1. INTRODUCTIONBy J. Lewis and N. L. Paddock(The Department of Chemistry, The Victoria University of Munchester)THE general pattern of the Report follows the layout used by the previousReporters. The section on complexes is restricted to carbonyl compoundsand organometallic compounds of the transition elements ; the chemistry ofthe organic derivatives of the typical elements is discussed in the Report onOrganic Chemistry.There have been no major developments in inorganic chemistry duringthe past year-perhaps the most interesting work has been the preparationof adducts of transition metals with carboranes, analogues to mcyclopenta-dienyl metal derivatives. The proceedings of the Eighth InternationalConference on Co-ordination Chemistry have been published as a book1 andthe plenary lectures of the Conference have been reported.2 The Pro-ceedings of the Chemical Society have been replaced by Chemical Communica-tions, which appears bi-monthly.The number of publications continues to rise sharply and the availablespace has allowed mention of rather less than half of those which would havebeen included on the basis of chemical interest.The Reports are thereforeillustrative rather than comprehensive. In references to Russian Journalsthe page number of the English translation has been given.ed. V. Qutmann, Springer-Verlag, Vienna/New York, 1964.“ Proceedings of the 8th International Conference on Co-ordination Chemistry,”Pure Appl. Chern., 1965,10, 1-702. THE TYPICAL ELEMENTSBy B. F. 0. Johnson, N.L. Paddock, and M. J. Ware(Department of Chemistry, The Victoria University of Manchester)MOST of the papers published in the year under review are concerned withthe chemistry of a single element, and are classified below accordingly.A few deal with donor-acceptor reactions of a range of compounds, usuallymetallic halides, in polar non-aqueous solvents, the extent of interactionbeing measured thermochemically (phosphorous oxychloride,lU dimethyl-formamide l b ) , conductometrically lC (acetic anhydride), and by infrared Id(acetone) and nuclear magnetic resonance le spectroscopy (dimethylforma-mide). The chemical reactions occurring in fused salts have been discussed ;zaand a general account has been given 2b of the co-ordination model for non-aqueous solvents [with special reference to POCl, and PO(OEt),].Thereactions of metal halides with ammonia and aliphatic amines 3a and withalkyl cyanides 3b have been reviewed. Eight-co-ordination has been achievedfor In, Sb, Pb, and Sb in complexes with tropolone and aminotroponimine,*a,nd recent work on cationic complexes has been reviewed.5 A detailedaccount has been published of the strengths of bonds from metals to carbon,6and the bonding of the species found in vapours of the elements has beendiscussed.7 A review on fluorocarbon derivatives of the metals 8 and aseries of papers on the industrial synthesis and application of organometallicshave been p~blished,~ the latter (248 pp.) having a much wider scope thanits title indicates.The effects of d-orbital hybridisation on the geometry of the halides ofGroups 11,111, and IV have been investigated.10 Some reviews of generalinterest have appeared on inorganic chain molecules,11 on redistribution andexchange reactions,l2 and on the intercalation of metals in graphite and inmetal chalcogenides 13 MX,.1 (u) V.Gutmann, F. Mairinger, and H. Winkler, Monatsh., 1965,96,524; (6) R. C.Paul, S. C. Ahluwalia, and S . S . Pahil, Indian J . Chem., 1965, 3, 300; (c) R. C. Paul,K. C. Malhotra and 0. C. Vaidya, ibid., p. 1 ; ( d ) I. M. Semenova and A. A. Osipov,J . Gen. Chem. (U.S.S.R.), 1964, 34, 2723; ( e ) S. J. Kuhn and J. S. McIntyre, Canad.J . Chem., 1965, 43, 375, 995.2 ( a ) W. Sundermeyer, Angew. Chern., 1965, 7'7, 241; ( b ) R.S. Drago and K. F.Purcell, Progr. Inorg. Ghena., 1964, 6, 271.3 ( a ) G. W. A. Fowles, Progr. Inorg. Chena., 1964, 6, 1; (b) R. A. Walton, Quart.Rev., 1965, 19, 126.4 E. L. Muetterties and C. M. Wright, J . Amer. Chem. SOC., 1964, 86, 5732; ibid.,1965, 87, 4706.ti H. A. Skinner, Adv. Organometallic Chcnz., 1964, 2, 49.* P. M. Treichel and F. G. A. Stone, Adv. Organometallic Chem., 1964, 1, 143.s " Industrial Synthesis and Application of Organometallics ," Ann. New YorEOthers are referred to in the main text.E. L. Muetterties, Pure Appl. Chem., 1965, 10, 53.B. Siegel, Quart. Rev., 1965, 19, 77.Acad. Sci., 1965, 125, Art. 1, pp. 4-248.34, 13.lo 0. P. Charkin and M. E. Dyatkina, J . Struct. Chem., 1965, 5, 415; 854; 858.*l H.A. Andrianov, I. Haiduc, and L. M. Khananashvili, Russ. Chem. Rev., 1965,l2 J. C. Lockhart, Chem. Rev., 1965, 65, 131.l3 W. Riidorff, Chimia (Switz.), 1965, 19, 489JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 133Group 0.