. Amer. Chm. SOC., 1966, 88, 3511.82 J. F. Ditter, J. R. Spielman, and R. E. Williams, Inorg. Chem., 1966, 5, 118.84 A. B. Burg and Yuan-Chin Fu, J. Amer. Chem. SOC., 1966, 88, 1147.8s I. G. Ryss and S. L. Idel's, Rust?. J . Inorg. Chem., 1966, 10, 424.86 I. G. Ryss and L. P. Bogdanova, Rws. J . Inorg. Chem., 1965,lO. 91.F. Basolo, J. Amer. Chem. SOC., 1966, 88, 2334.p. 100.J. C. Lockhart, J. Chem. SOC. (A), 1966, 809BURGESS : KINETICS O F INORGANIC REACTIONS 137may be SN2, as for NF,, or assisted XN1, but does not involve ionisation ofHNF2.s7 Rates of racemisation and deuteriation of the complex cation[Co(NH3),(CH3*NH-CH,.C0,)12' suggest retention of configuration aboutthe sarcosine-N atom for a kinetically significant, time after loss of theproton.Cleavage of Sn-Sn bonds in hexaphenylditin has been investigated byreaction with iodine.The second-order kinetics, e.s.r., and DPPH reactionexperiments give no evidence for a significant contribution from radicalreacti0ns.8~ Nor is there any evidence for the generation of radicals duringthe iodination of several other ditin compounds in a variety ofexcept from hexamethylditin under the most favourable condition^.^^ Pre-equilibrium with solvent followed by formation of an acyclic four-centretransition state seems the more usual mechani~rn.~~ Tin-phenyl bondcleavage in the reaction of Ph2SnC1, with oxine takes place both by simplebond breaking and by formation and decomposition of an adductPh,SnCl,,(~xine),.~~ The mechanism of reaction of tetra-alkyl lead com-pounds with iodine is SE2 substitution a t carbon; results in a variety ofsolvents indicate significant solvation in the transition state.93Anions.-Kinetics of hydrolysis of pyropho~phite,9~ pyrophosphate~,~~and peroxopho~phates,~~ of alcoholysis of polyphosphoric acidsYg7 and ofreaction of peroxo-di-phosphate with iodine have been reported.gs In allcases the variation of concentrations of variously protonated species a tdifferent pH values makes deduction of complete reaction mechanismshazardous if not impossible.Similar difficulties are encountered in halide-halate reactions, e.g., iodide-cWorite.99 The most informative work hasbeen the investigation of base hydrolysis of the dichromate ion by water,ammonia, hydroxide ion, and 2,6-lutidine. lo0 The order of reactivityparallels basicity if due allowance is made for electrostatic repulsion andfor steric effects in the cases of hydroxide and lutidine, respectively. Thebehaviour of Cr,0,2- is very similar to that of S,0,2-A. D. Craig and G. A. Ward, J. Amer. Chem. SOC., 1966, 88, 4526.88 B. Halpern, A. M. Sargeson, and K. R. Turnbull, J. Amer. Chem. SOC., 1966, 88,D. N. Hague and R. H. Prince, J. Inorg. Nuclear Chem., 1966, 28, 1039.O0 G. Tagliavini, S. Faleschini, G. Pilloni, and G.Plazzogna, J. OrganometaUk91 H. C. Clark, J. D. Cotton, and J. H. Tsai, Canad. J. Chem., 1966, 44, 903.OS D. F. Martin and R. D. Walton, J. OrganometaUic Chem., 1966, 5, 57.OS L. Riccoboni, G. Pilloni, G. Plazzogna, and G. Tagliavini, J . ElectroanaZyt. Chem.O4 R. E. Mesmer and R. L. Carroll, J . Amer. Chem. SOC., 1966, 88, 1381.O 5 R. P. Mitra, H. C. Malhotra, and D. V. S. Jain, Trans. Faraday SOC., 1966, 62,O 6 S. H. Goh, R. B. Heslop, and J. W. Lethbridge, J. Chem. SOC. ( A ) , 1966, 1302.9 7 F. B. Clarke and J. W. Lyons, J. Amer. Chem. Soc., 1966, 88, 4401.98 A. Indelli and P. L. Bonora, J. Amer. Chem. SOC., 1966, 88, 924.99 J. de Meeus and J. SigalIa, J. Chim. phys., 1966, 63, 453.4630.Chem., 1966, 5, 136.Interfacial Electrochem., 1966, 11, 340.173; C.A. Bunton and H. Chaimovich, Inorg. Chem., 1965, 4, 1763.loo P. Moore, S. F. A. Kettle, and R. G. Wilkins, Inorg. Chern., 1966, 5, 2203. THE TYPICAL ELEMENTS,By A. J. Downs(Inorganic Chenzistry Laboratory, South Park8 Road, Oxford)E. A. V. Ebsworth and J. J. Turner( Univer&ty Chemical Laboratory, Lensfceld Road, Cambridge)IN the past year there has been no particularly important advance in thechemistry of the typical elements. A series of papers deals with the electro-chemistry of organometallic compounds and the electrochemical formation ofmetal-metal b0nds.l Other work implies that two commonly used methodsof assessing the strengths of donor-acceptor bonds are of doubtful validity :manometric investigations of some sulphide adducts do not support a scaleof donor strengths based on adduct volatility;2a the variations in the (CkO)stretching frequency of perinaphthenone accompanying reaction with variousacceptors are not directly related to the formation constants of the com-plexes.2b For adducts of several Lewis acids, the relative strengths of basesappear to depend principally on the strength of the acid, and not neces-sarily on supplementary rc-bonding.2c The concept of the donor number hasbeen introduced into discussions of non-aqueous solvents.2dReviews have been published on the following topics : the structures andreactions of carbanionic organometallic compounds 3a of the elements ofGroups I-VI ; the preparation of methylmetal compounds using fusedsalts ; 3b the preparation and properties of pentafluorophenyl compounds ofmain group and transition elements ;3c organometnllic azides ;3d inorganicanalogues of carbenes ;3* five co-ordination ;3t the n.m.r.spectra of organo-metallic compounds.39 A monograph dealing with the hydrogen compoundsof the metallic elements 40 has appeared; a collection of articles about non-aqueous solvent systems has been p~blished,~b and a substantial study ofinorganic and general chemistry in liquid ammonia4c represents Part I ofVolume I of a series. A collection of data relating to the appearance poten-(a) R. E. Dessy, W. Kitching, and T. Chivers, J . Amer. Chem.Soc., 1966,88,453;( b ) R. E. Dessy, T . Chivers, and W. Kitching, ibid., p. 467; (c)R. E. Dessy, P.M. Weissman,and R. L. Pohl, ibid., p. 5117; (d) R. E. Dessyand P. M. Weissman, ibid., pp. 5124, 5129.a (a) H. A. Norris, N. I. Kulevsky, 31. Tamres, and S. Searles, Inorg. Chem., 1966,5, 124; ( b ) A. Mohammed and D. P. N. Satchell, Chem. and I d . , 1966, 2013; (c) D. E.Young, G. E. McAchan, and S. G. Shore, J . Amer. Chem. doc., 1966, 88, 4390; (d) V.Gutmaun and E. Wychera, Inorg. Nzcclear Chem. Letters, 1966, 2, 257.( a ) W. Tochtermann, Angew. Chem., Internat. Edn., 1966, 5, 351; (b) W. Sunder-meyer and W. Verbeek, ibid., p. 1 ; (c) R. D. Chambers and T. Chivers, OrganometallicChem. Rev., 196G, 1, 279; ( d ) J. S. Thayer, ibid., p. 157; (e) 0. M. Nefedov and M. N.Manakov, Angew. Chem., Internat. Edn., 1966, 5, 1021; (f) E. L. Muetterties and R.A.Schunn, Quart. Rev., 1966, 20, 245; (9) M. L. Maddox, S . L. Stafford, and H. D. Kaesz,Adu. Organometallic Chem., 1965, 3, 1.4 ( a ) I<. M. Mackay, “ Hydrogen Compounds 4: the Metallic Elements,” E. an:F. N. Spon, London, 1966; (b) T. C. Waddington,Academic Press, 1965; (c) J. Jander, Chemistry in Liquid Ammonia-I. Inorganicand General Chemistry in Liquid Ammonia,” Vieweg, Brunswick, and Interscience,New York-London, 1966.Non-aqueous Solvent SystemsDOWNS, EBSWORTH AND TURNER: THE TYPICAL ELEMENTS 139tials of volatile inorganic compounds has been made,5a and to the Sadtlercollection of the infrared spectra of 600 inorganic compounds5b have beenadded the spectra of 400 organometallic derivatives.5cGroup 0.-Noble-gas chemistry has been reviewed,6 and noble-gas rad-iation chemistry discussed.‘ Krypton difjluoride can be prepared by theexposure of a krypton-fluorine mixture fa daylight;gu E(Kr-F) has thesurprisingly low value 8b of 12 kcal.mole-1.There is no evidenceg for theformation of krypton-oxygen compounds from the ra.dioactive decay ofK83Br0,. The existence of XeF, and XeF, has not been confirmed.1°Electric discharge in a gas mixture of Xe, F,, and CCl, (or SiC1,) givescolourless crystals whose vapour shows a mass spectrum containing XeC1-;the formation of XeC1, is deduced;lla liquid chlorine and gaseous Xe underpressure slowly formed crysta1s,llb perhaps of XeCI,. Further investi-gation of the Xe-PtF5 system l2 has led to the preparation of XeF,+PtF,-,the XeF5+ ion being approximately square-pyramidal [Xe-F(4) = 1.90 8;Xe-F(1) = 1-77 8; F(4)-Xe-F(1) = 83’1.Heat-capacity data suggestthat there are three structural modifications l3 of solid XeF,; the non-octahedral structure o f gaseous XeF, has been ~ ~ I l f i r r n e d , ~ ~ and the structurediscussed theoretically.15 The magnetic susceptibility16 9 l7 of solid XeF,indicates the absence of a lom-lying triplet state; the l9F n.m.r. spec-trum l7 of solid XeF, and the I‘O n.m.r. spectrum l8 of liquid XeOF,have been examined. Further reported complexes are 4XeF,,SnF4,1g2XeF,,VF,, 2XeOF,,VF5,20 XeOF,,CsF, 2XeOF4,3RbF, Xe0F4,3KF,XeOF4,2SbF,, 21 XeFG,2NOF, and XeOF,,NOF ; infrared spectra suggest( a ) H. J. Svec, “Mass Spectrometry,” NATO Adv. Study Inst.Glasgow, 1964(publ. 1965); (b) “ High Resolution Spectra of Inorganics and Related Compounds,”Sadtler Research Laboratories, Philadelphia, 1965; ( c ) “ Infrared Grating Spectra ofOrganometallic Compounds,” Sadtler Research Laboratories, Philadelphia, 1966.R. Hoppe, Fortschr. Chem. Forsch., 1965, 5, 213; A. B. Neiding, Russ. Chem.Rev., 1965, 34, 403; G. J. Moody and J. D. It. Thomas, Rev. Pure AppZ. Chem., 1966,16, 1.J. P. Adloff, Radiochim. Acta, 1966, 6, 1; G. J. Moody and J. D. R. Thomas,Nature, 1965, 206, 613.* (a) L. V. Streng and A. G. Streng, Inorg. Clzem., 1966, 5, 328; (b) S. R. Gunn,J. Amer. Chem.Xoc., 1966, 88, 5924.A. N. Murin, T7. D. Nefedov, I. S. Kirin, S. A. Grachev, Yu. K. Gusev, and G. N.Shaplzin,J. Gen. Chem. (U.S.S.R.), 1965, 35, 2126.lo R.Weinstock, E. E. Weaver, and C. P. Knop, Inorg. Chem., 1966, 5, 2189.l1 (a) H. Meinert, 2. Chem., 1966, 6, 71; (b) S. F. a. Kettle, Chem. and I n d , , 1966,l2 N. Bartlett, F. Einstein, D. F. Stewart, and J. Trotter, Chem. Comm., 1966, 550.l3 J. G. M a h , F. SchrcL?er, 2nd D. W. Osborne, Inorg. Nuclear Chem. Letters, 1965,l4 K. Hedberg, S. H. Peterson, R. R. Ryan, and B. VVeinstock, J . Clzenz. Phys.,l5 R. D. Willett, Theor. Chim. Acta, 1966, 6, 186; L. S. Bartell, Trans. Amer. Cryst.l6 ( a ) B. Volaviiek, Monatsh., 1966, 9’7, 1531; (b) H. Selig and F. Schreiner, J . Chem.l7 R. Blinc, E. Pirkmajer, J. Slivnik, and I. ZupenEi6, J . Chem. Phys., 1966, 45,lS J. Shamir, H. Selig, D. Samuel, and J. Reuben, J . Amer. Chem.Soc., 1965, 87,l9 K. E. Pullen and G. H. Cady, Irzorg. Chem., 1966, 5, 2057.2o G. J. Moody and H. Selig, J . Inorg. Nuclear Chem., 1966, 28, 2429.a1 H. Selig, Inorg. Chm., 1966, 5, 183.1846.1, 97.1966, 44, 1726.ASSOC., 1966, 2, 134.Phys., 1966, 45, 4755.1488.2359140 INORGANIC CHEMISTRYthat the last two contain the NO+ ion.22 Infrared and X-ray evidence 11~23indicates that the Xe0,F- ion is not present in CsXe0,F. Mixtures of XeF,and XeF, in SbF, form green solutions 24 which from their e.s.r. spectra maycontain Xe(m). Raman spectra afford no evidence 25 for the formation ofXe0,F2 on addition of water to XeOF, in liquid El?; infrared evidence forthe formation of XeOF, at low temperatures has been presented.26 Thepreparations of CsHXeO, 27 and Am4(Xe0,),,40H,O 28 have been described.The negative interaction force constant 29 in KrF, has been simply ex-~lained.~*Group 1.-More information about alkali metal solutions in liquidammonia and amines emerges from measurements of heats of solution 31a andelectron spin resonance and electronic absorption ~pectra.3~~ One conclu-sion 31b is that the blue diamagnetic species present in moderately concen-trated solutions is most satisfactorily represented by (e22-)so1v.; in primaryamines31c RNH2 solvated atoms are present as well as solvated electrons, andthe spectroscopic properties are very dependent on R. The inversionalmotion of the ammonia molecule may be the basis of the conduction mechan-ism in dilute solutions of lithium in liquid ammonia.31d Certain propertiesof dilute alkali metal-ammonia solutions can be explained 32 by a modelinvolving equilibria between the solvated metal cation M+ and anion M-,the solvent S, the anion S-, and the ion-pairs M+M- and M+S-.Protonn.m.r. spectra of liquid ammonia solutions of alkali salts reflect ion-solvation,ion-association, and hydrogen- bonding effects. 33Magnetic resonances of the nuclei 23Na, 39K, 87Rb, and la3Cs in aqueousalkali salt solutions 34 disclose the following order of increasing shielding bythe anions: I- < Br- < C1- < F- < H20 < NO,-; overlap repulsive forcesbetween the closed-shell ions may account for the observed chemical shifts.Despite the relative insensitivity to structural effects, 'Li resonances mayprovide information about the solvation of Li+ ions in solution,35 and aboutorganolithium exchange rea~tions.~a Broad-line measurements on poly-23 G.J. Moody and H. Selig, Inorg. Nuclear Chem. Letters, 1966, 2, 319.23 R. D. Peacock, H. Selig, and I. Sheft, J. Inorg. Nuclear Chem., 1966, 28, 2561.2a B. Cohen and R. D. Peacoolr, J . lnorg. Nuclear Chem., 1966, 28, 3056.26 H. H. Selig, L. A. Quarterman, and H. H. Hyman, J . Inorg. Nuclear Chem.,2 7 B. Jaselkis, T. M. Spittler, and J. L. Huston, J . Amer. Chem. Xoc., 1966, 88,2s H. H. Claassen, G. L. Goodman, J. G. Malm, and F. Schreiner, J . Chem. Phys.,1965, 42, 1229.ao C. A. Coulson, J . Chem. Phys., 1966, 44, 468.31 (a) T. R. Tuttle, jun., C. Guttman, and S . Golden, J . Chew.Phys., 1966, 45,2206; ( b ) R. Catterall and M. C. R. Symons, J. Chem. SOC. ( A ) , 1966, 13; (c) R. Catterall,M. C. R. Symons, and J. W. Tipping, ibid., p. 1529; ( d ) E. C. Evers and F. R. Longo,J . Phys. Chem., 1966, 70, 426.1966, 28, 2063.J. S. Ogden and J. J. Turner, Chem. Comm., 1966, 693.Y. Marcus and D. Cohen, Inorg. Chem., 1966, 5, 1740.2149.32 S . Golden, C. Guttman, and T. R. Tuttle, jun., J . Chem. Phys., 1966, 44, 3791.33 A. L. Allred and R. N. Wendriclrs, J. Chem. SOC. ( A ) , 1966, 778.34 C. Deverell and R. E. Richards, MoZ. Phys., 1966, 10, 551.s 5 G. E. Maciel, J. K. Hancock, L. F. Lafferty, P. A. Mueller, and W. K. Musker,Inorg. Chem., 1966, 5, 554.36 L. M. Seitz and T. L. Brown, J. Amer. Chem. Soc., 1966, 88, 2174, 4140; K.C.Williams and T. L. Brown, {bid., p. 4134; G. E. Hartwell and T. L. Brown, ibid., p. 4626DOWNS, EBSWORTH AND TURNER: THE TYPICAL ELEMENTS 141crystallinelithium compounds 37a reveal structural effects like the two non-equivalent lithium sites in lithium nitride.37bOrganolithium compounds have been reviewed. 38 Kinetic experiments onmetallation reactions indicate a9a that organolithium aggregates can act askinetically active species ;denends on the structurethe extent of aggregation in basic solventsof the organometallic compound.39b Spectro-scipic data suggest 40 that in but-3-enyl-lithium interadion occurs betweenvacant orbitals on the hexameric lithium framework and the n-orbitals of thebutene moiety (1). The formation of specific organolithium-tetrahydrofurancomplexes is revealed by the electronic spectrum of 1 ,l-diphenyl-n-hexyl-lithium,41 the acidity of the Li+ cation varying with the extent of solvation.Evidence from several sources suggest,s that lithium bromide exists astetramers in diethyl ether solution.42 Lithium nitroxide, formed throughreaction of lithium atoms and NO in solid argon a t high dilution, has a bentmolecule 43 and is probably LiON rather than LiNO (LiON = 100" & 10").Microwave spectra, 44 of the gaseous hydroxide molecules CsOH and KOHconform, however, to the linear-molecule pattern, although a " quasilinear "structure cannot be excluded.Group II.-Organoberyllium hydrides, RBeH (R = Me, Et or Ph), canbe prepared as diethyl ether complexes from the appropriate diorgano-beryllium, beryllium bromide and lithium hydride ;45 the liquid 1 : 1 complexof methylberyllium hydride is a dimer, [MeBeH,Et,O],.Organoberylliumhydrides and related compounds add to unsaturated systems like olefins,aldehydes, and ketones; 45 reaction rates are sensitive to the presence(a) R. A. Bernheim, I. L. Adler, B. J. Lavmy, D. C. Lini, B. A. Scott, and J. A.Dixon, J . Chem. Phys., 1966, 45, 3442; ( b ) S . 0. Bishop, P. J. Ring, and P. J. Bray,ibid., p. 1625.38 T. L. Brown, Adv. Organometallic Chem., 1965, 3, 365.39 ( a ) T. L. Brown, J . Organometallic Chem., 1966, 5, 191; R. Waack, P. West, andM. A. Doran, Chem. and Ind., 1966, 1035; ( b ) R. Waack and P. West, J . OrganometallicChem., 1966, 5, 188.40 J.P. Oliver, J. B. Smart, and M. T. Emerson, J . Amer. Chem. Xoc., 1966, 88,2109.41 R. Waack, M. A. Doran, and P. E. Stevenson, J . Amer. Chem. Soc., 1966, 88,4101.42 M. Chabanel, J . Chim. phys., 1966, 63, 1143.43 W. L. S. Andrews and G. C. Pimentel, J . Chem. Phys., 1966, 44, 2361.44 R. L. Kuczkowski, D. R. Lide, jun., and L. C. Krisher, J . Chem. Phys., 1966,46 N. A. Bell and G. E. Coatea, J . C h m . SOC. ( A ) , 1966, 1069.A44, 3131142 INORGANIC CHEMISTRYof ether and to the site of unsaturation in the organic molecule. Onthe basis of n.m.r. spectr0scopy,4~ cis-trans isomerism of the dimerMe,N(Me)BeH,Be(Me)NMe, is indicated. Tetramethyltetrazene reacts withdialkylberylliums to give both 1 : 1 and 1 : 2 complexes(Me,N*N=N-NMe2,R2Be) ; 47pyrolysis of the latter leads to polymers of low molecular weight.Theberyllium derivatives of NNN'- trimet hyle t hylenediamine, 2 -met hoxyet hanol,2 -&met hylaminoethanol, and 2-dimet hylaminoet hanethiol range frommonomers to polymers.48 Spectroscopic properties of methylberylliumcompounds such as Na2[Me,Be,H,] and trimethylamine and tetramethyl-ethylenediamine complexes of Me,Be are correlated with the structural unitspresent,49 and a conformationally labile 6-membered ring structure isassigned to [MeBeNMe,],. Beryllium borohydride complexes, L,Be(BH,),(L = Et,O, Me,P, Me2PH, Et,P, Me,", and Me2NH) are liquid a t roomtemperature, and monomeric in benzene. 50 Interaction of beryllium acetyl-acetonats with phosphonitrilic derivatives like Ph2P( O)NPPh,OH producesboth mono- and di-substituted monomeric beryllium phosphonitrilates[typically (2)].51Ph, ,Ph Ph, ,'PhNI \ / \Ph Ph Ph -PhCH2 - Me2NL , Me1NMe - 1 2%N M g SCH2 - MeNL /'Me NMe2 - i"' CH2(3)A review of organomagnesium compounds 52a emphasises that the consti-tution of Grignard reagents depends on the concentration of the solution andthe nature of the organic group, halogen, and solvent. Current views onGrignard reagents are radically affected by the ambiguity 52b of the critical" no-exchange '' experiment involving Mg*Br2 and Et,Mg. In dilute ethersolution, R2Mg and MgX, (R = Et or Ph; X = Br or I) react rapidlyand exothermically, giving solutions indistinguishable from those of thecorresponding Grignard reagents;52c the main reaction appears to be :the equilibrium strongly favouring RMgX.A similar equilibrium with K m 4is consistent with the polarographic behaviour 5Zd of organomagnesiumspecies in 1,2-&methoxyethane. In ethereal solutions of the pentafluoro-phenyl Grignard reagent, C,F,MgBr and (C,F,),Mg (or species based on thesegroupings) coexist and exchange rapidly (on an n.m.r. timescale) a t ca.R2Mg + MgX2 + ZRMgX,4c N. A. Bell, G. E. Coates, and J. W. Emsley, J . Chem. SOC. (A), 1966, 1360.47 N. R. Fetter, J . Chem. SOC. ( A ) , 1966, 711.N. A. Bell, J. Chem. SOC. ( A ) , 1966, 548.4D N. A. Bell, G. E. Coates, and J. W. Emsloy, J . Chem. Soc. ( A ) , 1966, 49.L. Banford and G. E. Coates, J . Chem. Soc.( A ) , 1966, 274.61 K. L. Paciorelr and R. H. Krtttzor, Inorg. Chem., 1966, 5, 638.62 ( a ) B. J. Wakefield, Organometallic C h m . Rev., 1966, 1, 131; (b) R. E. Dessy,S. E. I. Green, and R. M. Salinger, Tetrahedron Letters, 1964, 1369; (c) M. B. Smithand W. E. Becker, Tetrahedron, 1966,22,3027; ( d ) T . Psarras and R. E. Dessy, J . Amer.Chem. SOC., 1966,88, 5132; (e) D. F. Evans and 35. S. Khan, Chem. Comm., 1966, 67DOWNS, EBSWORTH AND TURNER: THE TYPICAL ELEMENTS 14390"c. Complexes (1 : 1) of Me,&lg and Ph,Mg with tetramethylethylene-diamine and 1,Z-dimethoxyethane, monomeric in benzene, have been char-a ~ t e r i s e d , ~ ~ whereas with trimethylethylenediamine Me,Mg gives a dimericproduct, probably with the structure (3). Of the several alkylmagnesiumalkoxides recent,ly prepared,54 only those with chain-branching at the carbonatom a to oxygen are tetrameric in benzene; compounds like EtMgOPP andPriMgOMe under similar conditions have degrees of association of 7-804,and secondary aminomagnesium alkyls are dimeric, e.g., priMgNPri,],.Typical of some of the crystalline magnesium alkoxide-ether complexes pre-pared 54 is a derivative, which, being dimeric in benzene, probably has thestructure (4).For the gaseous metal dihalide molecules MX, (M = Be, Mg, Ca, Sr, Ba;X = F, CI, Br, I) the observed geometries are correlated 55 with the increas-ing importance of d-orbitals with increase of atomic number.The octa-hedral MgCl64- and pyramidal MgC1,- ions have been identified by Ramanspectroscopy 56 in molten MgCl, and MgCl,-KCl, respectively.The so-called '' alkaline-earth metal carbonyls '' formulated as M(CO), are mixturesof acetylenediolates, methoxides, and ammonium ~arbonate.~' On the basisof conductivity and freezing-point measurements, it is suggested 58 thatdissolution of calcium and strontium in their respective molten halides leadsto an equilibrium 2M2+ + 2e + (M2)2+; (BaJ2+ is, however, comparativelyunstable.Group IIL-Boron. llB n.m.r. spectroscopy remains a fruitful source ofstereochemical information ; recent results include a unique assignment of thellB spectra of 1 ,2-dicarbaclovododecaborane 59 and 2,4-dicarbaclovohepta-borane,60 confirmation 61 of the previously suggested structures for B&f8,C0and B,H,,PF3, spectroscopic characterisation of various mono- and di-alkyldiboranes,62 and structural assignments of several new polyborane andcarborane systems subsequently to be described. Extension of the quanti-tative theory of llB chemical shifts 63 beyond empirical correlations is5 3 G.E. Coates and J. A. Heslop, J . Chem. SOC. ( A ) , 1966, 26.64 G. E. Coates and D. Ridley, Chem. Comm., 1066, 560.5 5 E. F. Hayes, J . Phys. Chenz., 1966, 70, 3740.5 6 K. Balasubrahmanyan, J . Chem. Phys., 1966, 44, 3270.5 7 W. Biichner, Helv. Chim. Ada, 1966, 49, 907.58 A. S. Dworkin, H. R. Bronstein, and M. A. Bredig, J . Phys. Chem., 1966, 70,69 J. A. Potenza, W. N. Lipscomb, G. D. Vickers, and H. Schroeder, J . Amer.6o T. Onak, G. B. Dunks, R. A.Beaudet, and R. L. Poynter, J . Amer. Chena. SOC.,61 A. D. Norman and R. Schaeffer, J . Amer. Chem. Soc., 1966, 88, 1143.62 H. H. Lindner and T. Onak, J . Amer. Chem. SOC., 1966, 88, 1890.6s F. P. Boer, R. A. Hegstrom, M. D. Newton, J. A. Potenze, and W. N. Lipscomb,2384.Chem. SOC., 1966, 88, 628.1966, 88, 4622.J . Amer. Chern. Xoc., 1966, 88, 6340144 INORGANIC CHEMISTRYpossible for the icosahedral carboranes for which the shifts are primarily deter-mined by differences in paramagnetic shielding. Systematic surveys ofllB n.m.r. spectra show that, in trigonal boron systems, (i) the chemical shiftis determined principally by the atoms directly bound to boron, and (ii) n-bonding probably contributes to the shielding of the boron.lH n.m.r.measurements imply that the order of acceptor activity withrespect to acetonitrile 65a is BBr, > BCl, > BF,, and that the activities ofB(C,F,), and BF, are comparable.65b Comparison of donor and acceptorstrengths has also been an objective of (i) manometric studies of BF, andBCl, with sulphide ligands 2a and of BF,, BH,, and BMe, with phosphines,66u(ii) the characterisation of boron halide-phosphorus halide complexes,66b(iii) displacement reactions, vapour density, and kinetic studies of complexesof several boron acids? (iv) dissociation pressure measurements of adductsof Me,N and Me,P with 1,3,2-dioxaborolan and 1,3,2-dioxaborinan (implyingthat the &membered ring is the stronger acid).6Gc Differences in acceptorability presumably contribute to the variations in charge-transfer spectra andoxidation potentials of metal cyanide adducts Fe(phen),(CN,BX,), (X = Me,H, F, C1, and Br) wherein the BX, unit apparently decreases metal-liganda-bonding and increases n-bonding.Thermochemical estimates of the B-0bond energy of the complexes Y,B,OPX, (X, Y = C1 or Br)67 are an orderof magnitude less than " normal " B-0 bond energies. New borane adductsinclude a compound with the probable structure H,B,P,O,,BH,, andL,BH, and L,ZBH, species,68b where L is tetramethylethylenediamine, NN'-dimethylpiperazine, or triethylenediamine. Anomalous variations in thedipole moments of the amine boranes Me,NH,-,,BH, are attributed 6g t o thecombined polarising influences of the four ligands on the nitrogen lone-pair.Recent preparative developments have enlarged the range of metal-boron compounds.Essentially localised metal-boron bonds presumablyexist in the addition compounds L,Rh(CO)X,BY, (L = Ph,P or Ph,As;X = C1 or Br ; Y = C1 or Br),7Oa (n-C5H,),MH2,BX, and (n-C5HS),ReH,BX,(M = Mo or W; X = F or Cl),70b and [Cl,M,BX,]- (M == Ge or Sn; X = For Cl);?OC the aflhity of the cyclopentadienyl metal hydrides and MCl,-ions 7oc for Werent boron acids indicates '' hard base " character for themetal atoms. Substitution reactions of manganese carbonyls lead to theformation of Mn-B bonds in compounds of the type X,B*Mn(C0)4L andXB[Mn(CO),PPh,J, (X = Ph, Bu, C1, NR,,OMe; L = CO or PPh3);'la64 J. E. De Moor and (3. P. Van der Kelen, J . Orgartometallic Chem., 1966, 6, 235;H.Noth and H. Vahrenkamp, Chem. Ber., 1966, 99, 1049.65 (a) J. M. Miller and M. Onyszchuk, C a d . J . Chem., 1966, 44, 899; (b) A. 0.Massey and A. J. Park, J . Organmetallic Chem., 1966, 5, 218.66 (a) H. L. Morris, M. Tamres, and S. Searles, Inorg. Chem., 1966, 5,2156; ( b ) A. F.Armington, J. R. Weiner, and G. H. Moates, &bid., p. 483; (c) G. E. McAchran and 8. G.Shore, ibid., p. 2044; (d) D. F. Shriver and J. Power, J. Amer. Chem. SOC., 1966, 88,1672.6 7 A. Finch, P. J. Gardner, and K. K. Sen Gupta, J . Chem. SOC. ( A ) , 1966, 1367.6 8 (a) G. Kodama and H. Kondo, J . Amer. Chewa. Soc., 1966, 88, 2045; ( b ) A. R.Gatti and T. Wartik, Irtorg. Chem., 1966, 5, 329, 2075.6B J. R. Weaver and R. W. Parry, Inorg. Chem., 1966, 5, 713, 718.7 O (a) P.Powell and H. Nath, Chem. Comm., 1966,637; (b) M. P. Johnson and D. F.Shiver, J . Amer. Chem. SOC., 1966,88, 301; ( c ) M. P. Johnson, D. F. Shiver, and S. A.Shiver, &bid., p. 1588DOWNS, EBSWORl'H AND TURNER: THE TYPICAL ELEMENTS 1451lB magnetic resonances of new compounds suggest substantial back-donation of metald-electrons to the boron. Analogous compounds of cobalt andplatinum, viz., (Ph,PCH,CH,PPh,), Co(BPh,), and (Et,P),Pt(BPh,)Cl, havebeen ~repared.71~ Metal atoms have also been incorporated into delocalisedbonding units. Thus, metallation of decaborane is believed to give solvatedcomplexes wherein the metal atom (Al, Zn, or Cd) bridges the 6,9 positions ofdecaborane.72 Two carborane derivatives in which a metal atom occupiesthe twelfth icosahedral position in the otherwise open face of the C,B,Hll2-(or related) anion have been structurally characterised by X-ray methods ;the proposed structure of the [C,BsH,,Re(CO),]- ion has thus been con-hrmed,73Q whilst a new palladium compound 730 containing a tetraphenyl-cyclobutadiene ring and the [B&,C2Me212- ion has a similar structure (5).PhPh(5)[Reproduced from P.A. Wegner and M. F. Hawthorne, Chem. Comm., 1966, 861.1General reviews about B,-B, boron hydride~,~*~ carboranes, 7Pb* andorgano-substituted boranes 74b have appeared. The theoretical aspects ofbonding in boron hydrides continue to attract attention : Slater-type atomic'l (u) H. Noth and G. Schmid, 2. anorg. Chem., 1966, 345, 69; J.OrganometallicOhm., 1966, 5, 109; ( b ) G. Schmid and H. Noth, 2. Naturforsch., 1965, 20b, 1008.78 N. N. Greenwood and J. A. McGinnety, J . Chem. SOC. ( A ) , 1966, 1090; N. N.Greenwood and N. F. Travers, Imrg. Nuclear Chern. Letters, 1966, 2, 169.7s (a) A. Zalkin, T. E. Hopkins, and D. H. Templeton, Inorg. Chem., 1966, 5, 1189;Ann. Reports, 1965, 62, 139; ( b ) P. A. Wegner and M. F. Hawthorne, Chem. Cmm.,1966, 861.74 (a) B. M. Mikhailov and M. E. Kuimova, Rms. Chem. Rev., 1966,35, 569; ( b ) T.Onak, Adv. Orgunometallic Chem., 1965,3,263 ; ( c ) K. Issleib, R. Lindner, and A. Tzschach,2. Chem., 1966, 8, 1146 INORGANIC CHEMISTRYbasis functions have been used vSu to examine molecular charge distributions,overlap populations, and other properties of some boron hydrides; for thegeneral three-centre two-electron system ZHZ, the energy, ZHZ bond angle,and effective nuclear charge of Z are closely interrelated;75b application ofLC(Hartree-Fock)AO molecular orbital theory to the c2H6 and BaHs mole-cules indicates 75c that the different geometries hinge upon the contributionsof the heavy atom p-functions to molecular bonding. Mass-spectrometricprocedures have been devised to identify labile borane specie~.~6~ Hence, thepyrolysis of tetraborane( 10) has been shown 76b to produce B,H, as well as di-,penta-, hexa-, hepta-, octa-, and deca-boranes, and possibly nonaborane.Monomeric BH, has been clearly identified 76c in the pyrolysis of diborane, ashave the new molecular species H,&@, and H4B607 (probably boroxine deri-vatives) in the high-temperature reaction of boron with water vapour.76dSimilarly, the anions BH4-, B2H,-, B2H8-, B3H8-, B3H7-, B,H,-, B,H,-,and B5H1,- (all with lifetimes > 10-5 see.) have been identified 7Oe whenB2H6 is bombarded by krypton ions.The BZOHIa2- ion undergoes reversible isomerisati~n,~~~ to give a “ photo ”ion probably having the structure indicated (16).Another remarkablepolyborane, the adduct B2,H1,,3MeCN, contains the molecular unitB20H,a(NCMe)2 with the structure (17a), whose formation involves rearrange-ment of the B,, unit of B,H1, (17b), giving a new framework composed ofB1, and B,, icosahedral units with a common triangular face.120The synthesis of organohalogenoboranes has been reviewed,lzl anddifferences in disproportionation tendencies of alkylhalogenoboranes,122apparently due to thermodynamic factors, have been discussed.The difunc-tional Lewis acid 1,Z-bis(difluorobory1)ethane forms adducts of the typeC2H4(BF2),,2D (D = Me,O or THF),123 but with (Ph&O or MeOCPh,,1 : 1 complexes also result, probably with the structure (18). Infrared spectraof BE’, trapped in low-temperature matrices support earlier evidence ofassociation,12* being compatible with the formation of a bridged h e rspecies. Evidence is also presented 125 supporting the formation of theB,F,- ion in the reaction of amine tetrafluoroborates with BF,. To clarifythe status of certain fluoroborates, the interrelationship of the four primarycompounds BF,, B,O,, HI?, and H20 has been expressed in the form of a“ genealogical tree.” 126 Solvent- and concentration-dependent llB and19F n.m.r.parameters of the BF4- ion have been related to solvationeffects.127 The redistribution behaviour of boron halides and properties ofthe mixed halides have been correlated 128 with n-bonding effects.n-Bonding in aminoboranes has been the subject of molecular orbital cal-culations, and mass-spectrometric measurements.129aP b Analysis of thevibrational spectra of l0B-substituted dialkylaminoboranes, confirming theinteraction of B-N and G N stretching vibrations, 1m shows that infraredfrequency shifts attributed to B-N motions are not reliable indices of z-bonding; the same cautionary note applies to borazine systems.l3Qb Thefactors controlling the polymerisation of aminoboranes have been elabor-ated.l S 1 Novel aminoboranes include various N-silyl deri~atives.13~a~ b Di-p-tolylcarbodi-imide reacts with B-X groups (X = C1, Br, Ph, OMe,NEt,, or SBun) by insertion, to give substituted aminoboranes, e.g.,Y,B*NTol*C( :NTol)*X, whence the relative migratory aptitudes of differentgroups has been deduced. lS3 Dehydrohalogenation of amine-boranes affordsa useful route to a m i n ~ b o r a n e s , ~ ~ ~ ~ but only bulky amines like Et,N effectthis change 134 in C1,B,NHMe2; other amines yield, under similar conditions,bis-amine complexes formulated as [Amine(Me,hTH)BCl,]Cl. Properties ofthe aminoboranes include the formation of charge-transfer complexes withiodine, 35a thermal elimination reactions giving cyclic B-N compounds,1S2blZ4 J.M. Bassler, P. L. Timms, and J. L. Margrave, J. Chem. Phys., 1966, 45, 2704;lZ5 J. J. Harris, Inorg. Chem., 1966, 5, 1627.lZ6 S. Pawlenko, 2. unorg. Chem., 1966, 547, 1, 7.lZ7 R. Haque and L. W. Reeves, J. Phys. Ciaem., 1966, 70, 2753; R. J. Gillespieand J. S. Hartman, J. Chem. Phys., 1966, 45, 2712.M. F. Lappert, J. B. Pedley, P. N. K. Riley, and A. Tweedale, Chern. Comm.,1966, 788.12* ( a ) P. G. Perlks and D. H. Wall, J. Chem. SOC. ( A ) , 1966, 1207; (b) J. C. Baldwin,M. F. Lappert, J. B. Pedley, P. N. K. Riley, and R. D. Sedgwick, Inorg. Nuclear Chem.Letters, 1965, 1, 57.130 (a) H. J. Becher and H. T. Baechle, 2. ghys. Chem. (Frankfurt), 1966, 48, 359;(b) R.E. Hester and C. W. J. Scaife, Spectrochim. Acta, 1966, 22, 455, 755.131 M. F. Lappert, M. K. Majumdar, and B. P. Tilley, J. Chern. SOC. ( A ) , 1966, 1590.132 (a) R. L. Wells and A. L. Collins, Inorg. Chem., 1966, 5, 1327; (b) P. Ceymayerand E. G. Rochow, Monatsh., 1966, 97, 429, 437.133 R. Jefferson, M. F. Lappert, B. Prokai, and B. P. Tilley, J. Chem. SOC. (A),1966, 1584.134 H. Noth, P. Schweizer, and F. Ziegelgansberger, Chena. Ber., 1966, 99, 1089.135 ( a ) I. D. Eubanks and J. J. Lagowski, J. Amer. Chem. SOC., 1966, 88, 2425;cf. R. G. Steinhardt, jun., G. E. S. Fetsch and M. W. Jordan, ibid., 1965, 43, 4528.(b) N. N. Greenwood and J. Walker, Inorg. Nuclear Chem. Letters, 1965, 1, 65154 INORGANIC CHEMISTRYand redistribution rea~tions,~~5~ n.m.r.studies of which indicate the sequenceMezNBX2 < Et,NBX, < BX, < PhBX, for the relative rates of halideexchange. Monomeric boron imides, C,FE',B:NAr (Ar = p-T/leO*C,H, ormesityl), are produced 136 [with small amounts of the dimer (C,F,B*NAr)gwhen Ar = p-MeO*C,H4] from C,F,BCl, and ArNH,. Dimethylboronazide 13' associates reversibly in the liquid phase and forms 1 : 1 complexeswith bases like pyridine.Apart from proton n.rn.r. surveys 138 and vibrational analyses,13*b mostof the advances in borazine chemistry have been associated with preparativereactions ;139a among the new borazines synthesized are fluoro-aryl and -alkylderivatives,139b Linear polyborazines (formed by condensation reactions ofsimple borazines with diamines) ,lZgc and hydrolytically stable derivativeswith bulky B - s u b s t i t ~ e n t s .~ ~ ~ ~ The reaction of B-trichloroborazine withMeMgBr is reported to give a polycyclic B-methylborazine, but whether thishas a naphthalene- or biphenyl-like structure has yet to be re~olved.139~More derivatives of the cyclotetrazenoborane system have been charac-terised, thus confirming the generality of the preparative reaction betweenprimary amine-boranes and organic azides.140 Compounds containing boronbonded to the nitrogen of a pyrazole nucleus l 4 l may take the form of B-Nheterocycles and metal chelates. Cyclic species of composition (BH2NH2),(n = 2, 3, 5, and possibly 4), resulting from the reaction of NaNH, with[H2B(NH3),]BH, in liquid ammonia, have also been described,l42 as havemembers of a new class of heterocycles containing the elements boron, nitrogen,and phosphorus in the same ring.143 The preparation of numerous hetero-cycles containing carbon as well as boron and nitrogen has been r e p ~ r t e d , l ~ * ~for example, by the reaction of am-diamines with amin0boranes.l4*~ Thedimethylaminomethylborane cyclic dirner, [H,B*CH,*NMe,],, is relativelystable with respect to thermal dissociation, unlike the analogous amino-methyl(dimethy1)borane ;145 this is in line with simple Lewis acid-baseaffinities.Some characteristic features of the crystal chemistry of borates hare beenoutlined,146 and a review of organosulphur-boron compounds l 4 7 hasappeared.Convenient syntheses of boroxine lPgU and trimethylboroxine 14gbare described.Boroxine reacts rapidly14& with CO to give BH,,CO.H2B203 and &B@, have been identified in the gas-phase oxidation ofB,Hlo, B5H9, and BH,,CO; the short-lived species €330 or H2BOH andH,B02 (borane peroxide) are likely intermediate~.l4~ Reports have appearedof new derivatives of ring systems containing boron, carbon, and eitheroxygen or sulphur, e.g., 1,3,2-dioxaborinan 150° and 1,2-thiaboro1an;l50b theacceptor behaviour of some of these systems has been investigated.* 4- and6-membered B-S ring compounds have been prepared l5la by the reaction ofH2S with trialkylamine-boranes ; 5-membered 1,3,44rithiadiborolan ringsresult from the cleavage of polysulphur compounds (H2S,, S,, disulphides) byboron halides.151* Heating of 2,5-di-iodo-l,3,4-trithiadiborolan with BI,causes ring-expansion with the formation of 2,4,6-tri-iodo-l,3,5-trithiatri-borinan.151b 6-Membered B-P heterocyclic compounds substituted atphosphorus have also been characterised.1522,2’-Bipyridyl (bipy) forms para- and dia-magnetic chelate compoundsin which boronis stabilised in unusual oxidation states,lL3 e.g., (Me,N)2B(bipy).The status of boronium salts is ambiguous; although the absorption spectraof the diphenylboron and 9-borafluorene cations have been satisfactorilyinterpreted,l540 and salts of the type @3un2B( amine),]+Cl- are reported,154*attempts to characterise phenylboronium cations have been unsuc~essful.~~~The CF, groups of the compounds CF3BBu2 and CF3BF2 suffer CF,-elimina-tion only in the presence of catalysts;l55 in vacuo a t room temperature thecompounds are said to be “ stable for months.” The extent of B-C n-bondingin vinylboranes has been gauged from spectroscopic 156u and molecularorbital 166b considerations.The relative reactivities of competing B-X siteswith respect to organometallic compounds have been compared.l57Recent surveys concern general features of metal borides 1580 and thestructural properties of boron and borides containing polyhedral B,, units.15gbB,, icosahedra are the basic structural units of AIBl, (but not AIB1,, ap-parently),15& whereas ScB12 and YB,, contain cubo-octahedral arrays ofboron atoms.158d A boride of potassium, KB,, has been prepared for the firsttime.158eReviews of general interest have appeared on complexalumino hydr ides, 59a or g anoaluminium and aluminium-p hosp horus 161compounds. Advances in aluminohydride chemistry have included thesynthesis of hexahydroaluminates M,Al€& (M = Li or Na) by two differentmethods.159b The i.r. spectrum of the adduct LiAlH4,NEt3 suggests 159~ thatit is actually a complex of Et,N,AlH, and LiH. Clear, relatively stable solu-tions of aluminium hydride,162 prepared from 100% H2S0, and LiAlH, intetrahydrofuran, like related alurninohydrides, are useful reducing agents forspecific organic groups. LiAlH, reacts with B2H6 in ether solution giving asproducts LiBH, and solvated AlH,(BH,),-, (n = 0, 1, 2, 3); 163a in tetra-hydrofuran cleavage reactions lead to alkoxyaluminium compounds believedto be the previously reported " triple metal hydrides." LiAlH, reducesaluminium halides in a stepwise manner, giving hydridoaluminium halides,which have been characterised as triethylamine adducts ; 1 6 X b these presum-ably constitute the so-called " mixed hydride " reagents. Aluminium boro-hydride complexes with Et,N [Et,N,Al(BH,),H] 164a and ethers (e.g.,H2AlBH4,2THF) have been characterised ; in crystalline Me,N,Al( BH,),a t low temperatures the aluminium is surrounded by a distorted pentagonalbipyramidal array of ligands,l6& whereas at room temperature the con-figuration is essentially tetrahedral.The trigonal prismatic co-ordination of tris-(cis-lY2-diphenylethane-l ,2-dithio1ato)rhenium has been confirmed.135 Other trismaleonitriledithiolatecomplexes of manganese, iron, molybdenum, and tungsten are suggested ashaving this structure.The spectra of tris-dithiocarbamate, 2,2'-bipyridyl, and acetylacetonato-complexes of manganese(m) have been assigned.13' The 5Bg + 5T2gtransition occurs at N 20,000 cm.-l, t.he lower energy (5000--15,000 cm.-l)band being attributed to a charge-transfer process. Pentachloromangan-ate(=) complexes are formed 138 when concentrated hydrochloric acidreacts with potassium pernianganate in the presence of, e.g., 2,2'-bipyridyl ;at lower acidity, MnLCl,,H,O is formed, as well as MnLCl,. The thermaldecomposition of pyridine (py) adducts ReBr3,2py and [ReO,py,]Br has beenr e ~ 0 r t e d .l ~ ~ The spectra of K,ReCl, in molten dimethyl sulphone, diethyl-amine hydrochloride, or Li-KC1 eutectic reveal a, larger splitting l40 of theligand-field bands in the latter solvent.Crystals of technetium(Iv) chloridecontain zig-zag chains of octahedra sharing two edges.141 This compoundforms 142 octahedral adducts TcC14L2 (L = Ph,P or Ph3As), TcCl,bipyridyl,and [TcCl,( bipyridyl),]Cl,. Bisdiphenylphosphinoethane forms the tervalentcomplex [TcCl, (diphos) JC1.The physical properties of compounds MITcF, (MI = Na, K, Rb, Cs)have been studied.la3 A square-pyramidal structure is proposed 14, forthe [ReX,O]- ion (X = C1, Br, I). K3&O, is stable to at least 800°c,but K2Mn04 decomposes reversibly a t MO-680 OC. The initial decomposi-tion products on heating KMnO, are K,MnO,, &&O,, and MnO,. I n astudy of the oxidising power of metal hexafl~orides,l~~ it was shown thatReF6 oxidises nitric oxide, yielding NO+ReF6; with NOE', (NO),ReF, wasformed. The chemistry of rhenium-(Iv) and -(v) oxychlorides has beeninvestigated.147 In alkaline solutions, B+[ReOCZ,] (B+ = Ph,As, Et,N, oracridinium) disproportionates to rhenium-(Iv) and -( vr1).14g Rheniumhydride-phosphine complexes are harder to prepare than those of othermetals; compounds ReH,(PR,),, [ReH,(PR,),],, and ReH5(PR3), have beenis01ated.l~~ Barium and strontium nitrides react with rhenium to form l50the ternary species M,Re,N,, (M = Ba, Sr).Osmium only forms the bariumcompound. A thermally unstable compound Sr,,Re5N,, was also detected.Iron, Ruthenium, and Osmium.-Dinitrosyl iron, cobalt, and nickelhalides react with either tetraphenyldiphosphine or diarsine to give thefollowing (NO)2Fe(Ph2PPPh2)a, [(NO),Fe(Ph,PPPh,)J,, [X(NO),BeEPh,],,[ (NO),FeEPh,],, [X( NO),CoPh,EEPh,Co( NO),X],, [ (Ph,PPPh,) (NO)NiX),,and [X(NO)NiAsPh,], (E = P or As; X = halide).151 With iron and cobaltnitrosylcarbonyls and 1,2-bis( dipheny1phosphino)ethane ( = diphos) thecompounds [Fe( NO),( diphos)] , [Co(NO) (CO) (diphos)],[&(NO)( C0),l2( diphos), and [(NO),( CO)Fe( diphos)Co(NO) (CO),] wereisolated.l 5 2The complexes [FeS,C,(CF,),], [FeS,C,Ph,], and [CoS,C,Ph,] have beenreported to be metal-sulphur bridged dimers with structures analogous tothat of [Co,S4C4( CF3),],. Their electronic properties and reactions withphosphines and Fe( CO), were also given.153~S,C,(CF,),], (M = Fe or Co) shows the following one-electron reductionprocesses :The polarography of[MS4C4(CF,)& + [MS-iC,(CFd4]2- * CMS&I(CFJ~I-The isolation and magnetic properties of the mononegabive dimers, andof similar rnaleonitrile-dithiolate (mnt2-) and toluene-3,4-dithiolate (tdt2-)compounds were also described.154 Similar polarographic studies indicatedthe existence of [M(tdt)J2- and [M(tdt),]- complexes (M = Fe, Co, Ni, Pt,Cu, Au), but only the [M(tdt),]- (M = Fe, Co, Au) compounds could beisolated.155 The preparations and magnetic properties of some complexesof the types [Fe (NO)S,C,Ph,] -, [Fe( NO)S,C,Ph,] -, [Fe(NO)S,C,Ph,]o, and[Fe(NO)S,C,Ph,],- have also been reported.ls6A series of complexes of the type Fe phen,X, (X = C1, Br, NCS, NCSe,OCN, N,, HCO,, CH,CO,) have been prepared and shown to be high-spinwith peff in the range 5-1-5.3 B.M.l57 The magnetism and electronic spectraof the complexes with X = C1, Br, and N3 have been interpreted on the basisof molecular orbital models based on C,, of DPh syrnmetrie~.l5~ WhenX = NCS or NCSe the magnetic behaviour has been interpreted in termsof a 5T, + lAl eq~ilibrium.l5~ The magnetic susceptibility data over thetemperature range 77-300"~ and the Mossbauer spectral data of the com-plexes [Fe phen,X]nH,O (X = oxalato, n = 5 ; or X = malonato, n = 7)have been discussed in terms of a spin-triplet ground state.160 The relation-ship between peff and the Mossbauer quadrapole splitting parameter, dEQ,for the complexes Fe py4X, (X = Cl, Br, I, NCS, OCN) has been discussedwith the assumption that they are tetragonally distorted octahedral com-plexes.161 The Mossbauer spectra of iron(@ phthalocyaninedipyridine,162iron-(II) and -(m) substituted salicylaldo~irne,l6~ nucleotide, nucleic acids,and EDTA complexes 164 have been discussed in terms of the modes ofmetal-ligand bonding.Similar Mossbauer spectral studies coupled withinfrared and electronic spectra have been used to distinguish [FeCl,]- from[FeC1,I3- ions,165 and to discuss the structures of Fe phen,X, and[Fephen,]X, (X = Cl, Br, NCS, OCN, HC0,).166The changes, due to pressure, in the electronic absorption spectrum ofGillespite, BaFeSi,O,,, have been interpreted in terms of changes in metal-ligand distances causing spin-pairing.167 The absorption spectra of thecomplexes [M bipy3]Br,,6H,0, [M bipy3]S0,,7H20 (M = Fe, Ru, Co, Ni,Cu), [FeL,X,] (L = isoqinoline, /I- and y-picoline, 4-cyanopyridine, 3,5-dichloropyridine; X = halide), [M bipy2X2],, [M bipy2X,]X (M = Fe, Ru,0 s ; X = C1, Br, I), and [Ru(diamine),]X, (X Br, I, SCN, $S203) have beenreported and discussed in terms of deviations from octahedral symmetry,metal-ligand bonding, and ligand-field parameters.16* Further studies ofthe optical spectra of [Fe(CN),NOI2- have led to the suggestion of the156 J. Locke, J. A. McCleverty, E. J. Wharton, and C. J. Winscorn, Chem. Comm.,15' K. Madeja, W. Wilke, and S. Schmidt, 2.anorg. Chem., 1966, 346, 306.158 P. Spacu and C. Lepadatu, J. Amer. Chem. SOC., 1966, 88, 3221.159 E. Konig and K. Madeja, Chem. Comm., 1966, 61.160 E. Konig and K. Madeja, J. Amer. Chem. SOC., 1966, 88, 4528.161 R. M. Golding, K. F. Mok, and J. F. Duncan, Inorg. Chem., 1966, 5, 774.162 A. Hudson and H. J. Whitfield, Chm. Comm., 1966, 606.163 K. Burger, L. Korecz, I. B. A. Manuaba, and I?. Mag, J. Inorg. Nuclear Chem.,lB4 I. N. Rabinowitz, F. F. Davis, and R. H. Herber, J. Amer. Chem. SOC., 1966,G. M. Bancroft, A. G. Maddock, W. K. Ong, and R. H. Prince, J. Chem. SOC. ( A ) ,1966, 677.1966, 28, 1673.88, 4346.1966, 723.166 J. F. Duncan and K. F. Mok, J. Chem. SOC. ( A ) , 1966, 1493.16' R. G. J. Strens, Chem. Cornm., 1966, 777.168 D.35. L. Goodgame, M. Goodgame, M. A. Hitchman, and M. J. Weeks, Inorg.Chem., 1966, 5, 635; R. A. Palmer and T. S. Piper, ibid., p. 864; J. E. Fergusson andG. M. Harris, J. Chem. SOC. ( A ) , 1966, 1293; H. H. Schmidtke and D. Garthoff, Hdv.Chim. Acta, 1966, 49, 2039198 INORGANIC CHEMISTRYfollowing revised energy-level scheme :I69ZZ, YZ < XY < n*NO < Z' - y8 < Z'The infrared spectra of complexes MX2,2NH, (M = Fe, Co, Ni, Cu, Zn,Cd, Hg, Pd, Pt; X = C1, Br, I) in the range 4000-200 cm.