-The fluorination of krypton in an electrical discharge14 givesKrF,, not KrF, as reported earlier. Xenon difluoride, shown to be linearby its vibrational spectra,14J5 is formed from the element and fluorides ofoxygen ;I6 its association with xenon tetrafluoride in XeF,,XeF, is electro-static in origin, and depends on charge migration to flu0rine.l‘ Xenon hexa-fluoride forms the complexes18 XeF,,2SbF5, XeF,,SbF,, and 2XeF,,SbF5 ;an electron-diffraction study on the free XeF, molecule shows that it does nothave full octahedral symmetry.19 Xenon fluorides occur as intermediatesin those reactions of perfluoroalkanes which are photosensitised by xenon.20Reactivity with olefins decreases21 in the order XeF, > XeF, > XeF,.Reactions of the noble gases,22a and especially of xenon,22b have been reviewed,and the nature of the bonds in the xenon fluorides discussed. Dimericstructures of XeO, octahedra linked through oxygen have been suggested 23for the mono-alkali xenates, typically NaHXeO,,l.SH,O ; the combineddisproportionation and decomposition of the Xe0,4- ion in alkaline solutionstakes place via a complex of mixed oxidation state,24~ and the mechanism ofits reduction by water has been investigated.24b Vibrational analyses25show that the valence force constants of XeOF, are close to those of relatedinterhalogen c o r n p o ~ n d s .~ ~ ~ ~ ~ For xenon tetro~ide,~,~ the bond energyE(Xe:O) is26 21.1 kcal. mole-l. In the oxides, as in the fluorides, the bondenergy is only slightly dependent on the oxidation state of xenon.Group 1.-Alkali metals form stable paramagnetic solutions in hexamethylphosphoramide which are useful synthetically.27 The magnetic suscepti-bilities of dilute solutions of alkali metals in ammonia have been tentativelyexplained in terms of equilibria involving the metal negative ion.28 Fadedsolutions of potassium or rubidium in ethylamine can be regenerated byillumination in the amide absorption region, charge transfer occurring eitherto the alkali-metal (positive) ion or to the solvent.29 The electronic struc-tures of the adducts formed reversibly30 by alkali metals with aromaticl4 F.Schreiner, J. G. Malm, J. C. Hindman, J. Amer. Chem. SOC., 1965, 87, 25.l5 H. H. Claasen, G. L. Goodman, J. G. Malm, and F. Schreiner, J. Chern. Phys.,l6 S. I. Morrow and A. 33. Young, jun., Inorg. Chem., 1965, 4, 759; L. V. Strengl7 J. H. Burns, R. D. Ellison, and H. A. Levy, Acta Cryst., 1965, 18, 11.l8 G. L. Gard and G. H. Cady, Inorg. Chem., 1964, 3, 1745.l9 L. S. Bartell, R. M. Gavin, jun., H. B. Thompson, and C. L. Chernick, J. Chenz.Phys., 1965, 43, 2547.2o G. H. Miller and J. R. Dacey, J. Phys. Chem., 1965, 69, 143-1.21 Tsu-Chia Shieh, N. C. Yang, and C. L. Chernick, J. Amer. Chena. SOC., 1964, 88,503 I *2 2 (a) J. H. Holloway, Progr.Inorg. Chem., 1964, 6, 241; ( b ) J. G. Malm, H. Selig,J. Jortner, and S. A. Rice, Chem. Rev., 1965, 65, 199.23 T. M. Spittler and B. Jaselskis, J. Amer. Chem. SOC., 1965, 87, 3357.24 (a) C. W. Koch and S. M. Williamson, J. Anaer. Chern. SOC., 1964, 86, 5439,(cf. Ann. Reports, 1964, 61, 115); ( 6 ) E. H. Appelman and Rf. Anbar, Inorg. Chena.,1965, 4, 1066.25 (a) G. M. Begun, W. H. Fletcher, and D. F. Smith, J . Chenz. Phys., 1965, 42,2-336; (b) W. A. Yeranos, Bull. SOC. china. belges, 1965, 74, 40’7; (c) ibid., p. 414.26 S. R. Gum, J. Amer. Chenz. SOC., 1965, 87, 2290.27 G. Fraenkel, S. H. Ellis, and D. T. Dix, J . Amer. Chena. SOC., 1965, 87, 1406.28 S. Golden, C. Guttman, and T. R. Tuttle, jun., J. Amer. Chem. SOC., 1965, 87,29 35.Ottolenghi, K. Bar-Eli, and H. Linschitz, J. Amer. C’hem. Soc., 1965, 87, 1809.30 A. Rembaum, ,4. Eisenberg, and R. Haack, J. Amer. Chem. SOC., 1965, 87, 2291.1965, 42, 1229.and A. G. Streng, ibid., 1370.135134 INORUANIU CHEMISTRYhydrocarbons have been reviewed.21 Caesium has been separated from thelighter alkali metals by extraction with 24 a-methylbenzyl)-4-s-butylphenol,by taking advantage of its smaller tendency to hydration.32 The electronspin resonance spectra of the radical-ion complexes of alkali metals witho-dimesitoylbenzene show an unusually high splitting, which is attributed tothe occurrence of partial covalent bonding.33 Some sodium hydride isformed, at high temperatures and pressures, in the reaction between sodiumand water vapour ;34 its dissociation has been studied in the solid state 35 andin solution in s~diurn.~e The derived solubility of hydrogen in the metalagrees with a direct determination a t the solubility limit, but deviates a tlower pres~ures.~7 The nitrosyl formed from potassium and nitric oxide inammonia sg probably contains the cis-hyponitrite ion N2022-, rather thanNO -.Group 11.-Sodium hydride reacts with dimethylberyllium to giveNa(Me,HBe), from which Me,Be,H,, regarded as a mixture, is produced bytreatment with beryllium chloride.Both types of compound are decom-posed by donor molecules, with the formation of (e.g.) Me,B*NMe, and(MeBH*NMe,),. Bridged structures [typically as in (l)] are believed tooccur generally in all these compounds and in their solutions in ether,89@and have been found, as the Be,H, group, in the crystal structure of theetherate of sodium hydrid~diefhylberyllate,~~~ (NaOE t ,) ,(Et ,Be,H ,).Sodium beryllium hydride Na,BeH, is probably also p~lymeric.~gc Ethyl-beryllium hydride has been prepared from diethylberyllium and triethyltin-(IV) h~dride.,~" Beryllium borohydride forms a complex Be(BuiNH,) 4-(BH,), ; beryllium hydride and triphenylphosphine borane Ph,P*BH, areformed40 on decomposition of the complex (Ph,P),Be(BH,),.On the basisof its proton magnetic resonance spectrum, the structure (2) is assigned totrimeric bi~dimethylaminoberyllium,*~ prepared from dimethylamine anddiethylberyllium. The sodium derivative of hexamethyldisilazane reactswith beryllium chloride to form (Me,Si)&*Be*N(SiMe,),, for which vibra-31 E.de Boer, L4dv. Organometallic Chem., 1964, 2, 115.33 B. Z. Egan, R. A. Zingaro, and B. M. Benjamin, Inorg. Chena., 1965, 4, 1055.3 3 B. J. Herold, A. F. Neiva Correia, and J. dos Santos Veiga, J . Amer. Chem. SOC.,s4 C. C. Addison and J. A. Manning, J . Ghem. SOC., 1964, 4887.35 C. C. Addison, R. J. Pulham, and R. J. Roy, J . Chem. SOC., 1965, 4895.36 C. C. Addison, R. J. Pulham, and R. J. Roy, J . Chem. SOC., 1965, 116.37 D. W. McClure and G. D. Halsey, jun., J. Phys. Chem., 1965, 69, 3542.38 N. Gee, D. Nicholls, and V. Vincent, J. Chem. SOC., 1964, 5897.30 (a) N. A. Bell and G. E. Coates, J . Chem. SOC., 1965, 692 (cf. Ann. Reports, 1964,61, 117); (b) G. W. Adamson and If.M. M. Shearer, Chem. Cornm., 1965, 240; (c) N. A.Bell and G. E. Coates, ibid., p. 582.40L. Banford and G. E. Coates, J . Chem. SOC., 1964, 5591.41 N. R. Fetter and F. M. Peters, Cunud. J. Chem., 1965, 43, 1884.1965, 87, 2661JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEXENTS 135tional and proton magnetic spectra indicate both a linear N-Be-N skeleton(in the condensed phase) and planar BeNSi, groups. It does not reactwith strong donors.42 Diethylmagnesium and magnesium bromide reactalmost instantly in ethereal s0lution,4~ to form monomeric EtMgBr. Simi-larly, the precipitate formed by adding triethylamine to the solution isEtMgBr,Et ,N, no redistribution reaction occurring provided the donor isstrong enough.44 Alkaline earth nitride halides (e.g., M a x ) have beenprepared by sintering a mixture of halide and nitride in a nitrogen atmo-~phere.~5 Diacetamide, with salts of alkali and alkaline-earth metals, formscomplexes which appear (by infrared spectroscopy) to have chelate structures ;if all the ligands are bidentate, then the complexes of Ca,Sr,Ba, must beformulated as eight- and ten-co-ordinate.46Methylamine displaces fluoride ion from phosphorustrifluoride-borane PF,*BH, less rapidly than ammonia does, to give(MeNH),PF,_;BH, (x = 1-3).A substitution reaction also occurs withdimethylamine in the absence of a solvent, but in ether the base is dis-placed.47 Carbon monoxide-borane BK3C0, in ether adds methylamineor dimethylamine, the products being 1 : 1 electrolytes in water,48 typicallyMeNH,+[H,BC( O)NHMe]-. Unsymmetrical cleavage of diborane byMe,K or Et3N to form, e.g., [H,B(NH,Me),]+BH,- is favoured by lowtemperatures ;49 dimethyl sulphoxide reacts similarly.50 Bisamineboroniumions can be prepared conveniently by the oxidation of amineboranes withA new type of electron-deficient compound has been discovered inthe manganese carbonyl derivative HMn3( CO),,(BH,) ,, in which the twoborane groups link the three metal atoms through l~ydrogen.~~ The infra-red spectra of the blue-violet paramagnetic salts NiIIA(BH,),, where A is atetraclentate ligand, suggest that the borohydride ion is here bidentate.53aAluminium borohydride reacts with up to four donor molecules L, the finalproducts being53b LOBE, and LmAlH,.Alkynyl boranates Na[R,BC:CR’]and Na,[R,BC:CBR,] have been synthesised 54 from alkynes and sodiumtrialkylboranates.Triborane and tetraborane derivatives have been de-tected in the pyrolysis of diborane.55 The synthesis of a deuterium-labelledtetraborane p-B,H,D has been reported,56 and tetraborane-( 10) has beenGroup IlI.