-l have beenreported, and the M-N and M-halogen stretching frequencies discussed inrelation to the structures of the complexes.lV0 In the complexes[Ru,(OCOR),Cl] (R = Me, Et, Pr"), which contain ruthenium in the for-mal oxidation states II and m, the room-temperature magnetic momentssuggest that some of the ruthenium is in the spin-free state.lV1 The magneticmoments and electronic spectra of a number of iron(=), cobalt(@, nickel(n),copper(=), and zinc(n) Schiff base and other nitrogen-donor complexes havebeen used to suggest their structures.172The magnetic susceptibility data for several spin-paired iron(m) andruthenium(m) complexes,173 and the near-infrared spectrum of Os(acac),l74have been interpreted in terms of a ,TZg ground state which has been per-turbed by spin-orbit coupling and an axial ligand-field component.Thepreparation, magnetic properties, and structures of a binuclear and a mono-nuclear form of [Fe(salen)Cl] have been described.lV6 In the diethyldithio-carbamate complex, [Fe(S,CNEt,),Cl], magnetic susceptibility measurementsand an X-ray structure determination have shown it to contain five-co-ordinate (essentially square-pyramidal) iron(@ with a spin quartetground-state.lV6 The Mossbauer and proton n.m.r.spectra of several otheriron(m) dithiocarbamate complexes have been interpreted in terms of thesymmetry of the ligand field and iron d-electron delocalisation.177 Themagnetic exchange interactions in trimeric n-alkoxide complexes, [Fe,( OR),],have been interpreted in terms of a dipolar coupling scheme for a triangularcluster of spin-free iron(m) ions (8 = 5/2),178 whilst in the complexes[Fe,O(phen),]X, (X = C1, NO,) each interacting iron has been assumed tohave a spin-paired ground state (8 = +).l79Magnetic susceptibility, electrical conductivity, and infrared spectralmeasurements have been used t o deduce that in the complexes [FeBX,]Y(X = C1, Br, I, NCS; Y = ClO,, BF,, NCS; B = the quinquedentate2,13-dimethyl-3,6,9,12,18-penta-azabicyclo[ 12,3, lloctadeca- 1 ( 18) ,2,12,14,16-160 H.B. Gray, P. T. Manoharan, J. Pearlman, and R. F. Riley, Chem. Comm.,1966, 62.l70 R. J. H. Clark and C. S. William, J . Chem. SOC. (A), 1966, 1425.171 T. A. Stephenson and G. Wilkinson, J . Inorg. Nuclear Chem., 1966, 28, 2285.172 J. R. Allan, D. H. Brown, R. H. Nuttall, and D. W. A. Sharp, J . Chem. SOC. ( A ) ,1966, 1031; L. F. Lindsay, S. E. Livingstone, T. N. Lockyer, and N. C. Stephenson,Austral. J . Chem., 1966, 19, 1165; W. R. McClellan and R. E.Benson, J . Amer. Chem.SOC., 1966, 88, 5165; M. A. Robinson and T. J. Hurley, Inorg. Chem., 1965, 4 , 1716;H. M. Fisher and R. C. Stoufer, Inorg. Chem., 1966, 5, 1172; M. A. Robinson and T. J.Hurley, J . Inorg. Nuclear Chem., 1966, 28, 1747.173 B. N. Figgis, J. Lewis, F. E. Mabbs and G. A. Webb, J. Chem. SOC. ( A ) , 1966,422.174 R. Dingle, J . Mol. Spectroscopy, 1965, 18, 276.M. Gerloch, J. Lewis, F. E. Mabbs, and A. Richards, Nature, 1966, 212, 809.1 7 6 B. F. Hoskins, R. L. Martin, and A. H. White, Nature, 1966, 211, 627.177 E. Frank and C. R. Abeledo, Inorg. Chem., 1966, 5, 1453; R. M. Golding, W. C.Tennant, C. R. Kanekar, R. L. Martin, and A. H. White, J . Chem. Phys., 1966, 45,2688; R. M. Golding and H. J. Whitfield, Trans. Paraday SOC., 1966, 62, 1713.178 R.W. Adam, C. G. Barraclough, R. L. Martin, and G. Winter, Inorg. Chem.,1966, 5, 346.179 I,. N. Mulay and N. L. Hofmann, Inorg. Nuclear Chem. Letters, 1966, 2, 189BTABBS AND MACHIN: THE TRANSITION ELEMENTS 199pentaene} the iron is seven-co-ordinate with the group Y unco-ordinated.ls*From infrared and Raman spectral studies on [M(NH3)6]3+ and [M(ND3)6]3f,the skeletal vibrational modes have been assigned.ls1 On the basis of theirFaraday rotations the 24,100 and 32,900 cm.-l charge-transfer bands ofK,Fe(CN), have been assigned to the 2T20 -+ 2Tlzc and 2Tzg -+ 2T2u transi-tions, respectively.ls2Magnetic susceptibility and infrared spectral measurements on the com-plexes [Fe(diars),X,](BF,), (X = C1, Br) have been interpreted in terms of atetragonally distorted spin-paired iron( IV) complex with trans- halides.83The magnetic interactions in the complexes MRuO,, Sr,RuO,, and(BaBi6 Sr1/B)R~03 (M = Sr, Ca, Ba) have been discussed in relation to thestructures of these cornple~es.~~4 In the solid state,(NH,),[oS,o Cll,]H20 is diamagnetic, but in aqueous solution paramag-netism corresponding to four unpaired electrons has been observed. Thisbehaviour in solution was interpreted on the basis of a dimer .c- monomerequilibrium.185 The preparation and characterisation of OsF, has beendescribed. 186 The gas-phase infrared spectrum of OsO, has been interpretedon the basis of a normal co-ordinate analysis.ls7Cobalt, Rhodium, and Iridium.-Refluxing [ (Ph,P),RhCl] with carbondisulphide has led to the isolation of trans-[ (Ph,P),Rh(CS)Cl] which in turncan be oxidised with chlorine to [(Ph3P),Rh(CS)Cl,].18s Rhodium-boronbonds are reported to occur in compounds of the type [L,Rh(CO)X*BY,](X = Y = C1, Br; L = Ph3P or Ph,As).lsS The reaction between[Co(CN)J3- and sulphur dioxide or stannous chloride has led to the isolationof the complexes [(NC),Co-A-Co(CN),]6- (A = SO, or SnCl,), which containeither Co-S-Co or Co-Sn-Co linkages.190 Sulphur dioxide has been shownto addreversiblyto compounds of the type [MCl(CO)(Ph,P),] (M = Rh, Ir).lglA number of hydrido- and deuterio-iridium complexes, containing triphenyl-phosphine and carbon monoxide as other ligands, have been prepared andcharacterised using infrared and n.m.r. spectroscopy.lg2 Complexes of thetype [M(dp),]X [dp = C2H,(PPh,),; M = Co, X = ClO,; M = Ir, X = C1,Br, I, ClO,, BPh,] have been shown to add hydrogen, hydrogen halides,carbon monoxide, and sulphur dioxide. The iridium complexes add mole-cular oxygen reversibly, whereas the cobalt complex was oxidised tocobalt ( II) . l 9 3S. M. Xelson, P. Bryan, and I). H. Busch, Chem. Comm., 1966, 641.W. P. Griffith, J . Chem. SOC. ( A ) , 1966, 899.lS2 P. J. Stephens, Inorg. Cltem., 1965, 4, 1690.lS3 G. S. F. Hazeldean, R. S. Nyholm, and R. V. Parish, J. Chem. SOC. ( A ) , 1966, 162.la4 A. Callaghan, C. W. Moeller, and R. Ward, Inorg. Chem., 1966, 5, 1572.lS6 B. Jesowska-Trezebiatowska, J. Hanuza, and W. Wojciechowski, J . Inorg.lS6 0. Glemser, H. W. Roesky, K.-H.Hellberg, and H.-U. Werther, Chew Ber.,Nmlear Chem., 1966, 28, 2701.1966, 99, 2652.I. W. Levin and S. Abramowitz, Inorg. Chem., 1966, 5 , 2025.M. C. Baird and G. Wilkinson, Chem. Comm., 1966, 267.P. Powell and H. Noth, Chem. Comm., 1966, 637.lS0 A. A. VEek and F. Basolo, Inorg. Clzem., 1966, 5, 156.lgl L. Vaska and S. S. Bath, J . Amer. Chent. Soc., 1966, 88, 133.lS2 L. Vaska, Chem. Comm., 1966, 614; R. C. Taylor, J. F. Young, and G. Wilkinson,lv8 A. Sacco, M. Rossi, and C. F. Nobile, Chem. Comm., 1966, 589.Inorg. Chem., 1966, 5, 20200 INORGANIC CHEMISTRYThe existence of an electron-transfer series of the type [MD,]* (D = di-anion of o-phenylenediamine; M = Co, Ni, Pd, Pt; x = -2, - l , O , 3-1, +2)has been demonstrated, and some of the members of the series is01ated.l~~A series of complexes [(n-C,Hg)4N][M(S,C6X,Y2),] (M = Co, Ni, Cu;X = Y = H, Me, Cl, or X = H, Y = Me) have been isolated, and theirspectral and magnetic properties shown to be consistent with a molecularorbital energy scheme in which the highest filled orbitals are largely ligandin cornpo~ition.~~5The complex [Co(paphy)Cl,] [paphy = 1,3-bis-(2-pyridy1)-2,3-diazaprop-l-ene] has been isolated as a- and /3-modifications. An X-ray structuredetermination has shown the 8-form to be a five-co-ordinate monomer withessentially square-pyramidal geometry, whereas magnetic and spectral datafor the cc-form are consistent with an octahedral str~cture.~~6 The ligandtris-(2-dimethylaminoethyl)amine (tren Me) forms high-spin five-co-ordinatecomplexes of the type [M(tren Me)X]X [M = Co(n), Ni(n), Cu(rr); X = Cl,Br, I, NO,, ClO,] which are thought to have trigonal-bipyramidal struc-t u r e ~ .~ ~ ~ The proton nuclear magnetic resonance contact shifts for com-plexes [CoL,X,] [L = py, (Me,N),PO; X = C1, Br, I, NCS] and [ML,]M = Co, Ni; L = isoquinoline 2-oxide, quinoline l-oxide) have been inter-preted in terms of unpaired electron spin delocalisation through cr- and/orn-bonding mechanisms.lg8 Similar contact shift measurements for thecomplexes [M(acac),]- and [M(acac),(pyNO),] (M = Co, Ni) have been inter-preted in terms of electron delocalisation. The results were also used toestimate the magnetic anisotropy of[Co(acac),]- (KII - KL = -4280 x c.g.s.u.mole-l) and the M-0-Nangle (114-125') in the pyN0 complexes.199The structures of complexes of the types [Co L6]& ,O0 (L = hydrazine,NN'-dimethylacetamide, di-2-pyridylamine, 3-substituted urea ; X = halide,C104, NO,) and [CoL,X,j ,01 ( L = NN-dimethylthioacetamide, 4,4'-diethoxy-carbonyl- 3 , 3' ,5,5'- t e trameth yldip yrr ome t hane , substi-tuted pyridines, a-benzylene-2,1-benzimidazole, substituted thiourea ; X =halide, NCS, NO,) have been inferred from magnetic and spectral measure-194 A. L. Balch and R. H. Holm, J. Arner. Chem. SOC., 1966, 88, 5201.lS5 M. J. Baker-Hawkes, E. Billig, and H. B. Gray, J. Amer. Chem. SOC., 1966, 88,196 I. G. Dance, M. Gerloch, J. Lewis, F. S. Stephens, and F. Lions, Nutzcre, 1966,1 9 7 M. Ciampolini and N.Nardi, Inorg. Chern., 1966, 5, 41.198R. W. Kluiber and W. Dew. Horrocks, jun., J. Amer. Chem. SOC., 1966, 88,1399; B. €3. Wayland and R. S. Drago, ibid., p. 4597.lS9 R. W. Kluiber and W. Dew. Horrocks, jun., J . Amer. Chern. SOC., 1965, 87,5350; W. Dew. Horrocks, jun., R. H. Fischer, J. R. Hutchinson, and G. N. LaMar,ibid., 1966, 88, 2436.ZOOM. Goodgame, J. Chem. SOC. ( A ) , 1966, 63; D. Nicholls, M. Rowley, and R.Swindells, ibid., p. 950; P. S . Gentile and T. A. Shankoff, J . Inorg. Nuclear Chem.,1966, 28, 1283; S. K. Madan and A. M. Donohue, ibid., p. 1617; J. A. Costamagna andR. Levitus, ibid., p. 2685; B. B. Wayland, R. J. Fitzgerald, and R. S. Drago, J. Amer.Chem. Xoc., 1966, 88, 4600.201 J. deO. Cabral, H. C. A. King, S. M.Nelson, T. M. Shepherd, and E. Koros,J, Chem. SOC. ( A ) , 1966, 1348; J. Ferguson and B. 0. West, ibid., p. 1569; S . K. Madanand D. Mueller, J. Inorg. Nuclear Chem., 1966, 28, 177; S. K. Madan and C. Goldstein,ibid., p. 1251; G. Yagupsky, R. H. Negrotti, and R. Levitus, J. Inorg. Nuclear Chaem.,1965,27,2603; M. S. Elder, G. A. Melson, and D. H. Busch, Incwg. Chem., 1966,5,74.E - thio capr ola c t am,4870.210, 295MABBS AND MACHIN: THE TRANSITION ELEMENTS 201ments. The formation of octahedral cobalt(=) and tetrahedral cobalt(n)and copper (11) azido-complexes in methyl cyanide, dimethyl sulphoxide,and trimethyl phosphate has been demonstrated. 202 The infrared spectra of(Et4N),[Co(N,),] and (Et,N),[Zn(N,),] in the solid state indicata a non-linear M-N-N linkage.203 From similar studies on [M(~U)~X,] (M = Go, Zn,Cd; X = C1, Br, I; tu = thiourea), ~i(tu),]X, (X = Br-, NO,-), and[Ni( tu),Cl,], metal-sulphur and metal-halogen stretching frequencies havebeen identified.204 A study of the spectral and magnetic properties ofsolutions of bis-(8-keto-amino)cobalt (n) complexes show that a planar(S = 8) + tetrahedral (8 = 3/2) configurational equilibrium exists.205The electronic spectra of the complexes [Co(amine),X,] (X = C1, Br, I,NCS, NCSe) are virtually independent of the amine, except when they con-tain a-substituted pyridines which decrease the supposed 4B2 -+ 4A, transi-tion by as much as 1000 cm.-1.206 Although the free ligand dithioacetyl-acetone is not known, it has been stabilised in the complexes [M(SacSac),][M = CO(II), Ni(rr), Pd(n), Pt(n) ; SacSac = dithioacetyla~etonatoo].~~7 Atetrameric complex, [co,o( OCOCMe,)6], for which the magnetic momentindicates magnetic exchange interactions between the cobalt atoms, hasbeen isolated.208The absolute configurations of the complexes a-( +)-tris-L-alaninato-Co(m) ,09 and ( + )-cis-dinitrobis-( - )-propylenediamine-Co(m) chloridehave been determined by single-crystal X-ray determinations and correlatedwith their circular dichroism spectra. The circular dichroism, optical,and optical rotatory dispersion spectra of a number of cobalt (111) ethylenedi-amine, propylenediamine, cyclohexanediamine, and NNN'N'-tetrakis-(Z-aminoethy1)- 1,2-diaminoethane complexes 211 and of [CoX,I2- (X = C1,Br, I) have been reported and discussed in terms of the ligand-fieldsymmetries and configurational effects.The isolation of geometrical isomersof a number of tris- bidentate and hexa-co-ordinated mixed ligand cobalt (m)complexes have been reported, and in some cases their electronic spectra arediscussed. 21203 V. Gutmann and 0. Leitmann, Monalsh., 1966, 9'9, 926.203 D. Forster and W. Dew. Horrocks, jun., Inorg. Chem., 1966, 5, 1510.204 C. D. Flint and M. Goodgame, J. Chem. SOC. ( A ) , 1966, 744.2 0 5 G. W. Everett, jun., and R. H. Holm, J . Amer. Chem. SOC., 1966, 88, 2442.206 A. B. P. Lever and S. M. Nelson, J. Chem. SOC. (A), 1966, 859.207 R. L. Martin and I. M. Stewart, Nature, 1966, 210, 522.208 A. B. Blake, Chem. Comm., 1966, 569.209 M.G. B. Drew, J. H. Dunlop, R. D. Gillard, and D. Rogers, Inorg. Chem., 1966,5, 42.210 G. A. Barclay, E. Goldschmied, N. C. Stephenson, and A. M. Sargeson, Chem.Cornm., 1966, 540.211 B. E. Douglas, Inorg. Chem., 1965, 4, 1813; H. L. Smith and B. E. Douglas,Inorg. Chem., 1966, 5, 784; R. S. Treptow, ibid., p. 1593; A. J. McCaffery, S. F. Mason,and B. J. Norman, Chem. Comm., 1966, 661; J. R. Gollogly and C. J. Hawkins, ibid.,p. 873; S. F. Mason and B. J. Norman, J. Chem. Sbc. (A), 1966, 307; C. J. Hawkins,E. Larsen, and I. Olson, Acta Chem. Scund., 1965, 19, 1915.212 R. G. Denning, J. Chem. Phys., 1966, 45, 1307.213 E. Larsen and S. F. Mason, J. Chem. SOC. ( A ) , 1966, 313; K. Garbett and R. D.Gillard, ibid., p. 802; J. H.Dunlop, R. D. Gillard, and R. Ugo, ibid., p. 1540; J. I. Leggand D. TV. Cooke, Inorg. Chem., 1966, 5, 594; M. D. Alexander and D. H. Busch, ibid.,p. 602; R. G. Denning and T. S. Piper, ibid., p. 1056; B. E. Bryant, H. J. Hu, and W. H.Glaze, ibid., p. 1373; N. Matsuoka, J. Hidaka, and Y. Shimura, Bull. Chem. SOC. Japa202 INORGANIC CHEMISTRYThe preparation, and assignment of structures from spectroscopicmeasurements, of complexes of the types [Co(tetram)XY]+ (tetram is acyclic quadridentate-amine ; X and Y can be halide or pseudo-halide groups),[Co en2&YIn+ (X = a primary aliphatic amine; Y = C1, Br or X = glycin-ato, Y = Cl), [Co(dmg),XL] (dmg = dimethylglyoximato; X = thiourea;L = mono-deprotonated thiourea), and trans-[Rh en,X2]N03 (X = C1, Br)have been rep0rted.2~~ The peroxy-bridged complexes trans-[X( cyc1am)Co-O,Co(cyclam) XI2+ (cyclam = 1,4,8,11-tetra-azacyclotetradecane; X = C1,N3, NCS, NO,) have been isolated and converted into trans-[Co(cyclam)XY]+by reaction with acids HY.216 An X-ray structural study of the complex[(NH3),Co02Co(NH,)],(S0,)HS0,), has been interpreted in terms of abridging superoxide (02-) rather than a peroxide group.216[RhH(H20)(NH,)4]S0,,217 K2[RhH(CN)4H20],21g [IrHxY3-,L,] (x = 1,2, or3; Y = halogen; L = R3P, R,As), [IrH,(PR,),],219 and [IrH,(PMe,Ph),](Y = C1, Br, I, H, CN, SCN),220 have been given, and infrared and n.m.r.spectra used to determine stereochemistries.The infrared spectra of somebis-ethylenediamine-cobalt (III), halogeno-iridium(m) arsine or phosphinecomplexes, [RhCl,,SRCN], [RhCl,(TPP)], and [MX,(TPP),] (M = Pd, Pt,Hg; X, C1, Br; TPP = 1,2,54riphenylphosphole) have also been discussedin relation to the possible structures of the complexes.22lNickel, Palladium, and Plathum.-The compounds of stoicheiometryPt(PPh,) and Pt(PPh,), have been prepared, and the mono-derivative isshown to be tetrameric in benzene solution.222 A new and convenientpreparation of Ni(PF3)4 from nickelocene and PF, has been reported.223The reaction of Pt(PPh,), with hydrochloric acid has been shown to give aseries of hydride complexes, whereas the corresponding palladium and nickelcomplexes, and [M(Ph,P(CH2)2PPh2),] (M = Ni, Pd, Pt), gave only hydro-gen.224 The reaction between Pt(PPh,), and CS, or COS resulted in theisolation of monomeric compounds, [(Ph,P),Pt L] (L = CS,, COS).225The preparations of some hydrido-complexes, [RhH(NH,),]SO,,1966, 39, 1257; K.Ohkawa, J. Hidaka, and Y. Shimura, ibid., p. 1715; M. Shibatu,H. Nishikawa, and Y. Nishida, ibid., p. 2310; T. P. Emmenegger and G. Schwarzenbach,Helv. Chim. Acta, 1966, 49, 625; F. P. Dwyer, I. K. Reid, and A. M. Sargeson, Austral.J . Chem., 1965, 18, 1919; J. A. Broomhead, Nature, 1966, 211, 741.214 S. C. Chan and F. Leh, J. Chern. SOC. (A), 1966, 760; P. 0. Whimp and N. F.Curtis, ibid., p. 867; J. P. Collman and P. W. Schneider, Inorg. Chem., 1966, 5, 1380;M. D. Alexander and D. H. Busch, ibid., p. 1590; A. V. Ablov, B. A. Bovykin, andN. M. Samus, Russ. J. Inorg. Chem., 1966, 11, 31; R.D. Gillard, E. D McKenzie, andM. D. Ross, J . Inorg. Nuclear Chern., 1966, 28, 1429.215 B. Bosnich, C. K. Poon, and M. L. Tobe, Inorg. Chem., 1966, 5, 1514.216 W. P. Schafer and R. E. Marsh, J. Arner. Chem. SOC., 1966, 88, 178.217 J. A. Osborn, A. R. Powell, and G. Wilkinson, Chem. Comm., 1966, 461.218 D. N. Lawson, M. J. Mays, and C. Wilkinson, J. Chem. SOC. ( A ) , 1966, 52.21g J. Chatt, R. S. Coffey, and B. L. Shaw, J. Chem. Soc., 1965, 7391.220 J. M. Jenkins and B. L. Shaw, J. Chm. SOC. ( A ) , 1966, 1407.821 R. A. Walton, J. Chem. SOC. ( A ) , 1966, 365; J. M. Jenkins and B. L. Shaw,J . Client. SOC., 1965,6789; M. N. Hughes and W. R. McWhinnie, J. Inorg. Nuclear Chem.,1966, 28, 1659; B. F. G. Johnson and R. A. Walton, ibid., p.1901,Z z 2 R. Ugo, F. Cariati, and G. LaMonica, Chem. Comm., 1966, 868; R. D. Gillard,R. Ugo, F. Cariati, S. Genini, and F. Bonati, ibid., p. 869.223 J. F. Nixon, Chem. Comrn., 1966, 34.224 F. Cariati, R. Ugo, and F. Bonati, Inorg. Chem., 1966, 5 , 1128.226 M. C. Baird and G. Wilkinson, Chem. Comm., 1960, 614MABBS AND MACHIN: THE TRANSITION ELEMENTS 203Diamagnetic, square-planar dithiolate complexes [M(dt)2]2- [M = Ni,Pd, Pt, Cu; dt = S2CS2-, S2CNCN2-, S2CC(CN)22-] have been isolated.Z26It bas been proposed that the occurrence of isotropic g-values close to thefree-electron value, in complexes of the type [Ni(mnt),]-, is diagnosticevidence for the presence of cation-stabilised free radicals. 227 The existenceof an electrontransfer series of general formula [MLJ (M = Ni, Co, Cu,Zn, Cd; L = catechol, tetrachlorocatechol) has been demonstrated usingelectrochemical oxidation, e.s.r., and chemical methods.22* The complexesC]SI(S,C,Ph,),] (M = Ni, Pd) react with Ph,P(CH,),PPh,(diphos) to givecompounds [M( S2C,Ph2) (diphos)], whereas the corresponding platinum com-pound only gives an adduct, [Pt (S,C,Ph,),(diphos)].229The low-temperature single-crystal polarised spectrum of K2PtC14230 andthe circular dichroism of the [PtC1,I2- ion 231 have been discussed in relationt o their structures. A discussion of the effect of a distant asymmetric centreon the circular dichroism of the complexes truns-[PdCl,( -)amz] and trans-[PdCl,( -)amz] (am = l-phenylethylamine) has also been given.232The effect of spin-orbit coupling, an axial ligand-field component, andan orbital reduction factor, k, on the magnetic properties of the 3T1 termhas been calculated, and the results are used to interpret the observedmagnetic behaviour of a series of tetrahedral Ni(n) cornple~es.23~ Thediamagnetism of [Ni(diarsine),]( ClO,), has been interpreted on the basis ofan octahedral arrangement of ligands, which has electrical symmetry of D,,arising from 0- and n - b ~ n d i n g .~ ~ ~ The crystal-field terms which arise fornickel(@ in trigonal- bipyramidal and square-pyramidal stereochemistrieshave been calculated, and the predicted spectral transitions found to be insatisfactory agreement with those 0bserved.