--Boron.4 2 H. Biirger, C. Forker, and J. Goubeau, Moraatsh., 1965, 96, 597.43 M. B. Smith and W. E. Becker, Tetrahedron Letters, 1965, 3843.4 4 E. C. Ashby, J . Amer. Chern. Xoc., 1965, 87, 2509.46 H. H. Emons, D. Anders, G. Roewer, and F. Vogt, 2. anorg. Chena., 1964, 333,46 P. S. Gentile and T. A. Shankoff, J . Inorg. Nuclear Chem., 1965, 27, 2301.4 7 G. Dodema and R. W. Parry, Inorg. Clzem., 1965, 4, 410.4 8 J. C. Carter and R.W. Parry, J . Amer. Chem. SOC., 1965, 87, 2354.4D S. G. Shore, C. W. Hickam, jun., and D. Cowles, J . Amer. Chem. Soc., 1965, 87,5 0 G. E. McAchran and S . G. Shore, Inorg. Chem., 1965, 4, 125.s1 J. E. Douglass, J . Amer. Chem. SOC., 1964, 86, 5431.62 H. D. Kaesz, W. Fellmann, G. R. Wilkes, and L. F. Dahl, J . Amer. Chem.s3 ( a ) N. F. Curtis, J . Chem. SOC., 1965, 924; (b) P. H. Bird and M. G. M. Wall-64 P. Ringer and R. Koster, Tetrahedron Letters, 1965, 1901.s5 A. B. Baylis, G. A. Presley, E. J. Sinke, and F. E. Stafford, J . Amer. Chem.66 A. D. Norman and R. Schaeffer, Iizorg. Chem., 1965, 4, 1225.99; 1965, 335, 195.2755.Soc., 1965, 87, 2753.bridge, ibid., 3923.Soc., 1964, 86, 5358136 IN 0 R G AN IC CHEMISTRYconverted to the thermally unstable 2- bromo-derivativea57 The molecularstructure (of approximately tetragonal symmetry) of iodopentaborane(9)has been determined,58 and the base-catalysed conversion of 1 - bromopen-taborane(9) into the 2-bromo-isomer has been achieved.5g A new type (3)of organoborane6O has been prepared, by reaction of C,oH8(BC12)4 with(3) (4)LiBH,. Spectroscopic results suggest an octahedral configuration 61 (4)for monocarbahexaborane( 7 ), CB 5H (from 1 -methylpentaborane), and thenew hexahydroborate ion R6HG2-, prepared 62a from diborane and sodiumborohydride, is rigorously octahedral.62a,b Several B5- and B,-organo-carboranes have been found in the products of the reaction between ethyl-diborane and acetylene.63 The two hydrides B,H,, and (the new) BgHIghave been prepared by the decomposition of the B,HI 4- and the B,H,- ions,respectively, with polyphosphoric Hexaborane( 10) gives a1 : 1 adduct with triphenylphosphine, and a carborane Me,C2B6H, withdimethylacetylene;65 improved yields of C2B,H5, 1 ,2-C2B4H6, 1 ,6-C2B,H,,and C2B,H7 have been obtained 66 by the ultraviolet irradiation of 2,3-dicarbahexaborane( S) .The electronic polarisabilities and diamagnetic susceptibilities of n seriesof polyhedral boranes and halogenoborafies can be accounted for in terms ofa conducting-sphere model for the boron cage,,' with additive contributionsfrom the attached groups.IlB nuclear magnetic resonance spectroscopy isan important method for investigating the stereochemistry of polyboranes ;among recent results, the spectrum of B5H1, has been assigned,68a the 1-and 2-monochlorodecaboranes identified,,sb and all the dissimilar hydrogenatoms in B,,HL, distinguished.68C Most of the structural assignments re-ferred to below have been obtained in this way.Nucleophilic attack of amides on decaborane (BloH14) takes place57 J.Dobson and R. Schaeffer, Inorg. Chem., 1965, 4, 593.58 L. H. Hall, S. Block, and A. Perloff, Acta Cryst., 1965, 19, 658.59 A. B. Burg and J. S. Sandhu, J . Amer. Chem. SOC., 1965, 87, 3787.6 o M. Zeldin and T. Wartik, Inorg. Chenz., 1965, 4, 1372.61 T. Onak, R. Drake, and G. Dunks, J . Amer. Chem. SOC., 1965, 87, 2505.62 (a) J. L. Boone, J . Amer. Chem. SOC., 1964,86, 5036; ( b ) R. Schaeffer, Q. Johnson,63 R.Koster and G. W. Rotermund, Tetrahedron Letters, 1965, 777.64 ( a ) H. A. Beall and W. N. Lipscomb, Inorg. Chem., 1964, 3, 1783; ( b ) J. Dobson,65 R. E. Williams and F. J. Gerhar!, J . Amer. Chem. SOC., 1965, 87, 3513.6 6 J. R. Spielman and J. E. Scott, jun., J . Amer. Chem. SOC., 1965, 87, 3512.67 A. Kaczmarczyk and G. B. Kolski, Inorg. Chem., 1965, 4, 665.6 8 ( a ) R. E. Williams, F. J. Gerhart, and E. Pier, Irtorg. Chem., 1965, 4, 1239;( b ) R. E. Williams and E. Pier, ibid., 1357; (c) R. L. Pilling, F. N. Tebbe, M. F. Ham-thorne, and E. A. Pier, Proc. Chem. SOC., 1964, 402; P. C. Keller, D. Maclean andR. Schaeffer, Chem. Comm., 1965, 204.and G. S. Smith, Inorg. Chem., 1965, 4, 917.D. Gnines, and R. Schaeffer, J . Amer. Chem. SOC., 1965, 87, 4072JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 137through nitrogen to give preferentially 69 the 6,9-disubstituted derivatives(RCONMe,),B,,H,,. It is likely that the same positions are bridged byAlH,+ and GaH,+ in the new compounds 70 (Me,NH)+(B,,H,,AlH,)- and(Me,NH)+(Bl,Hl,GaH,)-.As a consequence of the electrophilic nature ofthe B,,H,, nucleus, hydrazines RNHsNH, add readily 71 across the nitxilegroups in (MeCN),B,,H,,; the importance of good n-acceptor, as well asn-donor properties in the ligand has been stressed.7, Dimethyl sulphoxidereacts readily under acid conditions with the B,,H,,2- ion, to give first the(dimethyl sulphide) nonahydrodecaborate (-1) ion, substitution occurringmainly in the apical position [see ( 5 ) ] .1,lO-Bis(dimethy1 sulphide)-decaborane(8) is converted on heating to the more stable 2,7-isomer.8 n9[Reproduced, with permission, from W. H. Knoth, W. R. Hertler, and E. L.Muetterties, Inorg. Chem., 1965, 4, 280.1Chlorine substitution on the cage facilitates izucleophilic cleavage of theC-S bond, whereas positively charged substituents decrease the reactivity. 