~~5 The effects of clustering,and of exchange interactions between nickel@) ions in some Perovskitefluoride complexes, on the electronic absorption spectra are reported.236The proton magnetic resonance contact shifts in a number of nickel@)Schiff base, nitrogen and oxygen donor, and diphosphine complexes havebeen used to suggest possible modes of electron-spin delocalisation and theexistence equilibria between complexes with different stereochemistries.2372 z 6 J. P. Fackler, jun., and D. Coucouvanis, J . Amer. Chem. SOC., 1966, 88, 3913;227 A. H. Maki, T. E. Berry, A. Davidson, R. H. Holm, and A. L. Balch, J . Amer.228 F. Rohrscheid, A. L. Balch, and R. H. Holm, Inorg. Chem., 1966, 5, 1542.22g V. P. Mayweg and G. N. Schrawzer, Chem. Comm., 1966, 640.230 D. S. Martin, jun., M. A. Tucker, and A.J. Kassman, Inorg. Chem., 1965, 4,231 B. Bosnich, J . Amer. Chem. SOC., 1966, 88, 2606; D. S. Martin, J. G. FOSS, M. E.232 B. Bosnich, J . Chem. Xoc. ( A ) , 1966, 1394.233 B. N. Figgis, J. Lewis, F. E. Mabbs, and G. A. Webb, J . Chem. SOC. ( A ) , 1966,a34 B. Bosnich, R. Bramley, R. S. Nyholm, and M. L. Tobe, J . Amer. Chem. SOC.,235 M. Ciampolini, Inorg. Chem., 1966, 5, 35.236 W. W. Holloway, jun., and M. Kestigian, J . Chem. Phys., 1966, 45, 639; J.Ferguson and H. J. Guggenheim, ibid., p. 1095.237 R. W. Kluiber and W. Dew. HOITOC~, jun., I w g . Chem., 1966, 5, 152; J. D.Thwaites and L. Sacconi, ibid., p. 1029; J. D. Thwaites, J. Bertini, and L. Sacconi,ibid., p. 1036; G. R. van Hecke and W. Dew. Horroclm, jun., ibid., p. 1968; R.HolmR. G. Werden, E. Billig, and H. B. Gray, Inorg. Chem., 1966, 5, 78.Chem. SOC., 1966, 88, 1080.1682; 1966, 5, 1298.McCarville, M. A. Tucker, and A. J. Kassman, Inorg. Chem., 1966, 5 , 491.1411.1966, 88, 3926204 INORGANIC CHEMISTRYAs with cobalt(@, infrared, electronic spectra, magnetic susceptibility,molecular weight, and conductivity data have been used to suggest structuresfor the following types of complexes: [ML,X,] (M = Ni, Pd, Pt; L can bemono thio - p- diket one, quinoline , i so quinoline , di methylp yridines , 2 -methyl-benzimidazole, 3 -methylis0 quinoline, 2 - methylbenzothiazole, 2 -, 3 - or4-cyanopyridine ; X can be C1, Br, I, NCS, dicyanamide, tricyanmethanide,substituted pyridines, bipyridyl, substituted 1 ,lo-phenanthrolines) ;23*[NiL,] (L = 1,5-diazacyclo-octane, Schiff bases derived from diketones andaromatic amines or from salicylaldehydes and substituted trimethylene-diamines) ; 239 [INiLYX] ,nH,O {L = 2,12-dimethyl-3,7 , 1 1,17- tetra-azabicyclo-[11,3,1]heptadeca-1(17),2,11,13,15-pentaene; Y = X = ClO,, n = 0 ;Y = X = C1,n = 0;Y = X = NCS,n = 0 ; Y = X = Br,n = l ; Y = Br,X = BF,, n = 1);24* [M,X,L] [M = Pd(rr), Pt(rr); X = Cl, Br, I, SCN;L = 1,4-di- (o-aminothiophenoxy)but-trans-2-ene]. The occurrence ofdiketones bonded through a carbon atom rather than the oxygena has beenreported in complexes of the type [Pt(diketone),X]- (X = C1, Br).Thesecomplexes can then co-ordinate, through the diketone oxygen atoms, toother transition metals to give compounds of the type M[Pt(acac),X],(M = Mn, Fe, Co, Ni, Cu, Zn, Cd, Pd).,,, The isolation of compoundsK3Ni(CN),,2H,0 and Mvi(CN),],2H20 {M = [Cr(NH,),I3+, [Cr en3I3+},which contain the [Ni(CN),]3- ion, and the stability of this ion towardsdecomposition to [Ni(CN),]2- has been reported.243A number of palladium(n), platinum(II), cadmium(n), and mercury(n)halide and silver(1) perchlorate complexes with the ligands Ph3PSe andPh,AsS have been prepared and their infrared spectra discussed with respectto P-Se and As-S stretching vibrations. Platinum-silicon and platinum-germanium bonds have been reported to occur in the complexes[Me3M-Pt(C1)(PEf3),] (M = Si, Ge),245 whilst the Pr,Sn, cluster is thoughtto be present in the ion [Pt3Sn,C1,,]4-.246 A cyclic structure, in whichapproximately square-planar NiS, units form the faces of it hexagonal prism,has been proposed for [Ni( SR),], comp0unds.~4~ Infrared absorption bandsG.W. Everett, jun., and W. Dew. Horrocks, jun., J. Anzer. Chem,. SOC., 1966, 88, 1071;B. B. Wayland, R. S. Drago, and H. F. Henneike, ibid., p. 2455; L. Morpurgo andR. J. P. Williams, J. Chem. SOC. ( A ) , 1966, 73.238M. Goodgame and M. J. Weeks, J . Chem. Soc. ( A ) , 1966, 1156; P. L. Gogginand R. J. Goodfellow, ibid., p. 1462; R. A. Walton, J . Inorg. Nuclear Chem., 1966, 28,2229; L. Sacconi and I. Bertini, Inorg. Nuclear Chem. Letters, 1966, 2, 29; S. H. H.Chaston, S. E. Livingstone, and T. N. Lockyer, Austral. J. Chem., 1966, 19, 1401;H. Kohler, H. Hartung, and B. Seifert, 2.Anorg. Chem., 1966, 34'7, 30.239 W. K. Musker and M. S. Hussain, Inorg. Chem., 1966, 5, 1416; L. Sacconi,N. Nardi, and F. Zanobini, ibid., p . 1872; S . Yamada, H. Xshikawa, and E. Yoshida,Bull. Chern. SOC. Japan, 1966, 39, 994.240 J. L. Karn and D. H. Busch, Nature, 1966, 211, 160.z41D. C. Goodall, J. Chem. Soc. ( A ) , 1966, 1562.242 J. Lewis, R. F. Long, and C. Oldham, J. Chem. SOC. ( A ) , 1965, 6740; D. Gibson,J. Lewis, and C. Oldham, J. Chem. SOC. ( A ) , 1966, 1453.2 4 3 W. C. Andersen and R. H. Harris, Inorg. Nuclear Chem. Letters, 1966, 2, 315;K. N. Raymond and F. Basolo, Inorg. Chem., 1966, 5, 949.244 P. Nicpon and D. W. Meek, Chem. Comm., 1966, 398.245 F. Glockling and K. A. Hooton, Chem. Comm., 1966, 218.R. V. Lindsey, jun., G.W. Parshall, and V. G. Stolberg, Inorg. Chern., 1966,5, 109.E. W. Abel and B. C. Crosse, J. Chem. Soc. ( A ) , 1966, 1377MABBS A N D M A C H I N : THE T R A N S I T I O N E L E M E N T S 205have been assigned to the various vibrational modes in nickel@), palla-dium(=), and copper( n) bis- (oxamido)-complexes,24~ to metal-nitrogenstretching vibrations in palladium( 11) , platinum(=) and rhodium( m) halideMeCN, PhCN, and bipyridyl cornple~es,~4~ and to stretching vibrations ofthe azide group in the compounds [Ph4As]2[Pt(N3)4]H20, [Ph,As],[Pt(N,),],and [Ph,As][Au(N,),]. The magnetic data, electronic and infrared spectraof Rb,~i(NO,),] were reported to be consistent with a distorted octahedralstructure involving nitrogen co-ordinated and either chelating or symmetri-cally bridging nitrite groups.251 Similar spectra measurements indicate thepresence of nitro groups in the complexes [NiL,(NO,),] (L = a substitutedethylenediamine), although in chloroform solution some of the complexesshowed an equilibrium between nitro and nitrito groups.252The complex (NO,+)[Ni(NO,),], which has peE = 4-54 B.M. a t 21"c,was reported to be the first known example of a high-spin Ni(m) c0mplex.~5~The reaction between palladium and nitric acid has been shown to give[Pd(NO,),(OH),], which can then react with N204 t o give [Pd(N03),2N204],or with N,O, to give the simple nitrate, Pd(N0,),.254 The reaction betweenbromine trifluoride and the compounds M,[PtCl,] (M = K,Rb,Cs,NO+)gave M',[PtC13F3], except in the case of M = NO+, when (NO),[PtF,] wasformed.255 The infrared and Raman spectra of K,[Pt(CN),Cl,] were re-ported, and the force constants for bond stretching calc~lated.~5~ Thepreparations and magnetic properties of the compounds M[PtF,] (M = XeF,,NO, NO,) have been described.257 The reaction between PtF, and ClF,gave a compound which infrared data suggest should be formulated as[ClF,] +[PtF,]-.With PtF, and tetrafluorohydrazine, PtF, and PtF4 wereproduced succe~sively.25~Copper, Silver, and Gold.-The infrared and Raman spectra of compoundscontaining the ions [Cu(CN),]-, [CU(CN),]~-, and [Cu(CN)JS- have beendiscussed in terms of possible stereochemistries and modes of bonding inthese ions.259 Infrared spectral studies on pressed discs of KBr andKAu(CN), showed that solid solutions were not formed, but that [Au(CN),]-groups remained in clusters.260 The preparations of complexes of the type[ML,]X (L = 8-methylthioquinoline, 8-benzylthioquinoline ; M = Cu, Ag ;248 P.X. Armendarez and K. Nakamoto, Inorg. Chem., 1966,5, 796.249 R. A. Walton, Canad. J . Chem., 1966, 44, 1480.250 W. Beck, E. Schuierer, and K. Feldl, Angew. Chem., Internat. Edn., 1966, 5,251 B. J. Hathaway and R. C. Slade, J . Chem. SOC. ( A ) , 1966, 1485.252 D. M. L. Goodgame and M. A. Hitchman, Inorg. Chem., 1966, 5, 1303.253 C. C. Addison and B. G. Ward, Cl2em. Cornrn., 1966, 819.2 5 4 C. C. addison and B. G. Ward, Chem. Cmm., 1966, 155.255 D. H. Brown, K. R. Dixon, and D. W. A. Sharp, J . Chem. SOC. ( A ) , 1966,256 L.H. Jones and J. M. Smith, Inorg. Chem., 1965, 4, 1677.257 T. I?. Gortsema and R. H. Toeniskoetter, Inorg. Chern., 1966,5, 1217; N. Bartlettand S. P. Beaton, Chem. Cotnm., 1966, 167; N. Bartlett, F. Einstein, D. F. Stewart,and J. Trotter, ibid., p. 550.258 F. P. Gortsema and R. H. Toeniskoetter, Inorg. Chem., 1966, 5, 1925.259 D. Cooper and R. A. Plane, Inorg. Chem., 1966, 5, 16; J. D. Graybeal and G. L.McKown, ibid., p. 1909; M. J. Reisfeld, and L. H. Jones, J. ~Wol. Spectroscopy, 1965,260 L. H. Jones and I K. Kressin, J . Chem. Phys., 1965, 43, 3956.249.1844.18, 222206 INORGANIC CHERTISTRYX = ClO,) have been described.261 The characterisation and suggestionsfor the structure of the ion [Au,(DPE),cl]+ (DPE = 1,2-bisdiphenylphos-phinoethane) have been reported.262 The reaction between [ (Ph,P),CuBH,]and perchloric or tetrafluoroboric acids resulted in compounds containing the[(Ph3P)2Cu(BH,)Cu(PPh3)2]+ ion, for which it structure with four bridginghydrogens between the copper and boron atoms was pr0posed.~6~ Thepresence of carbon bonded acetylacetone has been demonstrated in thecompounds [( R,P)A~(acac)].~~~ The rapid evolution of carbon dioxide fromsolutions of CuCl and CCl, in Me2S0 has been interpreted in terms of thefollowing reactions :2658CuCl + CCI, + Me,SO = [4cu(I) + ~CU(II) + 12C1-] + CO + Me,SThe preparations of [(Et,P)Au Y] [Y = alkyl or aryl mercaptides, SCN,SC (S)NEt, , SC( S) OEt , SC( NH,)&E€, +Br -1, [ (PhO),PAuCl] , [ ( R3P) ,Au] +(R = Et or Ph), and [R,Au XI (R = Bu, Ph; X = C1, Br, SCN) have beendescribed.266The magnetic susceptibilities of the following compounds have been inter-preted in terms of their probable structures and the occurrence of magneticexchange interactions (in some cases estimates of the magnitudes of theseinteractionsihave been made) : {Cu(02C[CH,],C02)} ;267 [(R,N)CU(CH,CO,)~X](X = NCS, NO,, Br);268 [Cu(RR’CHCO,),] (R = R’ = Et; R = H and(butanol)] (X = H, p-Me, p-MeO, p-Br, p-N02);270 [CuL2X2] and [CuLX,](L = substituted pyridine N-oxide; X = halide),271 [Cu(AO)X] A 0 =amino-alcoholates; X = halide) ;2’2 bis-(imidazolato)Cu(~~),~~~ and X-sal-c-aminophenol)Cu(11).274 In the copper acetate dimer support for the &bond-ing model for the metal-metal interaction has been obtained from 63Cunuclear magnetic resonance. 275Molecular orbital calculations on some bis- (p-diketone)Cu(n) complexeshave been reported, and the results compared with e.s.r.and electronicspectral measurements.276 Similarly, molecular orbital calculations have261 F. Hein and K.-H. Vogt, Annalen, 1965, 689, 202; F. Hein and K.-H. Vogt,2. anorg. Chem., 1965, 340, 46.262 L. Naldini, F. Cariati, G. Simonetta, and L. Malatesta, Chem. Comm., 1966, 647.263 F. Cariati and L. Naldini, J . Inorg. Nuclear Chem., 1966, 28, 2243.264 D. Gibson, B. F. G. Johnson, J. Lewis, and C. Oldham, Chem. and Ind., 1966,342.265 R. R. Lavine, R. T. Iwamoto, and J. Kleinberg, J . Amer. Chem. SOC., 1966, 88,366 (x. E. Coates, C. Kowala, and J. M. Swan, AustmE.J . Chem., 1966, 19, 539.267 L. Dubricki, C. M. Harris, E. Kokot, and R. L. Martin, Inorg. Chem., 1966, 5,268 D. M. L. Goodgame and D. F. Marsham, J . Chem. SOC. ( A ) , 1966, 1167.26D W. E. Hatfield, H. M. McGuire, J. S. Paschal, and R. Whyman, J . Chcm. SOC. ( A ) ,2 7 0 W. E. Hatfield, C. S. Fountain, and R. Whyman, Inorg. Chem., 1966, 5, 1855.2 7 1 W. E. Hatfield and J. C. Morrison, Inorg. Chem., 1966, 5, 1390; Y. Muto and273 E. Uhlig and K. Staiger, 2. anorg. Chem., 1966, 346, 21.273 M. Inoue, M. Kiahita, and M. Kubo, Bull. Chem. SOC. Japan, 1066, 39, 1352.2 7 4 W. E. Hatfield and F. L. Bunger, Inorg. Chem., 1966, 5, 1161.276 H. C. Allen, jun., J. Chem. Phys., 1966, 45, 553; F. A. Cotton and J. J. Wise,CO + Me,SO = CO, + Me,SR’ = CN, MeO, EtO, PhO, CT-ClC6H40, p-NO,C,H,O) ;269 [CU(X-CGH,CO2)2-4304.93; B.N. Figgis and D. J. Martin, ibid., p. 100.1966, 1194.H. B. Jonassen, Bull. Chem. SOC. Japan, 1966, 39, 58.D. J. Rogers, Inorg. Chem., 1965, 4, 1830.J . Amer. Chem. SOC., 1966,88, 3451; G. N. LaMar, Acta Chem. Scad., 1966,20, 1359MABBS AND MACHIN: THE TRANSITION ELEMENTS 207also been made for [cu(m3)6]2+9 [c~(H,o),]~+, and copper(II) in tetrahedral,square-planar, and octahedral chloride environments. 277 The interpretationof the optical and e.s.r. spectra of [CuC1,I2-, dissolved in Cs,ZnCl, and(Me4N),ZnC1, host lattices, has led to the proposal that the low symmetryof the ion is an intrinsic property, for which the dominant mechanism is theJahn-Teller effect.278Quinqueco-ordinated copper(n) was reported to occur in the complexes[X-salen-N(R)R’],Cu (R = H orMe and R’ = Me), [Cu(mepic),X](ClO,)(mepic = 6-methyl-2-picolylamine; X = halide), [(A)Cu-(CN)-Cu(A)](C1O4),(A = hexamethyltetra-azacyclotetradecadiene),27s and [Cu(bipy),X] (X =halide). This last compound is thought to have a compressed trigonal-bipyramidal structure. Based on spectral and magnetic evidence, tetra-gonally distorted octahedral structures have been assigned to the complexes[Cu(NH,),]X, (X = C1-, Br-, I-, BF4-, ClO,-) and [Cu(ben~imidazole)~X,](X = C1, Br, NO,, ClO,, NCS, +SO,).2s1The Raman spectra of powdered samples and solutions of compoundscontaining the ions [MX,]”- (M = Au; X = C1, Br, I; n = 1 : M = Pt:X = C1, Br, I; n = 2: M = Pd; X = C1, Br; n = 2) have been examinedand M-X stretching force constants estimated. 282 The compoundCs,K[AgF,] has been prepared and its magnetic moment reported to be2.6 BM.,83Zinc, Cadmium, and Mercury.-The bond stretching force constantsEl(Hg-Hg), E,(Hg-X) and the interaction constant, El,, between adjacentbonds in the compounds Hg,X, (where X = C1, Br H,O) have been estimatedfrom their Raman spectra.284 The isolation of compounds Hg2L4(C10,),[L = Ph,PO, pyN0, (CH,CH,CH,),SOJ, Hg,L,SiF, (L = Ph,PO,pyNO),Hg,(Me,SO)SiE”,,xH,O, Hg2(Me,SO),.,(C10,), and HgNO, has been re-ported.2s5 Metal-phosphorus vibrations in the complexes [(Ph,P),MX,](M = Zn, Cd, Hg; X = C1, Br, I) have been assigned to bands in the98-166 cm.-l region.286 Frequency assignments have also been made fromthe Raman spectra of [M en,]X, (M = Zn, Cd, Hg; X = andof aqueous solutions of Hg(CN), and halide ions.,g8The preparations of 1 : 1 addition compounds between 1 ,3,5-trithian9HgX, (X = C1, Br, I), and AgX (X = NO,, C1, Br, I)2s9 and of the com-plexes [ZnB,X,], [ZnB,X,], [ZnB,X,] (B = py, 4-Me py, %Me py; X = C1,277 P.Ros and G. C. A. Schuit, Theor. Chim. Acta, 1966, 4, 1; B. ROOS, A d a Chem.Scand., 1966, 20, 1673.278 M. Sharnoff and C. W. Reimann, J. Chem. Phys., 1965, 43, 2993.279 Y. M. Curtis and N. T. Curtis, Awtral. J. Chem., 1966, 19, 609; L. Sacconi andI. Bertini, Inorg. Chem., 1966, 5,1520; S . Utsuno and K. Sone, J . Imrg. Nuclear Chem.,1966, 28, 2647.2so H. Elliott, B. J. Rathamay, and R.C. Slade, J . Chem. SOC. ( A ) , 1966, 1443.281 M. Goodgame and L. J. B. Haines, J . Chem. SOC. (A), 1966, 174; H. Elliott andB. J. Hathaway, Inorg. Chem., 1966, 5, 885.282 P. J. Hendra, Nutwe, 1966, 212, 179.283 R. Hoppe and R. Homann, Naturwiss., 1966, 53, 501.286 R. A. Potts and A. L. Allred, Inorg. Chem., 1966, 5, 1066.286 G. B. Deacon and J. H. S. Green, Chem. Comm., 1966, 629.287 K. Krishnan and R. A. Pla.ne, Inorg. Chem., 1966, 5, 852.28* R. P. J. Cooney and J. R. Hall, J. Inorg. Nuclear Chem., 1966, 28, 1679.J. A. W. Dalziel and T. G. Hewitt, J . Chem. SOC. (A), 1666, 233.H. M. Gager, J. Lewis, and M. J. Ware, Chem. Comm., 1966, 616208 INORGAN%C CHENISTRYBr, I, NCS)290 have been described. From infrared spectra and the iso-morphous inclusion of cobalt(I1) ions, it was concluded that [ZnB,X2],[ZnB,X,], and [ZnB,X,] have tetrahedral, five-co-ordinate, and octahedralstructures, respectively.Mercury-silicon and zinc-germanium bonding isreported in [ (Ph,Si),Hg] 291 and [Zn(GePh,),], 292 respectively.290 D. P. Graddon, K. B. Henig, and E. C. Watton, Aust~al. J. Chem., 1966, 19,1801.2Q1 R. A. Jackson, Chena. Cmm., 1966, 827.2n2 E. Amberger, W. Stoeger, and R. Honigschmid-Grossich, Angew. Chem., Internat.Edn., 1966, 5, 5225. TRANSITION-METAL CARBONYLS ANDRELATED COMPOUNDSBy F. J. Kohl and J. Lewis(Department of Chemistry, University of Manchester)THE techniques for the preparation of metal carbonyls and olefin derivativeshave been summarised,l the reactions of ligands co-ordinated with transitionmetals have been reviewed,2 the application of n.m.r.in organometallicchemistry has been summarised,x and the chemistry of the Group VIBcarbonyls 4 and the nqture of sulphur- and phosphorus-bridged complexesof the transition metals have been ~urveyed.~ Reviews have appeared onthe cyclopentadiene and arene metal carbonyls,6 hydride complexes,‘nitrosyl-metal complexes,g metal cl~sters,~ the electronic structures oforganometallic molecules,1* and acylation reactions, l1 as well as fluorineorganometallic complexes,l2, 13 metal-ally1 complexes, l* and cyclic-organicmetal derivatives.l5 A n extensive survey of the chemistry of nickel-cyclo-octadiene systems has been given.16An English edition of “ Metal n-Complexes ” by Fischer and Werner hasbeen published;l7 books on metal hydrides l8 and benzoid-metal complexeshave also appeared. Seyferth and King have produced an annual survey oforganometallic chemistry, and this must be considered as one of the moreoutstanding texts of the year;20 it provides a valuable service to the field.Structure.-A theoretical assessment of the bonding in metal car-bonyls 21 and unsaturated hydrocarbon derivatives of iron and chromium 22H.F. Holtzclaw, jm., Inorg. Synth., 1966, 7, 178.J. P. Collman, Transition Metal Chem., 1966, 2, 2.S. L. Stafford and H. D. Kaesz, Adv. Organometallic Chem., 1965, 3, 1.G. R. Dobson, I. W. Stole, and R. K. Sheline, Adv. Inorganic Chemzstry Radio-chem., 1966, 8, 1.ti R. G. Hayter, Preparative Inorg.Reactions, 1965, 2, 211. * R. L. Pruett, Preparative Inorg. Reactions, 1965, 2, 187.A. P. Ginsberg, Transition Metal Chem., 1965, 1, 112. * B. F. G. Johnson and J. A. McCleverty, Progr. Inorg. Chem., 1966, 7, 277.O F. A. Cotton, Quart. Rev., 1966, 20, 389.lo D. A. Brown, Transition Metal Chem., 1966, 2, 2.l1 F. Calderazzo and K. Noack, Coordination Chem. Rev., 1966, 118; R. F. Heck,l2 R. D. Chambers and T. Chivers, Organometallic Chem. Rev., 1966, 1, 279.l3 F. G. A. Stone, Endeavour, 1966, 25, 33.l4 G. Wilke, B. Bogdanovid, P. Hardt, P. Heimbach, W. Keim, M. Kroner, W.Oberkirch, K. Tanaka, E. Steinbriicke, D. Walter, and H. Zimmermann, Angew. Chem.,1966, 78, 157.l5 P. M. Maitlis, Adv. Organometallic Chem., 1966,4,95; M. A. Bennett, ibid., p.353;H. Cais, Organometallic Chem. Rev., 1966, 1, 433.l6 B. Bogdanovic, M. Kroner, and G. Wilke, Annalen, 1966, 699, 1.l 7 E. 0. Fischer and H. Werner, “ Metal .rr-Complexes,” Elsevier, Amsterdam, 1966.l8 K. M. Mackay, “ Hydrogen Compounds of the Metallic Elements,” Spon, London,lo H. Zeiss, P. J. Wheatley, and H. J. S. Winkler, “ Benzoid-Metal Complexes,”2o D. Seyferth and R. B. King, Ann. Survey Organometallic Chem., 1965, 1.21 S. F. A. Kettle, J. Chem. SOC. (A), 1966, 1013, 420.2 2 B. J. Nicholson, J. Amer. Chem. Soc., 1966, 88, 5156.Adv. Organometallic Chem., 1966, 4, 243.1966.Ronald Press, New York210 INORGANIC CHEMISTRYtri-carbonyl has been discussed. The carbonyl stretching frequencies in theinfrared spectra of complexes have been considered theoretically, and changesin bonding forces shown to be associated with n-electron effects.23 Theintensity of both carbonyl and nitrosyl vibrations has been correlated tothe bond angle between the groups and the theory applied to an extensiveseries of comp0unds.~4 The relative intensities of the two % vibrations ofcompounds of the form XMh(CO), have been considered in terms of couplingand distortionof bond angles at themetal away from The low-frequencyspectra (700-200 cm.-l) of a series of manganese carbonyl derivativesMn(CO),L (L = halogen or alkyl) have been measured and discussed withrelation to the carbonyl stretching modes.26 Mass spectroscopic measure-ments are now being extensively applied to organometallic and carbonylsystems.The negative-ion mass spectra of nickel, iron, chromium, molyb-denum, and tungsten carbonyl have been determined.2' The utilisation ofmass spectra in the determination of the number of hydrogen atoms in thecarbonyl hydrides of manganese, rhenium, and ruthenium has been empha-sised,28 whilst the spectra of some polynuclear carbonyls and related com-pounds of manganese, molybdenum, rhenium, iron, ruthenium, osmium, andcobalt have been reported, and the fragmentation pattern associated withthe structure of these polynuclear cornpound~.2~-~~The study of the kinetics of substitution reactions of the Group VIcarbonyls with a variety of phosphines, amines, and oligo-olefins have shownthat the reactions proceed by an SNl dissociative mechanism a t low ligandconcentrations ( <0.025~),53 whereas at higher concentrations ( > 0 .0 5 ~ )phosphine exchange occurs by a dual path involving an additional SN2mechanism.34 The kinetics of mono- and di-substitution of mcyclopenta-dienylrhodium dicarbonyl by phosphines, phosphites, and isonitriles showthat the reaction is first-order in substrate and a reagent.35 The data onthe exchange of carbon monoxide and triphenylphosphine with nickelcarbonyl have been reassessed and indicate that the reaction proceeds by anon-dissociative first-order process. 36The structure of iron dodecacarbonyl has finally been resolved in thesolid state by X-ray diffraction, and is, as suggested in the previous AnnualReports, a triangular metal cluster in which one bridging group of the2s S.F. A. Kettle, Spectrochim. Acta, 1966, 22, 1388.2 4 W. Beck, A. Melnikoff, and R. Stahl, Chem. Ber., 1966, 99, 3721.2 5 A. R. Manning and J. R. Miller, J . Chem. SOC. ( A ) , 1966, 1521.26 R. W. Cettrall and R. J. H. Clark, J . Organometallic Chem., 1966, 6, 167.2 7 R. E. Winters and R. W. Kiser, J . Chem. Phys., 1966, 44, 1964.28 B. F. 0. Johmon, J. D. Johnston, J. Lewis, and B. H. Robinson, Chem. Comm.,2s J. Lewis, A. R. Manning, J. R. Miller, and 5. M. Wilson, J . Chem. SOC. (A), 1966,s1 B. F. G. Johnson, J. Lewis, and I. G. Williams, Chem. Comm., 1966, 391.8a D. W. Slocum, R. Lewis, and G. J. Mains, Chem. and Ind., 1966, 2095.8a H. Werner and R. Prinz, Chem. Ber., 1966, 99, 3582; J . Organometallic Chem.,84 R.J. Angelici and J. R. Graham, J . Amer. Chem. SOC., 1966,88, 3658.85 H. G. Schuster-Woldan, and F. Basolo, J . Amer. Chem. SOC., 1966, 88, 1657.86 L. R. Kangas, R. F. Heck, P. M. Henry, 5. Breitschaft, E. M. Thorateinson, and1966, 851.1663.R. B. King, J . Amer. Chem. SOC., 1966, 88, 2075.1966, 5, 79; H. Werner, ibid., p. 100.F. Basolo, J . Amer. Chem. Soc., 1966, 88, 2334KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 211Fe,(CO), system is replaced by an Fe(CO), The structure of arelated triphenylphosphine derivative, [Pe,( CO),1PPh,],39 has also beendetermined; one of the terminal carbonyl groups of the E’e2(C0)g unit iasubktituted by the phosphine. The two bridging carbonyl groups arcasymetrically bonded to the two iron atoms with iron-carbon distances of1.74 and 1.98A..The structure of the hexapyridineiron salt of the ion[Fe,(C0),,]2- has been determined by X-ray analysis; an Fe(CO), unit isco-ordinated to a basal Fe,(CO), fragment with the remaining carbonylgroup bridging the three irons of the E”e,(CO)g group.4o The structure ofthe tetracobalt dodecacarbonyl has been shown to involve the co-ordinationof a Co(CO), group to a plane of cO,(Co)g in which three of the carbonylgroups are bridging the three cobalt atoms in pairs.37 The correspondingiridium compound was found to have no bridging carbonyl groups, whilstthe infrared spectra indicate that the corresponding rhodium complex has asimilar structure to the cobalt complex.41 Baird and Wilkinson p2 haveshown that the sulphur analogue of carbonyl complexes may be obtainedfrom the reaction of carbon disulphide with rhodium and rutheniumsalts, e.g.,(Ph,P),Rh( CO)Cl+ (Ph,P),Rh( CS)Cl+ (Ph,P) ,Rh( CS)Cl,.The X-ray structure of the rhodium@) complex indicates a linearrhodium-carbon-sulphur In contrast, tetrakistriphenylphosphine-platinum( 0) reacts with carbon disulphide to give an addition complex(Ph,P),PtCS, in which the platinum is considered to bond to the carbonand one of the sulphur atoms.44Carbonyls and Carbonyl Halides.-A new low-pressure synthesis of ruth-enium carbonyl from ruthenium chloride with zinc in methyl alcohol under aCO pressure of less than 100 atmosphere is given.45 The reactivity of thiscarbonyl with phosphines, nitric oxide, and organic dienes has been investi-gated.4* With phosphines and dienes, trinuclear metal clusters occur inthe products, whilst in nitric oxide the dinitrosyldicarbonylruthenium isformed.A range of technetium carbonyl adducts has been prepared withphosphines, thiols, and halides as co-ordinated groups.47 Manganese penta-carbonyl-nitrate has been shown to react with pyridine and bipyridyl togive tricarbonyl adducts in which the nitrate group is still co-ordinated tothe metaL4* Anionic halogeno-rhenium carbonyl complexes have been pre-pared and both mononuclear and binuclear systems have been isolated.49cs, c1,s7 C. H. We; and L. F. Dahl, J . Amer. Chem. SOC., 1966, 88, 1821.D. J. Dahm and R. A. Jacobson, Chem. Comrn., 1966, 496.89 R.J. Angelici and E. E. Siefert, Inorg. Chem., 1966, 5, 1457.4 0 R. J. Doedens and L. F. Dahl, J. Amer. Chem. SOC., 1966, 88, 4847.41 W. Beck and K. Lottes, Chem. Ber., 1961, 94, 2578.42 M. C. Baird and G. Wilkinson, Chem. Cornm., 1966, 267.43 J. L. De Boer, D. Rogers, A. C. Skapski, and P. G. H. Troughton, Chem. Comm.,4 4 M. C. Baird and G. Wilkinson, Chem. Comm., 1966, 514.4 6 M. I. Bruce, F. G. A. Stone, Chem. Cormn., 1966, 684.J. P. Candlin, K. K. Joshi, and D. T. Thomson, Chem. and Id., 1966, 1960.W. Hieber, F. Lux, and C. Herget, 2. Nuturforsch., 1965, 20b, 1159.48 C. C. Addison and M. Kilner, J . Chem. SOC., ( A ) 1966, 1249.49 E. W. Abel, I. S. Butter, M. C. Ganorkar, C. R. Jenkins, and M. H. B. Stiddard,1966, 756.Inorg. Chem., 1966, 5, 25212 INORGANIC CHEMISTRYThe reaction of carbon monoxide with hexachlororuthenate-(n) and -(m)yields a variety of anionic ruthenium carbonyl-halide derivatives.50 Theformation of [Ru(CO)(H,O)C1J2- from ruthenium chloride and formic acidhas been studied kineti~ally.~~ The synthesis of the Rh(r) and Rh(m)complexes trans-[RhX(CO)L,] (X = C1, Br, I, SCN; L = PR,, AsR,) and[Rh(CO)L,X,] (X = C1, Br; L = PR,) is reported. The rhodium(1) com-pounds react with Ph2PCH,CH2PPh2 (diphos) to give the very stable saltRh( diphos),Cl. 52 The corresponding cobalt complex is obtained fromthe interaction of [Co(diphos),] and Co(diphos),X2,5S whilst the iridiumanalogue is prepared from either the dicarbonyl-amine-halide complexes,(CO),(amine)IrCl, with ph~sphine,~* or by the equivalent reaction used forthe rhodium salt.54 In the latter case the presence of a carbonyl inter-mediate [Ir(diphos),(CO)]Cl has been detected.This compound may alsobe prepared from the salt [Ir(diphos),]Cl with carbon monoxide.64 Theiridium salt reacts with oxygen to form [O,Ir(diphos),]Cl, and forms six-co-ordinate adducts with H,, HCl, HBr, H,S, and halogens, whilst five-co-ordinate adducts are formed with SO, and 54 Oxidative additionreactions of this type have been extensively reported for the iridium andrhodium d8 systems of the type [L,M(CO)X] (L = phosphine; X = halogen),to give L,M(CO)X,YZ (M = Rh; YZ = CH,COBr) 52 (M = f r ; YZ = HF,HC1, HBr, HI, H2S,55 RS02C1).56[( Ph,P),( CO)Cl,Ir( SO,R)], formed by this last reagent, lose sulphur dioxideif R = p-tolyl or phenyl, to give the aryl-iridium complex [L,Ir(CO)C1,R].56With boron trihalides 57 for rhodium and sulphur dioxide 58 with iridium,five-co-ordinate complexes are formed. The X-ray structure of the lattercompound [(Ph,P),Ir(CO)Cl(SO,)] has been determined and shows a tetra-gonal bipyrimidal stereochemistry with bonding of the sulphur dioxidethrough the s~lphur.5~ Tetracyanoethylene forms addition complexes withboth the rhodium and iridium series as also with the corresponding rhodiumthiocarbonyls [Rh(Ph,P),(CS)X] (X = Cl, Br); direct bonding of the olefingroup is postulated to occur in these complexes.g0 A kinetic study of theaddition of oxygen, hydrogen, and methyl iodide to the series trans-IrX(CO)(PPh,), (X = Cl, Br, I) establishes that the reaction of hydrogenand oxygen is similar and differs from that of methyl iodide.61 The re-markable nitrogen complex [(Ph,P),Ir(N,)Cl] is formed by the reactionof the complex [Ir(CO)Cl(PPh,),] with a number of acid azides; a band a t2095 cm.-l in the infrared spectrum is associated with the nitrogen-nitrogenThe iridium(=) X-sulphinatesJ. Halpern, B.R. James, and A. L. W. Kemp, J . Amer. Chem. SOC., 1966, 88,6142.s1 J. Halpern and A. L. W. Kemp, J . Amer. Chem. SOC., 1966, 88, 5147.52 J. Chatt and B. L. Shaw, J. Chem. SOC. ( A ) , 1966, 1437.63 A. Sacco, M. Rossi, and C. F. Nobile, Chem. Comm., 1966, 589.6* L. Vaskrt and D. L. Catone, J . Amer. Chem. SOC., 1966,88, 5324; W. Hisber and6s L.Vaska, J . Amer. Chem. SOC., 1966, 88, 6325.s6 J. P. Collman and W. R. Roper, J. Amer. Chem. SOC., 1966, 88, 180.5 7 P. Powell and H. Noth, Chm. Comm., 1966, 637.18 L. Vaska and S. S. Bath, J . Amer. Chem. SOC., 1966, 88, 1333.69 S. J. Laplaca and J. A. Ibers, Inorg. Chem, 1966, 5, 405.60 W. H. Baddley, J . Amer. Chem. SOC., 1966,88, 4546.61 P. B. Chock and J. Halpern, J. Amer. Chem. SOC., 1966,88, 9511.V. Frey, Chem. Ber., 1966, 99, 2607KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 213stretching frequency.62 This complex is related to the nitrogen adducts[(N,)Ru(NH,),]X, reported by Allen and Sen~ff,~, the X-ray structure ofwhich establishes a linear metal-nitrogen grouping. 64 A polymeric carbonylhalide of palladium, [PdCl(CO)],, has been obtained by passing moist airthrough a suspension of PdC1,CO.The complex is a red-violet solid which isinsoluble in organic solvents.65Nitrogen and Phosphorus Derivatives.-The synthetic use of tris( aceto-nitrile)tungsten tricarbonyl has been developed, and yields, with benzene,toluene, p-xylene, mesitylene, cyclohepta-1,3,5-triene, cyclo-octadiene,dimethylaminofulvene, the tricarbonyl adducts, whilst tetracarbonyl com-plexes are formed with norbornadiene and cyclo-octa-l,5-diene, and adicarbonyl complex with cyclohexa-1,3-diene, W(CO),(C6H,),.66 The photo-chemical production of pentacarbonyl amine complexes of the Group VIcarbonyls has been reported.67 Reactions of amines with molybdenumpentacarbonyl-halogen anions, [Mo(CO),X]-, yield, in addition to the penta-carbonyl amine complexes, the tetracarbonylbis( amine) adducts, the relativeproportions produced depending upon the halide anion involved.68 Thetetraethylammonium salts of the halogenopentacarbonyl anions of theGroup VI metals give mono-, bis-, and tris-isonitrile derivatives on reactionwith both alkyl and aryl i~onitriles.6~ Mixed phosphine or amine-bipyridylor o-phenanthroline complexes of the form M( CO),X,Y and M( CO),X2Y,[M = Cr, Mo; W, X, = phen, bipy; Y = py, NH,, Ph,P, (RO),P] havebeen reported.'O Potassium cyanide reacts with the (dicarbonyl)bis(bipyidyl)complexes of chromium, molybdenum, and tungsten with displacement ofthe nitrogen bonds, to give the salts K4[M(C0)2(CN)4] (M = Cr, Mo, W).'lOctamethyltetraphosphonitrile reacts with molybdenum carbonyl to give afetracarbonyl phosphonitrile complex.The phosphonitrile is considered tobond to the molybdenum through the two nitrogens at opposite ends of themolecule .71aIt has been suggested that succinonitrile bonds to manganese by an-interaction of the cyano groups in the complexes Mn( CO),(NCCH,CH,CN)X(X = C1, Br, I),72 whilst a normal a-bonding structure of the cyanide isconsidered to occur in the acrylonitrile dimer, [(CO),Fe(CH, = CHCN)],.The co-ordination number of the iron is attained by co-ordination of theolefin group, the acrylonitrile acting as a bridging group between the twometal ions.73 Nickel carbonyl reacts with diallylcyanamide to give thedimer [( R,N*CN),Ni( CO)], ; the structure is considered to involve bridging6 2 J.P. Collman and J. W. Kang, J. Amer. Chem. SOC., 1966, 88, 3459.63 A. D. Allen and C. V. Senoff, Chem. Comm., 1965, 621.64 F. Bottomley and S. C. Nyberg, Chem. Comm., 1966, 897.65 A. Treiber, Tetrahedron Letters, 1966, 2831.*6 R. B. King and A. Fronzaglia, Inorg. Chem., 1966, 5, 1837.67 W. Strohmeier, J. F. Guttenberger, H. Blumenthal, and G. Albert, Chern. Ber.,68 H. D. Murdoch and R. Henzi, J . Organometallic Chem., 1966, 5, 463.69 H. D. Murdoch and R. Henzi, J . Organometallic Chem., 1966, 5, 166.70 L. W. Houk and G. R. Dobson, Inorg. Chem., 1966, 5, 2119.71 H. Behrens, E. Lindner, and J. Rosenfelder, Chem. Ber., 1966, 99, 2744.'la J. Dyson and N. L. Paddock, Chem. Cmm., 1966, 191.12 M. F. Farona and N.J. Bremer, J . Amer. Chem. SOC., 1966, 88, 3735.7 s E. H. Schubert and R. K. Sheline, Inorg. Chem., 1966,5, 1071.1966, 99, 3419214 INORGANIC CHEMISTRYcarbonyl groups with the two nitrogens bonding and the diallylcyanamideacting as chelate.74 1,4-Diazabuta-l73-diene carbonyl complexes of nickeland molybdenum have been obtained, and the reaction of these with iodineand triphenylphosphine rep0rted.7~ The interaction of a series of newphosphine ligands with metal carbonyls has been reported recently.Tetrakis(diphenylphosphinomethy1)methane reacts as a double bidentateligand with chromium, molybdenum, tungsten, and nickel carbonyls, to yieldthe spirocyclic compounds M( GO),( Ph,P*CH,), and C( CH,P.Ph,),M( CO),(M = Cr, Mo, W, n = 4;76 Ni, n = 2 77).The nitrogen-phosphorus mixedligands Ph,PC,H,NEt,(NP), PhP(C,H,NEt,),(NPN), and(Ph,PC,H,),NEt(PNP) react with molybdenum carbonyl to yieldMo(CO),NP, Mo(CO),(NPN), and Mo(CO),(PNP),78 respectively, whilst thepotentially quadridentate group tris-(o-diphenylphosphinopheny1)phosphine(QP) reacts with manganese carbonyl compounds to give complexes inwhich the ligand is bidentate, [MnX(CO),(QP)] (X = halogen), terdentate,[Mn( CO),QP]+, or quadridentate, [Mn( CO),QP] +. The related ligands bis-(o-dipheny1phosphino)phenylphosphine (TP) and o-phenylenebisdiphenyl-phosphine (DP) yield the complexes [Mn( CO),TP]+ and [Mix( CO),DP].'@Oxidation of [Mn(CO),(diphos),]Cl with a range of oxidising agents yieldsthe paramagnetic manganese(=) ion [Mn( CO),(diphos),]2+.The first phosphine complexes of osmium carbonyl, Os(CO),(PPh,),, havebeen isolated from the reaction of OsX,(CO),(PPh,), (X = halogen) withzinc in the presence of CO.The carbonyl-phosphine complex reacts withhalogens to give the ions [Os(CO),(PPh,),X]+ (X = Br, I) and hydrogenchloride to give [0s(CO),(C1,)(PPh3),].~~ The preparation of cationic car-bony1 complexes, using the method of Fischer, Fichtel, and Oefele,82 hasbeen applied to rhodium and iridium carbonyl phosphine and stibene com-plexes, to yield the ions [M(CO),L,]+ [M = Rh, I r ; L = PPh,, P(C,H,J,,SbPh,].g3 With antimony, the hydrides HM(CO)(SbPh,),Cl, (M = Rh, Ir)were also isolated.A series of phosphine-substituted products of nickel carbonyl with theligand 2,8,9-trioxa- l-phospha-adamantane, P( OCH,),(CH,),, have beenobtained. They are of the general formulae Ni(CO),-,L, (x = 1,2,3,4).With iron, chromium, molybdenum, and tungsten, the corresponding mono-and di-substituted compounds were obtained.The reactions of nickelcarbonyl with the series of bifunctional phosphines (CF,)2POP(CF,)2,(CF,),PSP(CF,),, and (CF,),PN(Me)P( CP3), lead to polymers involvingbridging carbonyl groups.s57 4 H. Bock and H. tom Dieck, Chem. Ber., 1966, 99, 213.75 H. Bock and H. tom Dieck, Angew. Chem., 1966, 78, 549.76 J. Ellermann and K. Dorn, J . Organometallic Chem., 1966, 6, 157.7 7 J. Ellermann and K. Dorn, Angew. Chem., 1966, 78, 547.78 G. R. Dobson, R. Craig Taylor, and T. D. Walsh, Chem. Comm., 1966, 281.7 9 B.Chiswell and L. M. Venanzi, J . Chem. SOC. ( A ) , 1966, 417.8 0 M. R. Snow and M. H. B. Stiddard, J . Chem. SOC. ( A ) , 1966, 777.81 J. P. Collman and W. R. Roper, J . Amer. Chem. SOC., 1966, 88, 3504.8a E. 0. Fischer, K. Fichtel, and K. Ofele, Chem. Ber., 1962, 95, 249.83 W. Hieber and V. Frey, Chem. Ber., 1966, 99, 2614.84 D. G. Hendricker, R. E. McCarley, R. W. King, and S. G. Verkade, Inorg. Chem.,1966, 5, 639.86 A. B. Burg and R. A. Sinclair, J . Amer. Chem. SOC., 1966, 88, 5354KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 215Sulphur Derivatives.-The interaction of molybdenum and tungsten car-bonyls with nickel bis(dithioketone) yields the a-dithioketone complexesM(S,C,R,)(CO), (M = W, R = Me) and M(S,C,R,),(CO), (M = Mo, W,R = alkyl or aryl); the reactivity of the carbonyl groups in these moleculesto phosphine molecules has been investigated.86 The investigation of thereactions of thiols with rhenium and manganese carbonyl complexes hascontinued,*', 88 and the field has been extended with the formation of thecorresponding selenium ad duct^.^^A series of manganese carbonyl derivatives of dithiocarbonates andmonothiocarbonates has been reported 00'-dimethyl and -diphenyldithiophosphate complexes of manganese carbonyl have been studied, andin the bipyridyl complexes Mn( CO),( bipy) ( S,P(OR), the ligand appears tobe acting as a unidentate rather than a bidentate g r o ~ p .~ l The product ofthe reaction of bis(trifluoromethy1)dithietin with the cobalt carbonyl hasbeen established to be trimeric [C,F,S,Co(CO)], from the mass spectra.The complex is paramagnetic (p = 1-84 B.M.) as anticipated on this formula-tion.The isoelectronic nitrosyl iron compound has also been shown to betrimeric from the mass spectra, [E"e(NO)C,F6S,],.92Miscellaneous.-The preparation of compounds with boron-manganesebonds has been rep0rted.~3 Bisdimethylaminoboron chloride reacts withsodium manganesepentacarbonyl to give the compound (Me,N),B-lSh(CO),.The complex reacts with hydrogen a t 100 atmospheres to give manganesecarbonyl and bis( dimethylamino)borane, and with bromine to yield bis-(dimethy1amino)boron bromide and pentacarbonylmanganese bromide. TheIIB n.m.r. spectra are interpreted. as indicating back-donation from themanganese d-orbitals to the trigonal planar boron atom.A series of tri-phenylphosphine oxide and bipyridyl dioxide complexes of rhenium carbonylhalides is reported.94Hydrides.-The formation of bis- (n-cyclopentadieny1)zirconium dihydrideand the monohydride-borohydride adduct is reported to occur byaction of trimethylamine on the corresponding borohydride complex(n-C,H,),Zr(BH,),. The complexes are postulated to have a polymericbridging hydride structure S5 with the metal-hydrogen vibration occurringat 1540 cm.-l. The reaction of nitrogen with transition-metal complexesto give ammonia has been establi~hed.~6 For the system(n-C,H,),TiCl,-C,H,MgX, the e.s.r. spectra have been interpreted as indi-86 G. N. Schrauzer, V. P. Mayweg, and W. Heinrich, J . Amer.Ohm. Soc., 1966,88,5174; G. N. Schrauzer, V. P. Mayweg, H. W. Finck, and W. Heinrich, ibid., p. 4604.8 7 A. G. Osborne and F. G. A. Stone, J . Chem. SOC. ( A ) , 1966, 1143.88 E. W. Abel and B. C. Crosse, J . Chern. SOC. ( A ) , 1966, 1141.8g E. W. Abel, B. C. Crosse, and G. V. Hutson, Chem. and Id., 1966,238.go W. Hieber and M. Gscheidmejer, Chem. Ber., 1966, 99, 2312.O1 F. A. Hartman and A. Wojcicki, Inorg. Nuclear Chem. Lettes, 1966, 2, 303;g2 R. B. King and F. T. Korenowski, Chem. Comm., 1966, 771.CJ* H. Noth and G. Schmid, J . Organometallic Chem., 1966, 5, 109.O 4 U. Sartorelli, F. Canziani, and F. Zingales, Inorg. Chem., 1966, 5, 2233.96 B. D. James, R. K. Nanda, and M. G. H. Wallbridge, Chem. C m . , 1966, 849.CJ6 M. E. Vol'pin and V.B. Shur, Nature, 1966,209,1236; M. E. Vol'pin, V. B. Shur,K. N. Latyaeva, L. J. Vyshinskays, A. L. Shul'gaitser, Izvest. Akad. Nauk S.S.S.R.Ser. khim., 1966, 385.R. L. Lambert and F. A. Manuel, Inorg. Chem., 1966,5, 1287216 INORGANIC CHEMISTRYcating the presence of binuclear hydride bridges with nitrogen insertioninto those hydride bonds with formation of imine specie^.^'The wide-line n.m.r. spectrum of the manganese pentacarbonyl hydrideindicates that the H-Mn bond distance is 1*28A, and hence establishesthe presence of “ short ” metal-hydrogen bonds in these sy~tems.~gThe preparation and reactions of hydrido t e tracarbon yl t rip hen ylp hosp hine -manganese(@ has also been reported.99 The X-ray structures of theion [Cr,H(CO),,]- have been interpreted in favour of a linear Cr-H-Crgroup.100 The synthesis of [M,H(CO),,]- and [M2(CO),o]2- (M = Cr, Mo,and W), and the intercorrelation between the two sets of ions, has beenestablished ; the formation of mixed complexes [MM’H(CO),,]- has beendetected from the n.m.r.spectra, and the infrared and 11.111.13. data on theseries interpreted in terms of a symmetrical hydrogen-metal bridge.101 Theaddition of the Lewis acids BF, and BCI, to bis mcyclopentadienyl hydridesof molybdenum, tungsten, and rhenium leads to the formation of 1 : 1adducts.lo2 A new polynuclear hydride of rhenium HRe,(CO),, has beenreported lo1 and the exchange of 13C0 with the hydride studied; thisenables the preparation of stereospecific 13C0 labelled Re,(CO),, to beobtained.lo1 A comprehensive study of the rhenium hydride phosphinesystem has been carried and yields three classes of compounds,ReH,(PR,),, [ReHz(PR3)2]n, and [ReH,(PR,),].A nitrosyl hydride ofiron HFe(NO)(PF,), has been obtained by acidification of the potassiumsalt prepared by the action of potassium amalgam on the dinitrosylbis-trifluorophosphineiron complex. lo4Three new ruthenium hydrocarbonyls have been obtained, H,Ru,(CO),,and H2Ru,(C0),,.28, lo5 The first compound appears to exist in two differentforms, as the proton n.m.r. signals occur at z 18.5 and 23.5 for the twoisomers. The hydrogen-metal stretching vibration in some iridium andosmium carbonyl hydridophosphine complexes have been shown to becoupled to the carbonyl vibration when the hydrogen is trans to the carbonyl,but no interaction occurs in the cis-compounds.lo6 Some hydrido-complexesof iridium(@ with trichlorotin and a variety of phosphine ligands have beenreported. 107 The first pure hydrido- complexes with only non-n- bondingligands co-ordinated to the metal have been obtained by the zinc-dustreduction of chloropenta-amminerhodium(m) salts,1°8 in the anions[RhH(NH,),]2+ and [RhH(H20)(NH,)J2+.A related cyanide complex,K,[RhH(CN),(H,O)], has been obtained from rhodium carbonyl chloride0 7 H. Brintzinger, J . Amer. Chem. SOC., 1966, 88, 4305, 4307.98 T. C. Farrar, W. Ryan, A. Davison, and J. W. Faller, J . Amer. Chem. SOC., 1966,99 B. L. Booth and R. N. Haszeldine, J . Chem. SOC. ( A ) , 1966, 157.88, 184.100 L.B. Handy and P. M. Treichel, J . Amer. Chem. SOC., 1966, 88, 366.101 R. G. Hayter, J . Amer. Chem. SOC., 1966,88,4376; R. W. Hamil and H. D. Kaesz,102 M. P. Johnson and D. F. Shriver, J . Amer. Chem. SOC., 1966, 88, 301.lo3 J. Chatt and R. S. Coffey, Chem. Comm., 1966, 545.lo4Th. Kruckand W. Lang, Chem. Ber., 1966, 99, 3794.105 J. W. S. Jamieson, J. V. Kingston, and G. Wilkinson, Chem. Cmm., 1966, 569.L. Vaska, Chem. Comm., 1966; J . Amer. Chem. SOC., 1966,88,4100.107 R. C. Taylor, J . F. Young, and G. Wilkinson, Inorg. Ch., 1966,5, 20; A. Sacco,168 J. A. Osborn, A. R. Powell, and G. Wilkinson, Chem. Comm., 1966, 461.Inorg. Nuclear Chem. Letters, 1966, 2, 69; W. Fellmann and H. D. Kaesz, ibid., p. 63.R. Ugo, and A. Moles, J .Chem. SOC. ( A ) , 1966, 1670KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 217and cyanide ; the compound reacts with nitric oxide, tetrafluoroethylene,and oxygen to give K,[Rh(CN),(NO,)H,O], K3[Rh(CN)5C2F4H], andK4[ (CN),( H20)Rh0,Rh( CN),( H,O)], respectively. lo9A series of equilibria l10 have been established between zerovalentplatinum phosphine complexes and hydrido-phosphine complexes on reactionof the tetrakistriphenylphosphineplatinum(0) and tristriphenylphosphine-platinum(0) complexes with acids (L = triphenylphosphine).-L HC1 -LPtL, PtL, \k[PtHL,]Cl [PtHClL,]+L -TICXI lHCl+L KOHI k[PtH,C1,L,IUsing 110 this system, it has been possible to isolate a series of derivatives ofthe type [PtH(PPh,),]X (X = ClO,-, BF4-, HS04-, CH,0S03-) and[PtHY(PPh,),] (Y = CN-, SCN-).The reaction of the complex[PtH(PPh,),]HSO, with base in the presence of oxygen produces the zero-valent bistriphenylphosphineplatinum compound,lll [Pt(PPh,),]. The bis-phosphine chlorohydride platinum complex has been shown to react withtetracyanoethylene to give the first example of a carbon, with a cyanidegroup attached, bonding directly to a metal, (Ph,P),Pt(C6N,).ll2During the past year, continued interest in homogeneous hydrogenationusing transition-metal complexes as catalysts has been maintained. Anextensive discussion of the kinetics and mechanism of these reactions usingthe complexes (Ph,P),RhX (X = C1, Br, I) as catalysts has been given,113and the activity of the related compounds (MPh,),RhCl (M = As, Sb)assessed.ll4 Por the system (PtCl,C,H,), it is concluded that hydrogenationof the n-bonded ethylene occurs without the formation of a-diadsorbedintermediates.ll5 The homogeneous hydrogenation of aldehydes has beenaccomplished under hydroformylation conditions using a rhodium trichloridecatalyst ; rhodium carbonyl compounds are possible intermediates in thisprocess.lls The kinetics and mechanism of the homogeneous catalytichydrogenation of maleic and fumaric acids with a ruthenium(=) chloridecatalyst has been studied.Tracer studies indicate that the hydrogen atomsadded to the olefin group originate from the solvent rather than the hydrogengas.ll7Nitrosyls.