73Czesium tropenylium nonahydrodecaborate, the first member of a new classof organoboron compounds, and bistropenylium octahydrodecaborate 74 havebeen prepared (6). A series of derivatives B,,H,L-, B,,H,L,, B1,H,,L-,M. M. Fein, J. Green, J. Bobinski, and M. S. Cohen, Inorg. Chenz., 1965, 4, 583.iC”. N. Greenwood and J. A. McGinnety, Chem. Comin., 1965, 331.71 M. M. Fein, J. Bobinski, J.E. Paustian, D. Grafstein, and M. 5. Cohen, Inorg.7 2 J. J. Kaufman, J . Ilzorg. Nuclear Chem., 1964, 26, 2165.73 W. H. Knoth, W. R. Hertler, and E. L. Muetterties, Inorg. Chem., 1965, 4, 280.7 4 K. M. Harmon, A. B. Harmon, and A. A. Macdonald, J . Anzer. Chenz. SOC.,Chenz., 1965, 4, 422.1964, 86, 5036138 IN 0 RG A NI C C H E fix1 S TRYB, 2Hl.oL2 (L = sulphone, sulphonamide, urea, nitrile, nitrobenzene, oriodosobenzene) has been prepared by the acid-catalysed reaction of the baseswith the parent anions, typicallyH+ + BiJf1aa- + L + H, + B,oH&-;Oxygen-bonded ligands occupy equatorial, nitriles and iodosobenzene theapical positions.75 Dimethyl sulphide and trimethyl lamine derivatives ofBloH1,2- and B12H122- have been carbonylated with oxalyl chloride, to give(e.g.) 2,4- and 2,7($)-Me,NBl,HC80.The results in general confirm thatB1,HIo2- derivatives are more reactive than B12H1,2- derivatives to electro-philic attack, and also the preference for equatorial substitution, in spite ofthe lower electron densities calculated for these positions.76 Isomerisationoccurs a t high temperatures by polyhedral rearrangements rather than bygroup migrations.77 The N-protonated conjugate acid of the apical derivativeB,,H9N2Ar2- is obtained from B,,HlO2- and an aryl diazonium salt; azo-dyes are formed by cleavage and coupling with a second diazonium salt.'*Substitution of tghe normally inert halogenated ions B10X102-, B12X1 22- bynucleophiles such as CN- can be induced photochemically.79 The reactivityseems (reasonably) to be the inverse of that for electrophilic substitution,substitution going further for B12Br122- than for BloC1,,2-The B,oH182- ion is reduced by sodium in ammonia to B,,H,,4-, inwhich the two polyhedra are joined through equatorial boron atoms(7,eZ).Conversion into the other two forms, ae and a2, is catalysed by acid.80On the basis of kinetic measurements, a mechanism has been suggested 81 forthe attack of OH- on B2,H,82-.The CZB,Hll2- ion, an 1 l-particle icosahedral fragment, undergoes thereactionC,B,HIl2- + PhBCI, -+ PhC,B,oHll + 2C1-,the additional boron atom in the product probably occupying the twelfthicosahedral position in the otherwise open face of C2BgH,,2-. A similarlocation is likely 83 for the metal atoms in the [C,BgHllMn(CO),]- ion (S),[from BrMn(CO), and (C2BgH1,)2-J, in the Fe(C2BgHll)2- and in thecarborane analogues 84* of the cobalticinium ion, for which sandwich struc-tures of two icosahedral fragments are suggested.Piperidine extracts one boron atom from the lY2-carborane C2Bl,H127 5 H.C. Miller, W. R. Hertler, E. 1;. Muetterties, W. H. Knoth, and N. E. Miller,7 6 W. R. Hertler, W. H. Knoth, and E. L. Muetterties, Inorg. Chem., 1965, 4, 288.77 W. R. Hertler, W. H. Knoth, and E. L. Muett.erties, J . Amer. Chem. SOC., 1964,78 33. F. Hawthorne and F. P. Olsen, J . Arner. Chem. SOC., 1965, 87, 2366.5 9 S. Trofimenko and H. N. Cripps, J . Amer. Chem. SOC., 1965, 87, 653.8o M. F. Hawthorne, R. L. Pilling, and P. F. Stokely, J .Amer. Chern. SOC., 1965,M. F. Hawthorne, R. L. Pilling, and P. M. Garett, J . Amer. Chem. SOC., 1965,83 M. F. Hawthorne and P. A. Wegner, J . Amer. Chem. SOC., 1965, 87, 4392.83 M. F. Hawthorne and T. D. Andrews, J. Amer. Chem. SOC., 1965, 8'4, 2496.84 (a) M. F. Hawthorne, D. C. Young, and P. A. Wegner, J . Amer. Chem. SOC.,1965, 87, 1818; (b) M. F. Hawthorne and T. D. Andrews, Chem. Comm., 1965, 443.Inorg. Chena., 1965, 4, 1216.86, 5434.87, 1893.87, 4740JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEXENTS 1391 I267'1'1'Strmctzcre of the three possible B,,H,,-4 isomers in which two BloHQ-2 fragments are joinedby a two-centre B-B bend. [Reproduced, with permission, from M. F. Hawthorne,R. L. Pilling, and P. F. Stokely, J .Amer. Chem. SOC., 1965, $7, 1893.1A possible structure for (B&,Hll)3h(CO),- and (B,C,H,,)Re(CO),- (H atoms have[Reproduced, with permission, from M. F. Hawthorne and T. D. been omitted).Andrews, J . Amer. Chem. Soc., 