-The e.s.r. spectra of the metal pentacyanonitrosyl complexesof some of the first-row transition elements have been discussed.llg Theinfrared spectra of various metal nitrosyl complexes 119 have been measuredloB D.N. Lawson, M. J. Mays, and G. Wilkinson, J. Chem. Soc. (A), 1966, 52.110 F. Cariati, R. Ugo, and F. Bonati, Inorg. Chem., 1966, 5, 1128.ll1 R. Ugo, F. Cariati, and G. La Monica, Chem. Comm., 1966, 868.112 W. H. Baddley and L. M. Venanzi, Inorg. Chem., 1966, 5, 33.119 J. A. Osborn, F. H. Jardine, J. F. Young, and G. Wilkinson, J. Chem. SOC. ( A ) ,J. T. Mague and G. Wilkinson, J. Chem. SOC. ( A ) , 1966, 1736.115 K. E. Hayes, Nature, 1966, 210, 412.ll6 B. Heil and L. Mark6, Chem. Ber., 1966, 99, 1086.11' J. Halpern, J. F. Harrod, and B. R. James, J. Amer. Chem. Soc., 1966, 88, 6150.P. T. Manoharan and H.B. Gray, Incrg. Chem., 1966, 5, 823; B. A. Goodman,11* P. Gans, A. Sabatini, and L. Sacconi, Inorg. Chem., 1966, 5, 1877.1966, 1711.J. '€3. Raymor, and M. C. R. Symons, J. Chem. SOC., ( A ) 1966, 994218 INORGANIC CHEMISTRYbetween 4000 and 80 cm.-l. The approximate nitrosyl and carbonylforce constants have been calculated for the isoelectronic series Mn(NO),CO,Fe(NO),(CO),, Co(NO)(CO),, and Ni(CO),, and the variation of these valuesfor the substituted derivatives LMn(NO),, Ni(CO),L,, Fe(NO),L,, andCo(NO)L, discussed in terms of the n-bonding properties of the group L.120The presence of considerable n-bonding between nitrogen and chromium inthe complex ~-C,H,Cr(NO),Cl has been deduced from the X-ray structureof the compound.121 The presence of geometrical isomers of the series[C5H5Cr(NO)XI2 [X = NMe,, SR; (Y-PeSMe),, Y = (CO),, (NO),],[C,H,NiX], (X = SMe), and [C,H,Fe(CO)X], (X = SR, PPh,) has beenestablished,12, and their separation achieved.Nitrosyl-iron and -cobaltadducts of the ligands [S,C,R,] (R = C,H,, CF,, CN) have been isolated.l23A series of octahedral nitrosyl ruthenium complexes of the type Ru(NO)X,L,has been reported (X = halogen; L = pyridine, CH,CN, R,As, R,Sb, R2S,bipy, phen, diar~ine).12~ Both five-co-ordinate and six-co-ordinate binuclearcomplexes (NO)RuI,X, (X = pyridine, bipy, R,As) have been prepared.125The X-ray structure of the alleged seven-co-ordinate complex(NO)Ru(S2CNEt,), shows it to be six-co-ordinate, with one of the dithio-carbonate groups being bonded as a unidentate group.l26 Reaction of thecompounds Co(NO)(CO), and Fe(NO),(CO), with excess of diphos establishedthe presence of '' long lived " intermediates with the phosphine bondedthrough only one phosphorus atom, which react finally to give the disub-stituted derivatives.The diphosphine has been shown to act as a bridginggroup12' between two [Co(NO)(CO),] groups, and on reaction with bothcarbonyls forms the mixed complex (NO),Fe( C0)-diphos-Co( CO),(NO).In the complex C1(NO),Co-diphos-Co(NO),C1 a similar diphos bridge ispresent. Binuclear phosphido-bridged adducts, [(NO),M-PPh,], (M = Fe,Co) have also been obtained.l28? l Z 9 A series of cyanonitrosyl and cyano-carbonylnitrosyl anions of cobalt has been prepared from the reaction ofpotassium cyanide with nitrosyltricarbonylcobalt in liquid ammonia.130The kinetics and mechanism of the reactions of a variety of phosphines,phosphites, arsines, isonitrile, and pyridine derivatives with the complex[NOCo(CO),] have been elucidated,131 and the products [Co(NO)(CO),L]is01ated.l~~ A large range of mono- and di-nitrosyl complexes of cobalt withl a o Q.R. van Hecke and W. Dew, Inorg. Chem., 1966, 5, 1960.lal 0. L. Carter, A. T. McPhail, and G. A. Sim, J . Chem. SOC. ( A ) , 1966, 1095.laa M. Ahmad, R. Bruce, and G. Knox, 2. Naturforsch., 1966, 216, 289.lP8 J. Locke, J. A. McCleverty, E. J. Wharton, and C. J. Winscom, Chem. Comm.,la4 J. Chatt and B. L. Shaw, J . Chem. SOC., 1966, 1811; M. B. Fairy and R. J. Irving,mi R. J. Irving and P.G. Laye, J . Chem. SOC. (A), 1966, 161.18* A. Domenicano, A. Vaciago, L. Zambonelli, P. L. Looder, and L. M. Vemmzi,la' R. J. Mawby, R. Morris, and E. M. Thorsteinaon, and F. Basolo, Inorg. Chem.,128 W. Hieber and G. Neumair, 2. anorg. Chem., 1966, 342, 93.lze W. Hieber and R. Kummer, 2. anorg. Chem., 1966, 344, 292.l9O H. Behrens, E. Lindner, and H. Schindler, Chem. Ber., 1966, 99, 2399.ls4 E. M. Thorsteinson and F. Basolo, Inorg. Chern., 1966, 5, 1691.1966, 677.ibid., p. 475.Chem. C m m . , 1966,476.1966, 5, 27.E. M. Thorsteinson and F. Basolo, J . Amer. Chem. SOC., 1966, 88, 3929KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 219ethylenediamine, pyridine, and aniline as ligands has been e~tablished,l~~-l~~and the nature of the nitrosyl group in theredand black penta-ammine cobaltsalts discussed.135Transition-metal Carbonyl Complexes containing Metal-Metal Bonds.-An electrochemical study of a large range of compounds containingmetal-metal bonds has been reported, and the nucleophilicities of sometransition-metal complex anions studied.136 The metal-metal bond energyin manganese decacarbonyl has been determined 137 t o be 18.9 & 1.4 kcal.from mass-spectral data; this value falls near the range 34 & 13 kcal.determined earlier.138 Raman spectroscopy has been applied to somebinuclear metal carbonyl complexes, and shows that the approximateforce constants of the decacarbonyls M2(C0)10 follow the orderRe-Mn > ReRe > Mn-Mn.139 The infrared spectra of manganese deca-carbonyl and the bisphosphine substituted complexes l4O9 141 have beendiscussed in terms of the Cotton-Kraihanzelm0de1.~4~ The data imply thatthere is no n-bonding across the metal-metal bond.l4l The triphenyl-phosphine-manganese decacarbonyl system has been reinvestigated, and theadducts isolated are (Ph,P)Mn,(CO), and [(Ph,P)Mn(CO),],.The presenceof a monomeric paramagnetic species, [(Ph,P)Mn(CO),], has been refuted.143However, the kinetics of the reaction of Ph,P with iodine and manganesedecacarbonyl indicate that the primary step is fission of the metal-metalbond to give Mn(CO), radicals.ld4 The kinetics of carbon monoxide exchangeof a variety of carbonyls containing Hg-Co, Cd-Co, Sn-Coy Au-Coy andAu-Mn bonds have been carried and the rate of exchange is found tovary widely.Anisotropic electron-transport has been established in singlecrystals of the complexes Ir(acac)(CO), and Rh(aca~)(CO)~ (acac = acetyl-acetonate ion). Maximum electrical conductivity occurs along the axes ofthe metal-metal bonds.l*6The structure of the compound ( C,H5C,C6H,)Fe,(CO)g involves a triangleof iron atoms each with three terminal carbonyl groups. The organic groupis situated above this plane with one of the acetylenic carbon atoms bondedto all the iron atoms, whilst the other acetylene carbon is bonded to onlytwo of the iron atoms.147 A new osmium dodecacnrbonyl complex, with133 W. Beck, W. Hieber, and G. Neumair, 2. anorg. Chem., 1966, 344, 285.13p T. B. Jackson, M. J. Baker, J. 0. Edward, and D.Tutas, Inorg. Chern., 1966,136 J. B. Raynor, J . Chem. SOC. (A), 1966, 997.13$ R. E. Dessy, P. M. Weissman, and R. L. Pohl, J . Amer. Chem. SOC., 1966, 88,5117; R. E. Dessy, R. B. King, and M. Waldrop, ibid., p. 5112; R. E. Dessy, F. E.Stary, R. B. King, and M. Waldrop, ibid., p. 471.137 D. R. Bidinosti and N. S. McIntyre, Chem. Comm., 1966, 555.13* F. A. Cotton and R. R. Monchamp, J . Chem. Soc., 1960, 533.lBD H. M. Gager, J. Lewis, and M. J. Ware, Chem. Comm., 1966, 616.14* D. J. Parker and M. H. B. Stiddard, J . Chem. Soc., 1966, 695.141 J. Lewis, A. R. Manning, and J. R. Miller, J . Chem. SOC. (A), 1966, 845.I r a F. A. Cotton and C. S . Kraihanzel, J . Amer. Chem. SOC., 1962, 84, 4432.l r 3 H. Wawersik and F. Basolo, Chem.Comm., 1966, 366.144 D. Hopgood, and A. J. Po6, Chem. Cmnm., 1966, 831.145 S. Breitschaft and F. B ~ o l o , J. Amcr. Chent. SOC., 1966, 88, 2702.146 C. G. Pilt, L. K. Monteith, L. F. Ballard, J. P. Collman, J. C. Morrow, W. R.14' J. F. Blount, L. F. Dahl, C. Hoogzand, and W. Hiibel, J . Amer. Chem. SOP.,88, 2046.Roper, and D. Ulkii, J. Amer. Chem. Soc., 1966, 88,4236.1966, 88, 292.x220 INORGANIC CHEMISTRYosmium tetroxide is reported, OS,(CO)~~,OSO~, and is considered to involvebonding of the OsO, group through three oxygens to the plane of osmiumatoms.148 A silicon analogue of the dimer [Co,(CO),C], has been preparedby the reaction of tetraphenylsilane with cobalt carbonyl, and is the fistcazbonyl reported 149 with a silicon-silicon bond, [Co,(CO),Si], .The prepara-tion of the complex [Co(CO),],C .CH2CH2C0,H is reported.l5* The X-raystructure of bis(tricoba1t enneacarbonyl)acetone, obtained by heating thecompound [Co(CO),],CBr to 90°c, shows that insertion of a carbonyl groupbetween the two carbon atoms of the dimers to giveis involved.151 The interaction of 3,3,3-trifluoropropyne with cobalt carbonylhas been investigated,162 and the complexes [Co( CO)3],C*CH2CF, (I),[Co(CO),],HC*C*CF, (11), and [Co(CO),],[HC*C*CF,], (111) have been isolated.Compound (I) is considered to be a derivative of the [Co,(CO),C] cluster;(11) is related to the corresponding complex of hexafluorobut-2yne [(cF,c=cc~,)co,(co)6],153 whilst (111) is postulated to have bridgingo l e h groups. The preparation of a new type of metal cluster with manganeseand iron carbonyls has been reported in the ion [MIIF~,(CO)~,]-,~~~ and thecompound [Mn,Fe(CO)l,] .lS5 The crystal structure of the complexn-C,H,Fe(CO),Mn( CO), has been determined and shows that the moleculecontains a metal-metal bond.156 The preparation of the mixed carbonyls(CO),Re-Mn(CO),, (CO),Re-Co(CO),, and some derivatives has been effectedby a Wurtz-type reaction between anionic and cationic carbonyl species.l5'A bidentate gold ligand, Ph,P*AuC,H4C6H4Au*PPh2, has been used to pre-pare the first chelate complex containing metal-metal bonds, by interactionof the ligand with the anion l?e(CO),2-.158 Cationic complexes in whichmercury is bonded to iron,lS9 ruthenium, and osmium l60 carbonyl phosphinederivatives have been reported.For the iron complex, the stability of theproduct depends upon the nature of the phosphine. For ruthenium andosmium the compounds are formulated as [( CO),M L,(HgX)][HgX,],(L = Ph,P, X = C1, Br, I; M = Ru, 0s). Substitution reactions of thecompounds (XHg),Fe(CO), (X = CJ, Br), with a variety of nitrogen baseshave been studied.161 The interaction of mercuric chloride with cyclo-391.L. Marko, and B. Marko, Chem. Ber., 1962, 95, 333.14* B. F. G. Johnson, J. Lewis, I. 0. Williams, and J. Wilson, Chm. Comm., 1966,149 S. F. A. Kettle and I. A. Khan, J . Organometallic Chenz., 1966, 5, 588; M. G. Bor,150 G. Albanesi and E. Garezotti, Chimica e Industria, 1965, 47, 1322.151 G. Allegra, E. M. Peronaci, and R.Ercoli, Chem. Comm., 1966, 549.152 D. A. Harbourne, D. T. Rosevear, and F. 0. A. Stone, Inorg. N w b a r Chem.Letters15315415615815715815916016 1I, 1966, 2, 247.J. L. Boston, D. W. A. Sharp, and G. Wilkinson, J . Chem. SOC., 1962, 3488.U. Anders and W. A. G. Graham, Chem. Comm., 1966, 291.E. H. Schubert and R. K. Sheline, 2. Naturforsch., 1965, 206, 1366.P. J. Hansen and R. A. Jacobson, J . 0,rganometallic Chem., 1966, 6, 389.Th. Kruck, M. Hofler, and M. Noack, Chem. Ber., 1966, 99, 1153.B. Chiswell and L. M. Venanzi, J . Chem. SOC. ( A ) , 1966, 901.D. M. Adam, D. J. Cook, and R. D. W. Kemmit, Chem. Comm., 1966, 103.J. P. Co1lma.n and W. R. Roper, C h . Comm., 1966, 244.J. Lewis and S . B. Wild, J . Chem. SOC. ( A ) , 1966, 69KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 221pentadienylcobalt dicarbonyl162 yields the ionic complex[Co(CO),(C,H,)HgCl]Cl related to the phosphine carbonyl derivatives ofosmium and ruthenium discussed above.A wide range of tin-metal bonds has been prepared.A new preparativetechnique for the interaction of amido-tin complexes with transition-metalhydrides has been developed, and leads to the complexes (Ph,P),PtCl( SnMe,)and ( C,H,) (CO),W-SnMe,.C,H,(CO),Mo*Ti(OPri),, has been obtained using the same type of r e a ~ t i 0 n . l ~ ~The reaction of the anions [M(C,H,)(CO),]- (M = Cr, Mo, W) with the com-pounds R,MX (M = Ge, Sn, Pb; R = Me, Ph; X = halide) yields thecomplexes [C,H,( C0),M-M'R3]. The stability of these clusters increasesfrom chromium to tungsten.16, The preparation and spectroscopic pro-perties of the series Ph,M'-M(CO), (M' = Si, Ge, Sn, Pb; M = M i , Re) andX,Sn-M(CO), (M = Re, Mn, X = Me, C1, Br) have been investigated.Itis concluded that in these compounds the Br,Sn- and C1,Sn- groups arestrong n-acceptor ligands. l 6 5 The X-ray structure of the compoundPh,Sn-Mn(CO), is reported.lG6 The reaction of iron pentacarbonyl withtributyltin chloride yields the compounds [BuaSnFe(C0),],Fe(CO),,Bu,Sn,[Fe(CO),],, and Sn[Fe(CO)J,; the last compound may be obtaineddirectly from stannous chloride and iron carbonyl. The X-ray structureof this compound indicates a tetrahedral array of iron atoms around the tin,each iron having four terminal carbonyl groups and the iron atoms beingbonded to each other in pairs.167 The preparation and infrared spectra ofthe complex RSn[Co(CO),], (R = Ph, Me, CH, = CH, n-C4H5, C1, Br, I)have been reported.16s Interaction of rhodium and iridium carbonyl phos-phines, [L,M(CO),], with sodium amalgam in the presence of carbon monoxideand subsequent addition of trimethyltin halide, triphenylphosphinegoldhalide, or mercuric cyanide gives the compounds [Me,SnM(Ph,P)(CO),],[Ph,PAuIr(CO),Ph,P], and [Ph,P*Ir(CO),],Hg, (M = Ir, Rh) .169The use of insertion reactions for the preparation of metal-metalbonds has been applied to give the complexes [C,H5Fe(CO)2],SnC1,,170[(CO),LCo],SnX, [X = C1, Br, I ; L = CO, Ph,P, (PhO),P, B U , P ] , ~ ~ ~ , 172 and[C5H,(CO)Ni],SbC1,,171 when stannous halides are used.Other Group I11 orIV halides can also participate in insertion reactions, and thus the compounds[C,H,Fe(CO),],GeI,, [Co( CO),],InBr,THF, and XGa[Co(CO),],, THF(X = Br, I) 172 have been prepared. The germanium compound may reactwith methyl-lithium or borohydride to give the adducts X,Ge[Co(CO),],A molybdenum-titanium complex,162 D. J. Cook and R. D. W. Kemmitt, Chern. and Ind., 1966, 946.163 D. J. Cardin and M. F. Lappert, Chem. Comm., 1966, 506.164 H. R. H. Patil and W. A. G. Graham, I n o r g . Chem., 1966,5, 1401.166 W. Jetz, P. B. Simons, J. A. J. Thompson, and W. A, G. Graham, I n o r g . C h m . ,16' J. D. Cotton, J. Duckworth, S. A. R. &ox, P. F. Lindley, I. Paul, F. G. A. Stone,169 J. P. Collman, F. D. Vastine, and W.R. Roper, J. Amer. Chem. Xoc., 1966, 88,170 C. Edmondson and M. J. Newlands, Chern. and Ind., 1966, 1888.171 D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 1405.1966, 2217.H. P. Weber and R. F. Bryan, C h . Comm., 1966, 443.D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 2222.and P. Woodward, Chem. Comm., 1966, 253.5035.F. Ronati, 8. Cenini, D. Morellj, and R. Ugo, J. Chem. Xoc. ( A ) , 1966. 1052222 INORGANIC CHEMISTRY(X = Me, H).l75 The details have been given 174 for insertion of fluoro-olefins between the tin and manganese atoms in Me,Sn-Mn(CO),, brieflyreported last year. This is in contrast with the results for the correspondingreactions of the compound Me,GeMn(C0),.175OrganometaUic Compounds of the Transition Metals+Bonded Organometallic Compounds.-Reaction of dicyclopentadienyl-zirconium &chloride 176 with triethylaluminium is comidered to give thebridging group ZP-CH,CH2-ZrIV.The reaction 77 of diphenylacetylenewith biscyclopentadienyltitanium dicarbonyl gives the titanium heterocyclicring (1).The unstable alkyl zirconium methyl complexes Zr(CH,), and Li,Zr(CH,)6have been observed in the reaction between methyl-lithium and zirconiumtetrachloride.l78 Reduction of alkyl halides and olefins with chromous saltsis considered to involve chromium(m)-ally1 intermediates.179~ l80 Thekinetics of hydrolysis and the kinetics of the reaction of mercury chloridewith six complex penta-aquopyridiomethylchromium(m) ions are re-ported.lgl The preparation of some benzyl-chromium( m) complexes,[CrC&(py),L] (L = benzyl, o-chlorobenzyl, p-chlorobenzyl) has been re-ported, and the use of these as sources of benzyl anions and radicals hasbeen investigated.ls2 The conversion of o-aryl chromium complexes of thetype R3Cr(THP), into n-complexes by suitable solvents has been studied;whereas conversion was possible with the ligands C,H,-C,H, and CH,c,H,,the trimesityl complex failed to rearrange.lB3 The X-ray structure of oneof the first o-bonded arylchromium( m) complexes, CI,Cr(THF)#-tolyI, hasbeen published.The (3-0 bond trans to the p-tolyl group is significantlylonger than the other two Cr-0 bonds (3-21 and 2.04& respectively) andthis is attributed to a trans effect of the p-tolyl group.lg4 A series of aryl-173 N.Flitcroft, D. A. Harbourne, I. Paul, P. M. Tucker, and F. G. A. Stone, J . Chem.174 D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 1586; H. C. Clark175 H. C. Clark, J. D. Cotton, and J. H. Tsai, Inorg. Chem., 1966, 5, 1582.176 H. Sinn and E. Kolk, J . Organometallic Chem., 1966, 373.177 K. Sonogashira and N. Hagihara, Bull. Chem. SOC. Japan, 1966, 39, 1178.178 H. J. Berthold and G. Groh, Awgew. Chem., 1966, 78, 495.17n C. E. Castro, R. 0. Stephens, and S. MojB, J . Amer. Chem. SOC., 1966, 88, 4964.180 J. K. Kochi and P. E. Mocadlo, J . Amer. Chem. SOC., 1966, 88,4094.181 R. 0. Coombes and M. D. Johnson, J . C h m . SOC. ( A ) , 1966, 1805.182 R. G. Coombes and M. D. Johnson, J . C h m . SOC. ( A ) , 1966,177; R.P. A. Sneeden,18s G. Stolze, J . Organometallic Chem., 1966, 6, 383; G. Stolze and J. Hlihle, ibid.,lS4 J. J. Daly, R. P. A. Sneeden, and H. H. Zeiss, J . Amer. C h m . SOC., 1966, 88,SOC. ( A ) , 1966, 1130.and J. H. Tsai, &d., p. 1407.H. P. Throndsen, J . Organometallic Chem., 1966, 6, 542.p. 645.4287EOHL AND LEWIS : TRANSITION-METAL CARBONYLS 223chromium(m) aryl complexes related to some of the allyl derivatives dis-cussed in the previous Report has been obtained. The complexNa,[Cr( C,H,),Et20],2Ef,O has been obtained in diethyl ether from phenyl-sodium and CrCI,, (THF),. With excess of phenylsodium the hexaphenylcomplex Na,[Cr(C,H,),,xEt,O] is obtained; it is only stable in excess ofphenylsodium.185 Reaction of the pentaphenyl compound with thechromium trichloride adduct, CrCl,,(THF), in diethyl ether yields thecomplex Na,[ Cr,( C6H,),,3Et,0].Chromium( II) phenyl derivatives may beobtained by reduction of the corresponding chromium(m) phenyl complexeswith the production of biphenyl. The reduced paramagnetism of thesederivatives is associated with the presence of chromium-chromium inter-action of the type observed in chromous acetate.ls6A a-bemyl derivative of the composition C,H,( CO),MoCH,C6H5 has beenprepared from the reaction of benzyl chloride with the cyclopentadienyl-tricarbonylmolybdenum anion. On irradiation in hexane solution this isconverted into a n-benzyl derivative C,H&H,MO(C~)~( C,H,) (see below).l8'The reaction of chloromethyl isocyanate, with the same molybdenum anion,yields the complex [(CO),C,H,MoCH&CO] ; with the corresponding ironanion, [FeC,H,( CO),] -, the compound ( C,H,),Fe,( CO),( CH,NCO) wasobtained.l88 The preparation of the &st aryl-rhenium complexes has beengiven; the complexes formed are [Re(R),(PR,),], [ReR,(PR,),],, and[ReNR,(PR,),] (R : Ph, CH,C,H,; PR, = Ph,P or Et,PhP).lsg The X-raystructure of the iron carbonyl adduct with the Schiff base from p-toluidineand benzaldehyde has been reported.In [MeC,H,NCH,C,H,]E"e,( CO),, botho- and n-bonding between the iron and the arene ring are involved (2).With the azobenzene adduct [Fe(CO) ,],PhN=NPh, a different structure isobtained, with rupture of the nitrogen-nitrogen bond and rearrangementto form a o-semidine skeleton.lS0The preparation and structure of stable allyl cobaloximes RCo(D,H,)B(R = alkyl; D = dianion of 1,2-dioximes; B = base) has been established.The relationship of those systems to vitamin B,, derivatives is considered,and binuclear cobaloximes containing the unit Co(CH,),Co (n = 3,4) havelS6 F.Hein and K. Schmiedeknecht, J . Organometallic Chem., 1966, 5, 454.ls6 F. Hein and K. Schrniedeknecht, J . Organometallic Chem., 1966, 6, 45.la7 R. B. King and A. Fronzaglia, J. Amer. Cherra. SOC., 1966,88, 709.lgo P. E. Baikie and 0. S. Milk, Chem. C o m . , 1966, 707.R. B. King and M. B . Bisnette, Inorg. Chem., 1966, 5, 306.J. Chatt, J. D. Garforth, and G. A. Rowe, J . Chena. Soc. (A), 1966, 1834224 INORGANIC CHEMISTRYbeen synthesised.lgl The preparation of an extensive series of alkyl andaryl derivatives of cobalt(m) aetioporphyrin has been reported.The n.m.r.signals of the protons of the alkyl derivatives fall in the range z 1615.Crystalline ethyl and p-tolyl derivatives of iron(m) zetioporphyrin havealso been obtained.192 The stable organo-compounds RCo(BAE) andRCo(BAE33,O (BAE = bisacetylacetone-ethylenediamine ; R = CH,, C,H,,C,H,) have been formed by the reaction of Grignard reagents or aryl-lithiumwith the complexes [Co(BAE)(NH,),]Br or [Co(BAE)PPh,Br].lS3 Theutility of diethylbisbipyridylcobalt as a butadiene dimerisation catalyst hasbeen exp10red.l~~ The reaction of methyl Grignard reagents with the newcomplex C,H,CoI,Ph,P leads to the dimethyl derivative.lg5 Rhodium@)methyl adducts have been obtained by oxidative addition of methyl iodideto Rh' complexes; with the complex (Ph,P),RhCl the complexRhIMe(Ph,P),(MeI) was 0btained.1~~ The reaction of methyl iodide (andbromide) with the biscarbonylchloro-rhodium dimer in the presence of sodiumcyanide yields the complex K2[MeRh(CN),(H,0)].197 The reaction ofethylene with the hydride obtained from the action of hydrogen chloride gason the complex (Ph,P),RhCl in chloroform solution yields the ethyl complex(PPh,),RhC,H,Cl, ; with acetylene a vinyl adduct (PPh,),Rh( CH=CH,)CI,is obtained.198 The interaction of acrylonitrile and rhodium trichloride-pyridine yields a o-bonded complex (py),RhCI,-CH( CH,)CN, the sameligand was Qbserved when the hydride (Ph,MeAs),RhHCI, reacted withacrylonitrile to give (P~~~AS),R~C~,~CH(M~)CN.~~~ Some trimethyl-iridium phosphine derivatives Me,Ir(PR,) were obtained from the chloro-phosphine complexes by reaction with Grignard reagents ;lg9 a similarreaction occurs with tris(dimethy1 sulphide)rhodium( m) chloride, to givethe binuclear complex (Me,S),Me,Rh,I, which was transformed into thecyclopentadienyl complex C,H,RhMe,( SMe,) .The structures of these com-plexes are elucidated from the 103Rh-lH coupling constants.200 The pre-parations of the a-bonded nickel complexes R,Ni(bipy) (R = Me, Et),201s 202trans-NiXR(PMe,Ph),, and trans-NiR,(PMe,Ph), (R = o-tolyl, mesityl,naphthyl, pentachlorophenyl, pentafluorophenyl ; X 5 halogen) ,03 havebeen given. It was shown that the ligand tris-2- (2-biphenylyl) phosphitelgl G.N. Schrauzer and R. J. Windgassen, J. Amer. Chem. SOC., 1966, 88, 3738;G. N. Schrauzer and R. J. Windgassen, Chena. Ber., 1966, 99, 602.lea D. A. Clarke, R. Grigg, and A. W. Johnson, Chem. Comrn., 1966, 208.lQ3 G. Costa, G. Mestroni, G. Tauzher, and L. Stefani, J. Organometallic Chem., 1966,6, 181.lQ4 T. Saito, Y. Uchida, A. Misono, A. Yamarnoto, K. Morifuji, and S. Ikeda, J.Organometallic Chem., 1966, 6, 572.lQ5 R. B. King, Inorg. Chem., 1966, 5, 82.D. N. Lawson, J. A. Osborn, G. Wilkinson, J. Chem. SOC. ( A ) , 1966, 1733; M. C.Baird, D. N. Lawson, J. T. Mague, J. A. Osborn, and G. Wilkinson, Chem. Comm.,1966, 129.1Q7J. P. Maher, Chem. Comm., 1966, 785.lQ* K. C. Dewhurst, Inorg.Chem., 1966, 5, 319.lQ9 J. Chatt and B. L. Shaw, J. Chem. SOC. ( A ) , 1966, 1836.2oo H. P. Fritz and K. E. Schwarzhans, J. Organometallk Chem .,,. 1966, 5, 283.201 T. Saita, Y. Ushida, A. Misono, A. Yamamoto, K. Morifuji, and S. I. Keda,2 0 2 G. E. Wilke and E. Herrman, Angew. Chem., 1966, 78, 591.203 J. R. Moss and B. L. Shaw, J. Chem. SOC. (A), 1966 1793.J . Amer. Chem. Xoc., 1966, 88, 5198KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 225stabilises nickel-carbona- bonds in the complex [ ( C6H,-C,H4O),P],Ni( CH,),. 202A variety of allyl, aryl, and alkynyl nickel cyclopentadienyl compoundsof the type C,H,Ni(L)(R) (L = phosphine, arsine, stibine) has also been0btained.20~ Bistritylnickel was obtained by the interaction of bis-( cyclo-octa-1,3-diene)nickel(O) with hexaphenylethane, or nickel acetylacetone withhexaphenylethane in the presence of diethylahminium ethoxide.Thepure solid compound is not air-sensitive but decomposes in argon at 120'0and reacts with triphenylphosphine to give the tetrakistriphenylphosphine-nickel(0) ~omplex,~O~(Ph,C),Ni + 4PPh, +Ni(PPh,), + Ph,C--CPh,.A novel method for the preparation of ally1 derivatives of pIatinum(lr)has been observed ; octene reacts with lithium tetrachloroplatinate(n) inthe presence of formic acid in dimethylformamide to give [octylPt(CO)ClJ,which with acetylacetone and triphenylphosphine yields [octylPt(CO)(acac)]and the acyl adduct [octyl-C0.Pt(Ph3P),C1].206 The nature of a series ofplatinum-carbon bonded @-diketone compounds has been investigated, andthe utilisation of the unco-orhated carbonyl oxygens of these complexesas potential donor groups el~cidated.~O7 The X-ray structures of some cyclo-propane complexes of platinum have been determined. The complexC3H,Ptpy2C12 has been found to have a four-membered carbon-platinumI Et --cH' lbring system, whilst reaction of this complex with carbon tetrachloride orchloroform gives a compound having the structure shown in (3).Thebonding between the carbon group and the platinum is considered to bean ylide rather than a carbene structure.208 Bromination of the a-allyl-phenyldimethylarsine (L) complex of platinum, PtBr,( L)2, has been shownto lead to the formation of a platinum-carbon bond with concomitantrearrangement of one of the allyl arsine derivatives to give an isopropygrouping. An X-ray structure analysis of the ethoxy-derivative has beencarried out.209 The n.m.r.spectra of a large number of trimethylplatinum(rv)H. Yamazaki, T. Nishido, Y . Hatsumoto, S. Sumida, and M. Hagihara, J . Organo-metallic Chem., 1966, 6, 86.,05 (3. Wilke and H. Schott, Angew. Chem., 1966, 78, 592.206 D. Wright, Che'Ln. Comm., 1966, 197.$07 D. Gibson, J. Lewis, C. Oldham, J. C h m . SOC. ( A ) , 1966, 1453; J. Lewis and208 W. A. Bailey, R. D. Gillard, M. Keeton, R. Mason, D. R. Russel, Chem. Comm.,* O 0 M. A. Bennett, G. J. Erskine, J. Lewis, R. Mason, R. S. Nyholm, G. B. Robertson,C. Oldham, ibid., p. 1456.1966, 396.and A. D. C. Towl, Chem. Cmm., 1966, 395226 INORffANIC CHEMISTRY( a l l y l ) P d , ,, CH *C02EtCIderivatives have been obtained,210 and the structure of the hydroxy-compound, [Me,PtOH],, determined from n.m.r.and infrared data.211 Theconditions for the preparation of almost pure phenylcopper were reported.212A carbon-bonded p-diketone adduct of gold@) has been prepared by reactionof triphenylphosphine gold halides with thallous a~etylacetone.21~The X-ray structure of ethyl zinc iodide indicates that it is a co-ordinatedpolymer with iodide bridges.214 The molecularity of a series of alkylzincderivatives in benzene has been determined.215 The X-ray structure ofmethyl zinc methoxide shows it to have a tetrameric structure with the zincatom a t the corners of a tetrahedron.216The search for metal carbene complexes has continued during the pastyear.The X-ray structure of the methylmethoxycarbene-phosphine com-plex, Me(MeO)C.Cr(CO),(PPh,), has been carried The presence of ametal carbene intermediate has been postulated in the reaction of tetra-fluoroboric acid with the compound C,H,Fe( CO)2CH,0Me as the complex[C,H,Fe(CO),CH,] +BF,- ; norcarane is formed if the reaction is performedin the presence of cyclohexene, and cis-but-2-ene is transformed into cis-l,2-dimethylpropane.21* Di-p-dichloro-bis-n-allyldipalladium (4) is considered toreact with diazoacetate to give a carbene intermediate, as alkenes are con-verted into cyclopropane carboxylic esters. 219LRzC=CRz + I >C.H+CO,Et5J R? LDfazomethane reacts with the complex (Ph,P),IrCQCl to give a methyleneinsertion reaction, with the formation of (Ph,P),IrCO(CH,Cl). The reactivityof the product is explained in terms of the conversion into a methylenecarbene intermediate from the chloromethyl group.220A series of vinyl-metal complexes has been obtained.The reaction ofdiphenylketen with iron pentacarbonyl gives a compound whose X-raystructure establishes the complex as diphenylvinylideneoctncarbonyldi-iron. 221 A new cyclopentadienyl oxy-a-vinyliron group has been identifiedalo K. Kite, J. A. S. Smith, and E. J. Wilkins, J . Chew,. SOC. ( A ) , 1966, 1744.21a G. Costa, A. Camus, L. Gatti, and N. Marsich, J. Organonzetallic Chem., 1966,ala D. Gibson, B. F. 0. Johnson, J. Lewis, and C. Oldham, Chem. and Ind., 1966,342.214 P.T. Rloseley and H. M. M. Sheerer, Chem. Comm., 1966, 876.$16 J. Boersma and J. G. Nottes, Tetrahedron Letters, 1966, 1521; G. E. Coates and216 H. M. M. Shearer and C. B. Spencer, Chm. Comm., 1966, 194.*17 0. S. Mills and A. D. Redhouse, Chem. Comm., 1966, 814.G. L. Morgan, R. D. Rennick, and C. C. Soong, Inorg. C h m . , 1966, 5, 372.5, 568.D. Ridley, J. Chenz. Soc. ( A ) , 1966, 1064.P. W. Jolly and R. Pettit, J. Amer. Chem. Soc., 1966, 88, 5044.R. I(. Armstrong, J. Org. Chem., 1966, 31, 618.220 F. D. Mango and I. Dvoretzky, J. Amer. C h m . SOC., 1966, 88, 1654.z 2 1 0. S. Mills and A. D. Redhouse, Chem. Comm., 1966, 444KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 227from the X-ray structure of one of the reaction products from the interactionof iron pentacarbonyl with methylphenylpropiolate 222 (5).COzMecoPh' 'C02Mec=c'The reaction of acetylene with the hydride (Ph3P),RhHC1, yields thevinyl complex (Ph,P),RhCl,( CHCH,).lS6 l-Chloro-2,2-diphenylvinylsilverhas been obtained from the metathesis of the lithium compound and silverchloride.223Fluorine-containing a-Carbon Complexes.-The 19E' n.m.r. spectra of m-and p-fluorophenylplatium(n) compounds have been utilised to indicatethe relative n and 0 properties of other ligands in the molecule.224 Thepreparation of the compound (C,H,),Zr(C,E",), has been given; the compoundis chemically less robust than the titanium derivative.225 The comparisonof the metal-carbon bond lengths obtained by X-ray structure analysis othe complexes C,H,Mo(CO),X (X = C3F, and C,H5) indicates the presenceof n-bonding in the metal-carbon bond 226 for the fluorine compound.Thereaction of pentafluorobenzenethiol with the pentacarbonyl hydrides cfmanganese and rhenium yields the pentafluorophenylpentacarbonyl com-plexes C,F,M(CO), (M = a, Re) ;87 pentafluoropyridine and pentafluoro-benzonitrile react with manganese and rhenium pentacarbonyl anions togive the 3-substituted tetrafluoropyridine and tetrafluorobenzonitrile penta-carbonyl adducts, respectively. 227 The reaction of lithium pentafluorophenylwith the cation [C,H,Fe(CO),]+ gives a mixture of the pentafluorobenzoylcomplex C,H,Fe( C0),COC6F, and the 0- bonded pentafluorophenyl com-pound C,H,Fe ( CO),-C,F5 ; in contrast, the corresponding triphenylphosphinecation, [C,H,Fe( CO),PPh,] f, reacts to give addition of a pentafluorophenylgroup to the cyclopentadienyl ring with formation of a diene complex,(C,M,C,F,)Fe(CO)2(YPh3).228 The higher stability of metal-carbon o-bondsin fluoro-complexes is emphasised in the reaction of hexa>fluorobut-Zynewith the rhenium peiitacarbonyl amnion, yielding the first allene in which ao-bond to a tramition metal occurs, [(F2C=C=C) (CF,)*Re(CO),] ; a substitutedfluorocyclobuta,iie adduct is also obtained.229 a-Bonded rhenium peiita-carbony1 and cyclopentadienyliron dicarbonyl adducts of perfluorobuta- 1,3-diene have besn reported.229 The interaction of fluorinated olefins and2 t 2 L. F. Dahl, R. J. Doedens, W. Hubel, and J.Nielsen, J. A m r . Chenz. Soc.,1966, 88, 446.223 G. Kobrich, H. Frohlich, and W. Drischel, J . OrgunometuZZic Chem., 1966, 6, 194.224 E. W. Parshall, J. Amer. Chem. SOC., 1966, 88, 704.2a5 M. A. Chaudhari and F. G. A. Stone, J . Chem. SOC. ( A ) , 1966, 838.226 M. R. Churchill and J. P. Fennessey, Chsm. Comm., 1966, 695.227 B. C. Booth, R. N. Haszeldine, and M. €3. Taylor, J. Urgunometallic Chem., 1966,228 M. Green, W. Mayne, and F. G. A. Stone, Chem. Comm., 1966, 755.6, 570.P. M. Treichel and R. L. Shubkin, J . Orgunometallic Chem., 1966, 5, 488228 INORGANIC CHEMISTRYsubstituted fluorinated benzene compounds with manganese and rheniumpentacarbonyl anion and cyclopentadienyl iron dicarbonyl anion leads tothe formation of complexes with metal-carbon ~-bonds.~~O Heptafluoro-propyl iodide is found to react with the compound C,H,Co(CO)PPh, to yieldC,H,COI(C~F,)PP~,.~~~A new tetranuclear nickel cluster, [(CF3),C,],Ni,(C0),,has been obtained from the interaction of hexafluorobut-2yne and nickelcarbonyl ; the compound is formulated as involving hexafluorobut-2-enebridges.231 Perftuorovinyl complexes of platinum have been prepared byreaction of fluoro-olefins 232 and fluoroacetylenes 152 with platinum phos-phine hydride complexes, whilst addition of fluoro-olefins to tetrakistri-phenylphosphineplatinum( 0) yields the cyclic o-bonded complexes (6).(6)Reaction with perfluoroacetone yields a novel three-membered ring complexin which the platinum bonds to both the oxygen and the carbon of the per-fluoroacetone molecule, (Ph3P),Pt(CF3)2C0.233 Addition of fluoro-acetylenecomplexes to tetrakistriphenylphosphine complexes of palladium 234 andplatinum 152 yield the bistriphenylphosphine cyclic a-bonded olefin metalcomplexes (Ph,P),M(C,RR) (M = Pd, R = R’ = CP3; M = Pt, R’ = CF,,R = H).Complexes of bisperfluoroallyl mercuric complexes with a varietyof oxygen and nitrogen ligands have been described.235Carbonylation and Related Reactions.-The stereochemistry of carbonylinsertion reactions of methylmanganese pentaFarbony1 using phosphines asthe attacking ligands has been studied; a stereospecific reaction to give thecis-acyl adduct has been observed with the phosphine P( OCH,),-CCH3. 236The presence of rotational isomers in the acylpentacarbonyl manganesesystem, CXH,COMn(CO),, CHX,COMn(CO), (X = F, Cl) has been detectedby infrared measurements over a range of temperature.237 The variation inthe formation of acyl compounds with metal complex has been extendedby a study involving some novel ligand molecules.2-Chloroethyldimethyl-amine reacts with the iron anion [Fe(CO),(C,H,)]- to give the acyl complex[Me,NCH,CH,COFeCO(C,H,)I and the salt[C5H5Fe(CO),*NMe2CH2CH2Fe( CO),C,H,]CZ ; N-l-chloroethylpiperidinereactsto give C,H1oNCH,CH,Fe( CO),C,H,, and analogous complexes are obtainedwith 2-chloromethylpyridine with both the anions [Fe(CO),(C,H,)]- anda30 M. I. Bruce and F. G. A. Stone, J . Chern. SOC. ( A ) , 1966,1837; M. I. Bruce, P. W.231 R. B. King, M. I. Bruce, J.R. Philips, and F. G. A. Stone, Inorg. Chern., 1966,z33 M. Green, R. B. L. Osborn, A. J. Rest, and F. G. A. Stone, Chem. Comm., 1966,2 3 4 E. 0. Greaves and P. M. Maitlis, J . Organometallic Chem., 1966, 6, 104.zs6 H. B. Powell and J. J. Lagowski, J . Chern. SOC. ( A ) , 1966, 1282.z36 M. Green and D. C. Wood, J . Amer. Chem. SOC., 1966,88, 4106.337 F. Cdderazzo, K. Noack, and U. Schaerer, J. Organometallic Chem., 1966,6, 265.Jolly, and F. 0. A. Stone, ibid., p. 1602.5, 684.H. C. Clark and W. S. Tsang, Chem. Comm., 1966, 123.602EOHL AND LEWIS : TRANSITION-METAL CARBONYLS 229[W(CO),C,H,]-. With the molybdenum anion [n-C,H,Mo(CO),]-, however,2-chloropyridine yields an acyl complex, [NC,H,CH,COMo( CO),C5H5].The manganese pentacarbonyl anion gives a cyclic acyl product with2-chloroethyldimethylamine, [NMe,CH,CH,COMn( CO),], and with 2-chloro-methylpyridine [NC,H,CH,COMn( CO),].238Acyl derivatives of the type trans-[MX(COR)(PEt,),] (M = Pd, Pt;X = Cl, Br, I, R = Me, Et, or Ph) have been obtained by the reaction ofcarbon monoxide with the appropriate alkyl or aryl c0mplex.23~Insertion reactions analogous to carbonylation have been found to occurwith sulphur dioxide, to yield Mn(CO)&302R complexes (R = Me; CH,Ph)by reaction of the alkyl pentacarbonyl manganese with liquid sulphurdioxide. 240 A large range of cyclopentadienyl iron sulphinatodicarbonylcomplexes is obtained by a similar process, and alternative methods of pre-paring these compounds have been illustrated.241Decarbonylations of a variety of organic acyl and aryl compounds withthe complex (Ph,P),RhCl have been investigated. 242Olefin-Metal Complexes.-The mechanism of the isomerisation of olefinsby transition-metal ions has been discussed in terms of the alkyl and ally1the0ries,24~ and the mechanism of hydrogen migration in cycloheptatriene-molybdenum tricarbonyl complexes has beenMono-o1efins.-The kinetics and mechanism of the hydrolysis of thepalladium-ethylene system to acetaldelyde have been investigated.245 Amolecular orbital treatment of the ultraviolet polarised crystal spectrum ofZeise’s salt, K[Pt(C,H,)Cl,]H,O, has been reported.246 The proton n.m.r.spectra of Zeise’s salt and related molecules have been used to determine theorientation of the olefin to the plane of the platinum-chlorine system.247The far-infrared spectra of a series of ethylene-platinum complexes havebeen observed,2** and a normal co-ordinate analysis of the infrared spectraof Zeise’s salt was carried 0ut.2~9A number of compounds have been reported in which, in addition toco-ordination of the olefin, bonding of the ligand occurs a t other centres.Iq the complex Me,AsC=C(AsMe,)CF,CF,[Fe( CO),], one of the iron atoms isoctahedrally co-ordinated to three CO groups and the two arsenic atoms witha metal-metal bond in the sixth position; the remaining iron has trigonal-bipyramidal stereochemistry with three carbonyl groups, a metal-metal1 1238 R.B. King and M. B. Bisnette, Inorg. Chem., 1966, 5, 293.23s G.Booth and J. Chatt, J. C h . SOC. ( A ) , 1966, 634.e40 I?. A. Hartman and A. Wojcicki, J. Amr. Cham. Soc., 1966, 88, 844.241 J. P. Bibler and A. Wojcicki J. Amer. Chem. SOC., 1966, 88, 4862.J. Tsuji and K. Ohno, J . Amer. Chem. SOC., 1966,88,3452; J. Blum, Tetrahedronars R. Cramer, J. A m . Chem. SOC., 1966, 88, 2272; R. Cramer and R. V. Lindsey,244 W. R. Roth and W. Grimme, Tetrahedron Letters, 1966, 2347.a p 5 R. Jira, J. Sedlmeier, and J. Smidt, Annakn, 1966, 693, 99.a 4 7 H. P. Fritz, K. E. Schwarzhans, and D. Sellman, J. OrganometaUic Chem., 1966,24a H. P. Fritz and D. Sellmann, J. Organometdic Chem., 1966, 6 , 558.2 4 9 M. J. Grogan and K. Nekamoto, J. Amer. Chem. SOC., 1966, 88, 5454.Letters, 1966, 1605; J. Tsuji and K. Ohno, ibid., p.4713.ibid., p. 3534.J. W . Moore, Acta Chem. Scad., 1966, 20, 1154.8, 551230 INORGANIC CHEMISTRYbond, and co-ordination to the olefin group of the cyclobutene ring.250The ligand 2-allylphenyldiphenylphosphine (AP), CH,=CH*CH,*C6H4PPh2,acts as a chelate with an olefin and phosphorus group bonding to give thecompounds (AP)M(CO), (M = Cr, Mo, W),251 whilst in the complex trans-2,2'-di- (di-o-tolylphosphino)stilbenerhodium chloride, the organic group actsas a terdentate ligand, bonding by two phosphorus atoms and the o l e hgroup.252 A new type of zerovalent metal complex tris(methy1 vinyl ketone)-tungsten has been reported; co-ordination of both the olefm and the 60group to give a bidentate chelate are postulated.66The photochemical preparation of some new iron tetracarbonyl complexesof vinyl chloride, styrene, propene, and ethyl vinyl ether is reported. Theinfrared data imply that the organic groups are co-ordinated through theirolefinic double bond.252 The X-ray structure of the fumaric acid-irontetracarbonyl complex confirms that co-ordination of the acid to the metaloccurs through the double bond.253 A series of gold chloride olefin complexeswith a large range of cyclic mono- and di-olefins has been reported.254 TheX-ray structures of the following silver(1) olefin adducts have been carriedout : the norbornadiene adduct C,H,,2AgN0,,255 the bulvalene complexCloHlo,3AgBF4,256 and the complex C6H,-Ag*AlC1,.257 The structure of thecopper complex C6H,CdC1, is analogous to that of the benzene silvercomplex.25,Polyene Systems.-The study of the proton n.m.r. spectra over a tempera-ture range for a series of cyclo-octatetraene metal carbonyls, C,H,M(CO),(M = Cr, Mo , Pe), together with 1,3,5,7-tetramethylcyclo-octafefraene-molybdenum tricarbonyl and an extensive range of substituted cyclo-octa-tetraeneiron tricarbonyl adducts, indicates the presence of valence tautomer-isation in these systems. The bonding of the complexes has been interpretedin favour of both 1,3-diene and 1,5-diene co-ordination of the ring systemto the metals.259 For the tungsten analogue, c,H,w(Co),, the n.m.r. spectraa t room temperature show the anticipated four sets of hydrogen signals.66From the n.m.r. spectrum, valency tautomerism has also been suggested tobe present in cyclo-octatetraenecobalt cyclopentadienyl.260 In both thecyclobutadiene and butadiene iron tricarbonyls, carbon- 13 and proton n.m.r.spectra have been interpreted as indicating that the carbon atoms involves60 F.W. B. Einstein, W. R. Cullen, and J. Trotter, J . Amer. Chern. Soc., 1966, 88,'ti1 I;. V. Interraate, M. A. Bennett, and R. S. Nyholm, Inorg. Chem., 1966, 5, 2212.M. A. Bennett, R. Bramley, and P. A. Longstaff, C h m . Comm., 1966,806; E . K.P. Corrandi, C. Pedone, and A. Sirigu, Chem. C m n . , 1966, 341.254 R. Huttel, H. Reinheimer, and H. Dietl, C h m . Ber., 1966, 99, 462; R. Huttel256 N. C. Baenziger, H. L. Haight, R. Alexander, and J. R. Doyle, Inorg. Chem.,266 M. Gary Newton and I. C. Paul, J .Amer. Chem. SOC., 1966, 88, 3161.257 R. W. Turner and E. L. Amma, J . A w . Chem. SOC., 1966,88, 3243.2s8 R. W. Turner and E. L. Amma, J . A w . Chem. SOC.. 1!366,88, 1877.259 C. E. Keller, B. A. Shoulders and R. Pettit, J . Amer. Chem. Soc., 1966, 88, 4760;C. G. Kreiter, A. Maasbol, E. A. L. Anet, H. 0. Kaesz, and S. Winstein, ibid., p. 3444;F. A. Cotton, J. W. Faller, and A. MUSCO, ibid., p. 4506; F. A. Cotton, A. Davison, and6670.von Gustorf, M. C. Henry, and C. Di Pietro, 2. Nalurforsch., 1966, 21b, 42.and H. Reinheher, ibid., p. 2778.1966, 5, 1399..W. Faller, ibid., p. 4507.260 S. Otsuka and A. Nakamura, Inorg. Chem., 1966, 5, 2059KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 231essentially sp2-hybridisa.tion, and are consistent with bonding of the dienesto the metal in a similar manner to the ferrocene system.261It has been found possible to add 1 mol.of carbon monoxide to thecomplexes C,H,Mo(CO), and (cyclo-octa-l,3,5-triene)Mo(CO), to yieldthe tetracarbonyl complexes. The n.m.r. proton spectra indicate thatin the resultant complex the ligands are co-ordinated as 1,5-cyclo-octa-tetraene and 1,5-cyclo-octatriene adducts.26sThe reaction of triphenylphosphine with a series of dieneiron tricarbonylcomplexes to yield some triphenylphosphineiron dicarbonyl diene com-plexes 263 has been studied. Vitamin A aldehyde reacts with iron penta-carbonyl to give a diene iron tricarbonyl complex. The X-ray structure ofthis compound has been determined.264 A number of /?-ionone iron tri-carbonyl compounds have been prepared, and their properties reported.265Butadiene reacts with ruthenium trichloride in 2-methoxyethanol togive dichloro(deca-2,6,10-triene-1,12-diyl)ruthenium(1v).~~~ The complexes[Ru(CO)CI,(diene)], (diene = cyclo-octa- 1,5-diene and norbornadiene) havebeen ~repared.~67 Reaction of titanium tetrakisbutoxide with cyclo-octa-tetraene in the presence of triethylaluminium produces bis( cyclo-octa-tetraene)titanium and the dimer Ti,(COT), 268 (7) ; the crystal structure ofthe dimer has been determined; a series of new n-complexes of iron(0) andruthenium(0) with seven- and eight-membered cyclic olefins have been pre-pared, and the n.m.r.spectra of these complexes assigned.,'*The use of the intermediates [(olefin),RhCI], (olefin = cyclo-octene,cycloheptene, and norbornene) for the preparation of a series of diolefhcompounds, [(dioleh),RhCl], has been exploited ; 271 a similar series ofreactions has been established for iridium.,' The rhodium carbonyl chlorideh e r , [Rh(CO),Cl],, reacts with cyclohexa-1,3-diene and 2,3-dimethyl-butadiene to give the adduct [Rh(CO),Cl],diene.It is suggested that therslH. G. Pmton and J. C. Davis, J . Amer. Chem. SOC., 1966, 88, 1585; H. L.Retcofsky, E. W. Franke1;and H. S. Gutowsky, ibid., p. 2711.a62 S. Winstein, J . Amer. Chem. SOC., 1966, 88, 1319.a63 F. M. Chaudhari and P. L. Pauson, J . Orgamtallic Chem., 1966,5, 73.864 A. J. Birch, H. Fitton, R. Mason, G. B. Robertson, and J. E. Stangroom, Chem.886 M. Cais and N.Maoz, J . Organometallic Chem., 1966, 5, 370.28s J. K. Nicholson and B. L. Shaw, J. Chem. SOC. ( A ) , 1966, 807.267 S. D. Robinson and C. Wilkinson, J . Chem. SOC. ( A ) , 1966, 300.268 H. Breil and G. Wilke, Angew. Chem., 1966, 78, 942.