1965, 8'7, 2496.140 INORGANIC CHEMISTRY(barene) ;8Su in the resulting piperidinium salt of the C,B,H,,- ion, a secondmolecule of the base is present as a hydrogen-bonded ~pecies.8~~ C-Metal-lation of the 1,2-carborane with sodamide occurs readily, further treatmentwith CO, giving 86 the acid (9). Further evidence of the acceptor propertiesof the carborane nucleus is provided by the easy cleavage of the exocyclicC-C bonds in the ester HC=B,,H1,*C*CO,Et (by NaOEt) and in the amideHC(B,,H1,)C*CONMe, (by LiAlH,).87 A study of the properties of sub-stituted phenyl groups Ax in dicarbaclovododecaborane (12) HC( B,,H,,)CArhas provided no evidence for delocalisation over both aryl group and car-borane system in the ground state of the 1,2-compounds, though weakelectron-donation to the phenyl group occurs by delocalisation in the 1,7-compound (neocarborane) .88 Hydroxymethylcarboranes have been used 89for the preparation of exocyclic derivatives such as the phosphate (10). Thecourse of electrophilic substitution on the carborane icosahedron is deter-mined by the positions of the more electronegative carbon atoms. Bro-(9) (10)rnination occurs less readily and completely than chlorination,gO substitutionbeing limited in carborane and neocarborane to HC*B,,H,Br,-CH andHC.B,,H,Br,*CH respectively.g0a The C-H groups are more acidic thanin the parent carborane.The planar anionic layers in ScB,C2 have a tessellated structure of 5- and7-membered rings containing both boron and carbon,gl and such compoundsmay be useful synthetically.Small amounts of B-H compounds have beenobtained by the hydrolysis of alkaline-earth borocarbides 92a MC,B andMC4B2 but not from simple b0rides.~2b The preparation and properties ofheterocyclic organoboranes have been reviewed. 93A further example of cis-trans-isomerism about the B-N bond has beenfound in EtO(Me)B.N(Me)Ph; many other compounds of the type X,B-NY,,s5 (a) L. I. Zakharkiii and V. N. Kalinin, Tetrahedron Letters, 1965, 407; ( b ) 31. F.Hawthorne, P. A. Wegner, and R. C.Stafford, Inorg. Chem., 1965, 4, 1675.86 L. I. Zakharkin, V. I. Stanko, and Yu. A. Chapovskii, Bull. Acad. Sci. U.S.S.R.,1963, 517.L. I. Zakharkin and Yu. A. Chapovskii, Bull. Acad. Sci. U.S.S.R., 1964, 723.88 M. F. Hawthorne, T. E. Berry, and P. A. Wegner, J. Amer. Chenz. SOC., 1965,87, 4746.as J. Green and A. P. Kotloby, Inorg. Chem., 1965, 4, 599; N. N. Schwartz, E.O'Brien, S . Karlan, and M. M. Fein, ibid., p. 661 ; N. Mayes and J. Green, ibid., p. 1082.(a) H. D. Smith, T. A. Knowles, and H. Schroeder, Inorg. Chem., 1965, 4, 107;( b ) L. I. Zakharkin, V. I. Stanko, and A. I. Klimova, Bull. Acad. Sci. U.S.S.R., 1964,722.91 G. S. Smith, Q. Johnson, and P. C. Nordine, Acta Cryst., 1965, 19, 665.9 2 ( a ) L. Ya. Markovskii and X. V. Vekshina, J .Appl. Chem. U.S.S.R., 3'7, 2102,2107; ( b ) N. N. Greenwood, R. V. Parish, and P. Thornton, J . Chein. SOC., 1965, 545.93 R. Koster, Adc. Organonzetallic Chent., 1964, 2, 257JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 141both monomeric 94 and dimeric, 95 have been investigated spectroscopically.Isocyanato- and isothiocyanato-boranes have been ~repared,~6 and theazido-derivatives (XB,N,),, (X = GI, Br), have D3h symmetry.97 Severalsymmetrical N-fluor~alkyl-,~~~ B-flu~roaryl-,~~~ and B - t r i e t h y n ~ l - ~ ~ ~ andunsymmetrical N-methyl- 98c and B-propoxy- borazines gsd have been pre-pared by conventional methods. B-Trichloro-N-trhethylborazine reactsnormally with C-lithiocarborane~.~~ A determination of the crystal struc-ture of hexaethylborazine 100 confirms that the ring is planar regular hexa-gonal, and measurements of the heats of hydrolysis of B,H,N&e,,B,H,N,H,, and B,Cl,N,H, show that the B-N bond is weakest in the lastcompound.lol The reduction potentials of phenyl-substituted borazines,determined polarographically, have been related to a molecular-orbitaltheory of their structure.lo2 Borazine B,N3H6 and borazanaphthaleneB,N,H8 take up respectively three and five moles of hydrogen chloride orbromide, the original planarity being lost.The hydrogen halide is eliminatedstereospecifically.lQ3The preparation of some 5- and &membered rings containing carbon aswell as boron and nitrogen has been described.104 1,8,10,9-Triazabora-decalin on reaction with LiMe and Me,N.BClPh gives the boryl derivative(1 la), from which the tricyclic compound (1 lb) is obtained by transaminationwith aniline.NN-Dimethylhydrazine reacts analogously. The triaza-broadecalin ring is expanded by phenyl isocyanate or isothiocyanate to git-0fused %membered ring structures.10594 H. T. Baechle and H. J. Becher, Spectrochim. Acta, 1965, 21, 579.95 A. J. Banister and N. K. Greenwood, J . Chem. SOC., 1965, 153-1.96 M. F. Lappert, H. Pyszora, and M. Rieber, J . Chem. Soc., 1965, 4256.97 P. I. Paetzold, M. Gayoso, and K. Dehnicke, Chem. Ber., 1965, 98, 1965.98 (a) A. Meller, M. Wechsberg, and V. Gutmann, Monatsh., 1965, 96, 388; ( b ) H.Watanabe, T. Totani, and T. Yoshizaki, Inorg. Chem., 1965, 4, 657; (c) A. Meller andR. Schlegel, Monatsh., 1965, 96, 1209; ( d ) A.Meller, R. Schlegel, and V. Gutmann,ibid., 1964, 95, 1564.D9 J. L. Boone, R. J. Brot,herton, and L. I. Petterson, Inorg. Chem., 1965, 4, 910.loo M. A. Viswanlitra and S. K. Vaidya, 2. Krist., 1965, 121, 472.Iol B. C. Smith and L. Thakur, Nature, 1965, 208, 74.Io2 D. F. Shriver, D. E. Smith, and P. Smith, J. Amer. Chem. Soc., 1964, 86, 5153.lo3 A. W. Laubengayer, 0. T. Beachley, jun., and R. F. Porter, Inorg. Chenz., 1965,4, 578.lo4 G. Hesse and A. Haag, Tetrahedron Letters, 1965, 1123; H. Witte, ibid., p. 1127;G. Hesse and H. Witte, Annulen, 1965, 687, 1 ; J. Tanaka and J. C. Carter, TetrahedronLetters, 1965, 329; J. Casanova, jun., H. R. Kiefer, D. Kuwada, and H. A. Boulton,ibid., p. 703.lo5 P. Fritz, K.Niedenzu, and J. W. Dawson, Inorg. Chena., 1965, 4, 886142 INORGANIC CHEMISTRYVery high pressures and temperatures are required for the synthesis ofB20, regarded as a n " unsymmetrical " analogue of graphite.lOg The inter-conversion of boroxine H&O3 and H2B203, believed to have the structure(12), has been studied thermochemically.107 The new thioperboratesMBS,, M2B2S5, (M = Na,K), are less stable to moisture or to heat than theiroxygen analogues.lo8The heat of formation of difluoroborane, prepared from BF3 and bor-oxine, has been determined, and its infrared spectrum and that of HBBr,assigned. O Potassium pentafluor ophen yl trifluoro b ora t e K ( C 6F, BF 3) hasbeen obtained ll0a by condensing pentafluorophenylboron diftuoride 11Ob intoan aqueous solution of potassium fluoride.The 1 : 1 complex BP3,NH20Kis acidic,lll and forms the salt K[BF,ONH,]. Vapour pressures over Br3-fluoroborate-CK,Cl2 mixtures have been interpreted 112 in terms of thecondensed ions B2H7-9 B3H1,-. Co-ordination of BCI, to the oxygen atomof NN-dimethylformamide increases 113 the barrier to rotation about theC-N bond from 6.2 to 14.5 kcal.mole-1. The central bond in B2F4 is split bypropionic acid :114B,F, + 2EtC0,H -+ 2EtCO,BF, + H,.1,2-Bis(dichloroboryl)ethylene is a less good acceptor than the correspond-ing ethane derivative ;l15 partial disproportionation of the methylamineadduct occurs, to form Me3N,BCl,. The mass spectrum of B,Cl, showspeaks characteristic of the progressive removal of chlorine atoms from theparent molecule.116 No B,, peaks were observed for B,,Cl,,, the highestbeing that for BllClll+.Aluminium.Monomeric alane AlH, dimerises readily,l17 and the firstderivative of dialane has been prepared by the reactionTHFMe,N.AlCIH -+ Me,N.Al,H,.NaAlH,Substitution and addition reactions of phenylacetylene a,nd organoalanesR,AlH (R = Me,Et,Ph) are suppressed by triethylamine.ll9 The perfluoro-phenyl derivatives C,F,AlBr, and (C,F,),AlBr are obtained 120 from AlBr,and the mercurial MeHgC,F,, and reaction of lithium aluminium hydride withC6F,Br yields,121 after disproportionation, the benzene-soluble LiAl( C6F5)3Br.The temperature-dependence of the proton magnetic resonance spectra oflog H. T. Hall and L. A. Compton, Inorg.Chem., 1965, 4, 1213.lo' L. Barton, S. K. Wason, and R. F. Porter, J . Phys. Chem., 1965, 69, 3160.lo* F. Chopin and P. Hagenmuller, BUZZ. SOC. chim. France, 1965, 3031.Ion R. F. Porter and S. K. Wason, J . Phys. Chem., 1965, 69, 2208, 2461.110 (a) R. D. Chambers, T. Chivers, and D. A. Pyke, J . Chem. Soc., 1965, 5144;ll1 I. G. Ryss and S. L. Idel's, Russ. J . Inorg. Chem., 1965, 10, 383.112 S. Brownstein and J. Paasivirta, Caiaad. J . Chem., 1965, 43, 1645.113 E. X. Gore, D. J. Blears, and S. S. Danyluk, Canad. J . Chem., 1965, 43, 2135.l l * A . K. Holliday, G. N. Jessop, and F. B. Taylor, J . Chem. SOC., 1965, 1551.116 C. Chambers and A. K. Holliday, J . Chem. Xoc., 1965, 3459.A. G. Massey and D. S. Urch, Chem. and Ind., 1965, 607.117 P.Breisacher and B. Siegel, J . Amer. Chem. SOC., 1964, 86, 5053.l l s A . R. Young, jun., and R. Ehrlich, J . Amer. Chem. SOC., 1964, 86, 5359,llS J. R. Surtees, Austral. J . Chem., 1965, 18, 14.lZo R. D. Chambers and J. Cunningham, Tetrahedron Letters, 1965, 2389lZ1 R. S. Dickson, Chem. Conam., 1965, 68.