* 7 0 J. Miiller and E. 0. Fischer, J . Organometallic Chem., 1966, 5, 275.271 L. Porri and A. Lionetti, J . Organometallic Chem., 1966, 6, 422; G. Winkhaus272 G. Winkhaus and H. Singer, Chem. Bm., 1966, 99, 3610.Cornm., 1966, 613.H. Dietrich and H. Dierks, Angew. Chem., 1966, 78, 943.and H. Singer, Chem. Ber., 1966, 99, 3602232 INORGANIC CHEMISTRYdiene acts as an additional bridging ligand across the rhodium atoms ofthe carbonyl chloride dimer.,V3 The structure of cyclo-octenylnickel(n)acetylacetone has been determh~ed,~v~ and also that of the related platinumcomplex methoxydicyclopentadienechloroplatinum dimer.275 In both com-plexes the ligand co-ordinates through both a n- bonded metal-olehand a o-metal-carbon bond.The reactivity of diene-palladium and-platinum complexes towards nucleophilic attack, with the formation ofcompounds typified by the last two structures, has been studied withacetylacetonate ani0ns~7~ and methoxide ions.277, ,7* The n.m.r. spectraof a series of methoxy-derivatives has been used to determine the stereo-chemistry of these products. 278 The carbonylation of cyclo-octa- 1,5-dieneto ethyl cyclo-octene-4-carbonylate has been accomplished using the palla-dium-cyclo-octa-l,5-diene chloride complex. 279 Buta- 1,3-diene and cyclo-octa-l,3-dienepalladium dichloride complexes have been obtained byligand exchange with bisbenzonitrilepalladium dichloride or the corres-ponding pentene complex.The diene complexes are dimers, [(diene)PdCl],,and are considered to bond through only one olefin group. The butadienecompound isomerises a t room temperature to a mallyl compound. 280The use of cyclobutadieneiron tricarbonyl as an intermediate in organicchemistry for the production of cyclobutadiene has been illustrated.281 Thereaction of chloromethylcyclobutadieneiron tricarbonyl with antimonypentachloride abstracts the chloride to give cyclobutadienemethyleneirontricarbonyl cations.282 Tetraphenylbutatriene reacts with iron ennea-carbonyl to give two complexes corresponding to the addition of Fe(CO),and Fe,(CO), units to the ligand; 2B3 the structure of the Fe(CO),L adductshows that the iron is co-ordinated to the central carbon double bond 284(8).A&l Complexes.-The isomerisation of labelled olefins by iron and cobaltcarbonyls has been interpreted in favour of an ally1 intermediate.285 TheG. Winkhaus and H.Singer, C h . Ber., 1966, 99, 3593.274 0. S. Mills and E. F. Paulus, Chem. Comm., 1966, 738.a15 W. A. Whitta, H. M. Powell, and L. M. Venanzi, Chem. Comm., 1966, 310.276 B. F. G. Johnson, J. Lewis, and M. S. Subramaniam, C h m . Comm., 1966, 117.277 R. G. Schultz, J . Organmetallic Chem., 1966, 6, 435.278 J. K. Stille and R. A. Morgan, J . Amer. Chem. SOC., 1966, 88, 6135.278 J. Tsuji, S. Hosaka, J.Kiji, and T. Susuki, Bull. Chem. SOC. Japan, 1966,39,141.280 M. Donati and F. Conti, Tetrahedron Letters, in the press.281 J. C. Barborak, L. Watts, and R. Pettit, J. Amer. Chem. SOC., 1966, 88, 1328.283 K. K. Joshi, J . Chem. SOC. ( A ) , 1966, 598, 594.as4 D. Bright and 0. S . Mills, C M . Comm., 1966, 211.485 B. Fell, P. Krings, and F. Asinger, C h m . Bw., 1966, 99, 3688.J. D. Fitzpatrick, L. Watts, and R. Pettit, Tetrahedron Letters, 1966, 1299KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 233bonding of n-ally1 complexes to transition metals has been discussed withparticular reference to the stereochemistry of n-allylpalladium chloride andacetate.286 The detailed structure of acetylacetonate cyclo-octa-2,4-dienyl-palladium is reported; 287 a co-ordinated n-aUyl and free olefin group withinthe same organic ring has been established from the X-ray structural analysisof the binuclear azulene complex Cl,H8Pe2(C0),.288 One of the productsof the reaction of cyclo-octatetraene (COT) with iron enneacarbonyl,(COT)Fe,(CO),, has been shown to involve two symmetrically placed ally1groups, one each bonding to an iron atom with the two remaining carbonsof the ring bonding through two three-centre bonds to the two irons and abridging carbonyl group.A rapid valence tautomerism with rotation of theiron groups around the ring is postulated 289 in order to explain the n.m.r.rtpectra. The structure of perfluorocyclopentadienedicobalt heptacarbonylhas shown the presence of a Co(CO), fragment a-bonded to the cyclo-pentadiene ring and a Co(CO), group bonded via a n-ally1 system to thering.The variation in the proton n.m.r. spectra over a temperature range of anumber of metal-ally1 compounds have been studied and have been inter-preted on the basis of the presence of n-a-ally1 equilibria and rotation of theCH, groups of the n-ally1 system; various allyl complexes of zirconium,291rhodium,292 and palladium 203 have been studied, and the n.m.r.spectrautilised to determine the kinetics of the reaction of the complex (C4H,PdC1),with The a-n-character of the allyl bond in the complex chloro-(triphenylphosphine)(methylallyl)palladium(n), discussed in last year’sReport, has been substantiated by the X-ray structure of the compound.295However, the importance of viewing this as a n-ally1 derivative rather thana mixed n-olefin and a-carbon bonded species has been e m p h a s i ~ e d .~ ~ ~ ~ 294A novel n-ally1 system was identified in (n-benzy1)molybdenum cyclopenta-dienyl tricarbonyl in which two of the carbons of the benzene ring and themethylene carbon comprise the co-ordinated n-ally1 group. In order tointerpret the n.m.r. proton spectra of this compound it is postulated thateither the mbenzyl group may rotate about the two-fold axis of the benzylring or that an equilibrium between n- and a-structures occurs.192A new synthesis of allylbis( cyclopentadienyl) titanium( m) derivativeshas been reported. 296 The chemistry of a a-allylmolybdenum(n) complexhas been extended. One obtains a series of mononuclear allyl derivatives286 S.F. A. Kettle and R. Mason, J . Organometallic Chem., 1966, 5, 573.288 M. R. Churchill, Chem. Comm., 1966, 450.288 E. B. Fleischer, A. L. Stone, R. B. K. Dewar, J. D. Wright, C. E. Keller, and291 J. K. Becconsdl and S. O’Brien, Chem. Comm., 1966, 302.2g2 H. C. Volger and K. Vrieze, J . OrganometaZZic Chmn., 1966, 297; J. K. Becconsalland S. O’Brien, Chem. Comm., 1966, 720.293 G. L. Statton and K. C. Ramey, J . Arner. Chem. Soc., 1966, 88, 1327; K. C.Ramy and G. L. Statton, ibid., p. 4387; K. Vrieze, C. Maclean, P. Cossee, and C. W.Hilbers, Rec. Trav. chim., 1966, 85, 1077.2Q4 K. Vrieze, P. Cossee, C. MacLean, and C. W. Hilbers, J . Organometallic Chena.,1966, 6, 672.2Q5 R. Mason and D.R. Russel, Chem. Cmm., 1966, 26.2*6 If. A. Martin and L. Jellinek, J . Organometallic C h . , 1966, 6, 293.M. R. Churchill, Inorg. Chem., 1966, 5 , 1608.R. Pettit, J . Amer. Chem. Soc., 1966, 88, 3158.P. B. Hitchcock and R. Mason, Chem. Comm., 1966, 503234 INORGANIC CHEMISTRYby splitting the bridge of the salts of tri-~-chlorobis-(2-methyl-n-allyl-dicarbonylmolybdenum) anion. 297 The preparation of three acetyl- orbenzoyl-allylmanganese tetracarbonyl derivatives by interaction of methyl-or phenyl-manganese pentacarbonyl with butadiene has been de~cribed,~Qaand the mechanism of this reaction in~estigated.2~~ The reaction of allenewith tri-iron dodecacarbonyl and cobalt octacarbonyl has been reported. Arapid valence tautomerism between a 2,2’-bi-n-allylene hexacarbonyl di-ironstructure and a butadiene structure is deduced from the proton n.m.r.spectra.300 Trimethylenemethane has been stabilised as a ligand with aniron tricarbonyl fragment by reaction of iron enneacarbonyl with 1 ,l-dichloro-methylethylene, CK2=C(CH2C1), to give [ (CH,),C]Fe(CO),. 301A series of 0- and n-ally1 complexes has been isolated from the reactionof triphenylphosphinerhodium chloride with allyl chloride in solution.302Tris-n-allylrhodium has been prepared by reaction of the (bis-n-allylrhodiumchloride) h e r , [(C,H?),RhCl],, with allylmagnesium chloride.The n.m.r.spectra indicate that each n-ally1 group is symmetrically bonded but thatthey are not stereochemically e q ~ i v a l e n t . ~ ~ ~ ~ 302 The preparation of allyl-palladium chloride from chloropalladite and allyl chloride in the presence ofcarbon monoxide is considered to occur through an oxidative hydrolysis.This concept has been developed to prepare a number of rhodium allylcomple~es.~0~ A series of n-ally1 and alkyl nickel phosphine compounds hasbeen reported ; 304 the preparation of 1,4,7-trimethylenecyclononane from1 ,I-bischloromethylethylene, (ClCH,),CCH,, and nickel carbonyl is con-sidered to occur through a n-ally1 complex.3o5 With iron carbonyl a stableallyl intermediate is obtained (see above).The preparation of allylpalladium(n) anions, [ (n-allyl)PdX,] - (X = halo-geIi), is described; they are obtained by reaction of excess of halide and thecorresponding n-ally1 halogen dimem306 The reaction of allene with chloro-palladate ( 11) yields ( p- 3 - chloropr o p - 1 -en- 2 - y 1) allyl and 2 - chlor opr o p - 2 - enylpalladium complexes.307Csclopen tadiene Complexes .-T he analogy between met al-carb oranederivatives and cyclopentadienyl compounds is emphasised by the X-raystructure determination 308 of the anion, [ (B,C,H,,)Re(CO),], which has thestructure previously proposed.309 The complexes of carboranes with palla-dium(n) have been established with the preparation of the tetraphenylcyclo-2Q7 H.D. Murdoch and R. Henzi, J. Organometallic Chem., 1966, 5, 552.298 W. D. Bannister, M. Green, and R. N. Haszeldine, J . Chem. SOC. (A), 1966, 194.29s M. Green and R. I. Hancock, Chem. Comm., 1966, 572.300 A. Nakamura, Bull.Chem. SOC. Japan, 1966, 39, 543.aol G. F. Emerson, K. Ehrlich, W. P. Giering, and P. C. Lauterbur, J . Amer. Chem.308 J. Powell and B. L. Shaw, Chern. Comm., 1966, 323.J. Powell and B. L. Shaw, Chem. Comm., 1966, 236; J. K. Nicholson, J. Powell,SOC., 1966, 88, 3172.and B. L. Sha,w, ibid., p. 174.804 B. Bogdanovic, H. Bonnemann, and G. Wilko, Angezu. Chm., 1966, 78, 591.805 E. J. Corey and H. F. Semmelhack, Tetrahedron Letters, 1966, 6237.306 R. J. Goodfollow and L. M. Venanzi, J . Chem. Xoc. ( A ) , 1966, 784.807 M. S. Lunin. J. Powell. and B. L. Shaw, J. Chem. SOC. ( A ) , 1966, 1687; B. L. . .Shrtw, ibid., p. f6S8.308 A. Zalkin and T. E. Hopkins, Inorg. Chem., 1966, 5, 1189.M. F. Hawthorne and T. P. Andrews, J. Amer. Chem. SOC., 1965, 87, 2496KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 235butadiene compounds [n-( Ph4C4)Pd(n-BgC2H,,)] and[z~-(P~*CJP~(~-B~C,H,(CH~),)].~~~The electron diffraction pattern of ferrocene in the vapour phase indicatesD,,, symmetry for the equilibrium conformation; the CH bonds are bentaway from the plane of the C5 ring by 5" towards the metal.311 The equiva-lence of the protons of the a-bonded cyclopentadiene group in the n.m.r.spectrum of the compound (C,H,)Fe(CO),( C5H5) has been investigated bymeasuring the spectra over a temperature range and by the determinationof the X-ray structure.The data are interpreted in terms of an intra-molecular reorientation process.312 The mass spectra of some cyclopenta-dienyl-metal derivatives 3l3 have been obtained, and the nature of thet etr ac y anoe t h ylene adduc ts of ferrocene and co balo cene elucidated .A new preparation of biscyclopentadienyltitanium(n) has confirmed thediamagnetism of the c0mplex.3~5 Titanium and zirconium cyclopentadienealkylphosphide complexes, [C,H,MPR,], (M = Ti, Zr; R = C2H5 or n-C41Pg)have been synthesised,"16 and tetrakiscyclopentadienylzirconium was re-in~estigated.3~7 Diphenylketen complexes have been obtained by reactionof the keten with biscyclopentadienylvanadium and with biscyclopentadienyltitanium dicarbonyl, respectively, to give [C5H5M(Ph2C=C=O)] (M = Ti, V).The keten reacts with the metal through the olefin and oxygen groups ofthe diphenylketen.3'8 The interaction of the cyclopentadienyl carbonyls ofiron and vanadium with sulphur yields319 the polymeric complexes[ ( C,H5),V2S5] and [C5H5FeS],, and whereas cyclohexene sulphide reactswith the cyclopentadienyl' carbonyl of vanadium 319 to give the samepolymeric vanadium product, the complex [ ( C5R5)MoS2C,H11], is obtainedfrom [C,H,MO(CO),],.~~~~ 320 The X-ray structure of the iron adduct hasbeen 321 The complex C,H,V(acetate), is considered to be adimer in the solid, and the magnetic moment (p = 1.49 B.M.) is indicativeof interaction between the metal ions.322 A series of maleonitrile dithiolatecomplexes of some cyclopentadienyl complexes of titanium, molybdenum,tungsten, iron, and cobalt has been 0bserved;~~3 a related cobalt adduct,C5H5Co [S,C, ( CF,),], 324 has been obtained with (trifluoromethy1)dithione.310 P.A. Wegner and M. F. Hawthorne, C h m . Comm., 1966, 861.311 R. K. Bohn and A. Haaland, J . Organometallic Ckem., 1966, 5, 470.312 M. J. Bennett, F. A. Cotton, A. Davison, J. W. Faller, S. J. Lippard, and S . M.313 F. J. Preston and R. I. Reed, Chent. Comm., 1966, 51; E. Schumacher and R.314 R. L. Brandon, J. H. Osiecki, and A. Ottenborg, J . Orgunometallic Cilem., 1966,315 G. W. Watt, L. J. Baye, and F. 0. Drammond, J . Amer. Chent. SOC., 1966,88,1138.316 K. Issleib and H. Hackert, 2. Naturforsch., 1966, 21b, 519.317 E. 31. Brainina, M. Rh. Minacheva, and R. Kh. Freidlina, Bull. Acad. Sci.,slsP. Hong, K. K. Sonogashira, and N. Hagiham, Bull. Chem. SOC. Japan, 1966,s19 R. A. Schunn, C. J. Fritchie, and C. T. Prewitt, Inorg.Chem., 1966, 5, 892.320 P. M. Treichel and G. R. TVillces, Inorg. Chem., 1966, 5, 1182.321 C. H. Wei, G. R. Wilkes, P. M. Treichel, and L. F. Dahl, Imorg. Chem., 1966,322 R. B. King, Inorg. Ch8?n., 1966, 5 , 2231.s2s J. Locket and J. A. McCleverty, Inorg. Chem., 1966, 5, 1157.a24 H. W. Baird and B. M. White, J. Amer. Chcwt. SOC., 1966, 88, 4744.Morehouse, J . Anier. Chern. SOC., 1965, 88, 4371.Taubenest, Helv. C'lzim. Actn, 1966, 49, 1447.31, 1214.U.S.S.R., 1965, 1839.39, 1821.5, 900236 INORGANIC CHEMISTRYAn extensive group of arylazo-derivatives of molybdenum cyclopentadienylcarbonyl have been prepared, RN,Mo(CO)~(C,H,).~~~ The product of thereaction of tetraphenylcyclopentadienone with triphenyltin manganesepentacarbonyl has been reformulated as (tripheny1stannoxy)taphenylcyclopentadienylmanganese tricarbonyl.326 The preparation of benzenecyclopentadienyl manganese ( I) and a related series of biphenyl dimericspecies has been described.327, 328 Tropylium derivatives have been obtainedfrom the Friedel-Crafts acetylation of the chromium and manganese cyclo-pentadienebenzene complexes.328 The compounds C,H,Mo(CO),X, (X = C1,Br, I) have been obtained by direct halogenation of the cyclopentadienyl-molybdenum tricarbonyl ~Iimer,~,~ and the reaction of the cyclopentadienylcarbonyl chlorides of iron and tungsten with unidentate nitrogen and phos-phorus ligands rep0rted.3~0 The electronic and structural similarities ofcyclopentadienyl-carbonyls and pure carbonyls have been emphasised in thepreparation of the complexes [C,H,Fe( C0)l4 and [C,H,Co(CO)],, and com-parison with the carbonyls [Co(CO),], and Ru,( CO),,, respectively.331mCyclopentadieneiron tricarbonyl, (C,H,)Fe( CO),, has been obtained fromcyclopentadiene and iron enneacarbonyl ; the compound decomposes at140" to give the cyclopentadienyliron dicarbonyl dimer.332 Some newmethods for the preparation of alkoxycarbonyl cyclopentadienyl complexesof iron, manganese, and molybdenum have been de~eloped.~33 The carbonmonoxide insertion reaction of the compound C,H,Fe( CO),CH3, to giveC,H,Fe(CO)(COCH,)L, has been studied with a variety of phosphines(L),334, 335 and the ions [C,H,I?e(CO),L]f are obtained by reaction of thephosphines with the complexes C,H,Fe(CO),X (X = C1, Br, I).335 Stablemonomeric alkyl and aryl mercaptide complexes, C,H,Fe( CO),SR, havebeen isolated ; the controlled transformation into pairs of isomeric binuclearcomplexes [ (RS)Fe( CO)C,H,], has been reported.336 Some alkyl and aryltrithiocarbonates of iron, [C,H,Fe(CO),CS,R] (R = CH,, C,H,, c6H,), havebeen obtained; these lose carbon monoxide in ultraviolet light to yield thechelated monocarbonyls, [C,H,Fe( CO)CS3R].337 The preparation of thefist trifluorophosphine cyclopentadienyl cobalt complex has been reported,C,H,CO(PP,),.~~~ The structure of the trimer, [C,H,Rh(CO)],, indicatesa triangular array of rhodium atoms with bridging carbonyl groups and acyclopentadienyl group associated with each rhodium atom. 339 Dicyclo-335 R. B. King and H. B. Bisnette, Inorg. Chem., 1966, 5, 300.326 R. D. Gorsich, J. Organometallic Chem., 1966, 5, 105.3 2 7 R. G. Denning and R. A. D. Wentworth, J. Amer. Chem. SOC., 1966, 88,4619.328 E. 0. Fischer and S. Breitschaft, Chem. Ber., 1966, 99, 2213.329 R. J. Haines, R. S. Nyholm, and M. H. B. Stiddard, J. Chem. SOC. ( A ) , 1966, 1606.330 E. 0. Fischer and E. Moser, J. Organometallic Chem., 1966, 5, 63.331 R. B. King, Inorg. Chem., 1966, 5 , 2227.332 R. K. Kochhar and R. Pettit, J. OrganometaZZic Chem., 1966, 6, 272.533 R. B. King, M. B. Bisnette, and A. Fronzaglia, J. Organometallic Chem., 1966,334 J. P. Bibler and A. Wojcicki, Inorg. Chem., 1966, 5 , 889.335 P. M. Treichel, R. L. Shubkin, K. W. Barnett, and D. Reichard, Inorg. Chem.,336 M. Ahmad, R. Bruce, and G. R. Knox, J. Organometallic Chem., 1966, 6, 1.337 R. Bruce and 0. R. Knox, J. Organomctallic Chem., 1966, 6, 67.338 Th. I<ruck, W, Hieber, and W. Lang, Angew. Chem., 1966, 78, 208.539 0. S. Mills and E. F. Paulus, Chem. Comm., 1966, 815.5, 391.1966, 5, 1177KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 237pentadienylrhodium(n), and -iridum(n) have been shown to be paramagneticmonomers a t liquid-nitrogen temperature and in the gas phase, but to bediamagnetic dimers at room temperature.340 Base adducts of tricyclo-pentadienyl complexes of a series of lanthanide elements of the form(C,H,),M,L (M = Y, Nd, Tb, Ho, Yb, L = cyclohexyl isonitrile; M = Yb,L = PPh,, OC4H,, NH,) have been 0btained.~~1 The preparation of tri-cyclopentadienyleuropium 342 and dicyclopentadienylytterbium 343 has beengiven.343 The syntheses of the transuranic cyclopentadienyl compounds(C,H,),NpC1344 and Am( C5H5),345 have also been reported.Metal-Arene Complexes.-The low-temperature studies of the X-raystructures of dibenzenechromium favour the symmetry D,, for the mole-cule.346 The e.s.r. spectrum of the ion [(HMB),Fe]+ (HMB = hexamethyl-benzene) suggests that the two rings are oblique to each 0ther.~47 TheX-ray structures of (HMB)Cr( CO), and (C6H,)Cr( CO), indicate a staggeredconfiguration of the rings to the carbon triangle of the carbonyl groups,whereas in the anisole derivative an eclipsed configuration is observed ; in con-junction with these results, and from the structure of the (o-toIuidine)Cr(CO),complex, it is concluded that these effects are related to electronic rather thansteric factors.348 The X-ray structure 349 of 1,6-methanocyclodecapentane-chromium tricarbonyl prepared recently 350 has been reported, and thehigh-field shift of the methylene group is shown not to be associated withdirect metal interaction. The temperature dependence of the proton n.m.r.spectra of isopropylbenzenechromium tricarbonyl is associated with restrictedrotation of the arene nucleus. 351 The X-ray structure of the charge-transfercomplex of (aniso1e)chromium tricarbonyl with 1,3,5-trinitrobenzene hasbeen 0btained.~5~The reaction of benzene and methyl-substituted benzene tetracarbonylvanadium cations, [(arene)V(CO)4]+, with borohydride to give the z-cyclo-hexadienyl derivatives has been reported. The n.m.r. and infrared spectrain the region 2770-2820 cm.-l are assigned to the methylene group and notmetal-hydrogen interaction. 353 The preparation of some cyclopentadienyl-chromium tropylium cations have been rep0rted,~54 and the photochemical340 E. 0. Fischer and H. Wawersik, J. Organometallic Chem., 1966, 5, 559.341 E. 0. Fischer and H. Fischer, J. Organometallic C h . , 1966, 6, 141.342 M. Tsutsui, T. Takino, and D. Lorenz, 2. Naturforsch., 1966, 216, 1.343 F. Calderazzo, R. Pappalardo, and S. Losi, J. Inorg. Nuclear Chem., 1966, 28,344 E. 0. Fischer, P. Laubereau, F. Baumgartner, and B. Kanellakopulos, J. Organo-345 F. Baumgartner, E. 0. Fischer, B. Kanellakopulos, and P. Laubereau, Angew.346 E. Keulen and F. Jellinek, J. Organometallic Chem., 1966, 5, 490.3 4 7 H. Brintzinger, E. Palmes, and R. H. Sands, J . A m . Chem. SOC., 1966, 88, 623.348 0. C. Carter, A. T. McPhail, and G. A. Sim, Chem. Comm., 1966, 212.349 P. E. Baikie and 0. S. Mills, Chem. Comm., 1966, 683.350 E. 0. Fischer, H. Riihle, E. Vogel, and W. Grimme, Angew. Chem., 1966,78, 584.351 D. E. F. Gracey, W. R. Jackson, W. B. Jennings, S. C. Rennison and R. Sprott,C h m . Comm., 1966, 231.352 0. L. Carter, A. T. McPhail, and G. A. Sim, J . Chem. Soc. (A), 1966, 822; G.Huttner, E. 0. Fischer, R. D. Fischer, 0. L. Carter, A. T. McPhail, and G. A. Sim,J . Organometallic Chem., 1966, 6, 288.353 F. Calderazzo, Inorg. Chenz., 1966, 5, 429.354 E. 0. Fischer and S. Breitschaft, Chem. Ber., 1966, 99, 2905.987.metallic Chern., 1966, 5, 583.Chem., 1966, 78, 112238 INORGANIC CHEMISTRYsubstitution of carbonyl groups in arenechromium tricarbonyl complexesdescribed. 355 The reaction of hexamethylbenzene with metal chlorides ofGroup IV and V in the presence of aluminium chloride and aluminium powdergives a series of new n-hexamethylbenzene derivatives, Nb2[ (HMB),],Cl,,[Nb,(HMB),Cl,]CI, [Ta,(HMB),Cl,]Cl, [Ti,(HMB),Cl,]Cl, and[Zr,(HMB),CI,]Cl. The reduction of dibenzenerhenium cation and thecorresponding hexamethylbenzene complex with sodium in liquid ammoniayields arene-cyclohexadienyl complexes, but with lithium at 200 Oc reductionof the metal occurs and a paramagnetic complex [Re(HMB),] is formed; thishas also been converted into a diamagnetic dimer, [Re(HMB),],.357 Thecation [bis-(6,6'-diphenylfulvene)cobalt] + has been obtained, and is the firstexample of a molecule with two fulvene groups not containing carbonylgroups.35*