( b ) R. D. Chambers and T. Chivers, ibid., p. 3933JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 143alkylaluminiums indicates breakage of a bridge bond, which is then re-formedwith a digerent alkyl group ; 122a the corresponding redistribution reactionbetween AlMe, and AlEt, is very slow in pyridine.122b The benzlonitrileadducts of R3,!!1 (I3 = Me,Et,Ph) and Me2Al@1 rearrange to the dimericbenzylideneamino-derivative~,~~~~ e .g., (PhMeC:NAlMe,) %.Alkyl cyanidesreact similarly, [ (MeCH:NAlMe,), appears to exist in cis- and trans-forms],but further elimination of a hydrocarbon can occur, to give polymericThe (dimeric) phosphinoalane (Et,Al.PPh,), has also beenprepared.124 The electrochemistry of organoaluminium compounds has beenre~iew6d.l~~ Measurements of the conductivity of adducts of organo-aluminium compounds with Lewis bases provide evidence for solvatedAlX,+ ions, and blue aluminium-containing radicals have also been obtainedelectrolytically.126 In the complex [Al(OPri)3]2,C,H4(NH,)2, rapid ex-change of the alkoxy-groups takes place both within the molecule and withthe s01vent.l~' On the basis of freezing-point measurements, it is sug-gested128 that aluminium dissolved in AlBr, or All, may be present asdi-atoms or the associated dimers A14Br, and A&.Gallium, Indium, and Thallium.Nuclear magnetic resonance spec-troscopy using 'lGa shows, among other that two types of galliumatom are present in GaCl, and GaBr,. Complexes of GaI have been inves-tigated by Raman spectroscopy,130 and In+ has been detected polarogra-phically as an intermediate in the electrolytic oxidation of indium,131 Gal-lane and jndane, studied rnass-spectrometrically in a flow system, aremonomeric (unlike NH,, and contrary to earlier reports) .132 The complexesMe,N,GaH,-,X, (X = Cl,Br,I,n = 0-3) have been prepared from thesimple gallane adducts and the hydrogen halides;l33 GaH,Cl is displaced fromits trimethylamine complex by BF,.The more st'able dichlorogallane,synthesised according to the equationMe,SiH f GaC1, + Me,SiCl + RGaC1,is (unlike gallane itself) dimeric in benzene; it decomposes to Ga(GaC1,) onheating.134 Organometallic compounds behave comparably to the hydridesin that wit,hin the group, only the alkyls of aluminium are associated;l35aPhGaX,, Ph,GaX, on the other hand, form halogen-bridged dimersin benzene.13jb Methane can be eliminated from the complexes of122 (u) K. C. Ramey, J. F. O'Brien, I. Hasegawa, and A. E. Borchert, J . Phys. Chem.,1965, 69, 3418; (b) T. Mole, Austral. J . Chem., 1965, 18, 1183.123 ( a ) J. E. Lloyd and K. Wade, J . Chem. SOC., 1965, 2662; (b) J. R. Jennings, J. E.Lloyd, and K. Wade, ibid., p. 5083.13* A. W. Johnson, W. D. Larson, and G.H. Dahl, Canad. J . Chem., 1965, 43, 1338.125 Yu. M. Kessler, N. Bl. Alpatova, and 0. R. Osipov, Russ. Chem. Rev. 1964, 33,119.las H . Lehmkuhl and H. D. Kobs, Tetrahedron Letters, 1965, 2505; H. Lehmkuhl,G. Fuchs, and R. Koster, ibid., p. 2511.127 V. J. Shiner, jun., and D. Whittaker, J . Amer. Chern. Soc., 1965, 87, 843.128 J. Thonstad, Canad. J . Chem., 1964, 42, 2739.lZD J. W. Akitt, N. N. Greenwood, and A. Storr, J . Chem. SOC., 1965, 4410.l 3 0 L. A. Woodward and M. J. Taylor, J . Inorg. Nuclear Chem., 1965, 27, 737.131 R. E. Visco, J . Electrochem. SOC., 1965, 112, 932.132 P. Breisacher and B. Siegel, J . Amer. Chem. SOC., 1965, 87, 4255.133N. N. Greenwood and A. Storr, J . Chem. SOC., 1965, 3426.134H. Schmidbaur, W.Findeiss, and E. Gast, Angew. Chem., 1965, 7'7, 170.135 ( a ) N. Muller and A. L. Otermat, Inorg. Chem., 1965, 4, 296; (b) P. G. Perkinsand M. E. Twentyman, J . Chem. Xoc., 1965, 1038144 INORGANIC CHEMISTRYMe,M (M = Al,Ga,In) with primary and secondary aliphatic phosphines, togive e.g., (Me,Ga*PMe,),, which forms six-membered rings in s01ution.l~~Complexes of the type [M(diars),X,][MX,] (M = GaT1l,Inlll) areformed from halides of the metal and a ditertiary arsine.13' The unusualanions Ga,Cl,,- and In(diars)I,- are formed from GaCl, and 1111,; for theformer, a bridged structure (13) is suggested.Indium(II1) also forms six-co-ordinate cationic complexes with bidentateligands such as 2,2'-bipyridy1;138 other complexes of Inrrr have beenstudied .I39Thallic chloride forms the chlorothallate ion TlCl,- with the halides oflarge univalent cations, and T1C13,2py with pyridine.The thallic complexTl(Et,N*CS,), is a non-conductor, and is presumably trichelate.l40 Thefluorothallate(rrr) compounds (Li,Na)T1F4 have a fluorite-type structure,and do not contain TlF,- ions.lel Raman spectra of aqueous TllI1 chloridecomplexes show the presence of T1C12+, TlCl,', TlCl,, TiCl, -, and TlC163-, butno polymeric species ; comparison with the crystal spectra suggests that bothtetrahedral and octahedral structures are distorted by interaction with waterm01ecules.l~~Bis(pentafluorophenyljthallium(I1J~ bromide (C6F,),T1+Br- gives 1 : 1complexes with bidentate ligands, in which the metal may be five-co-ordinated.With halides of large cations, the anions [(C6F,),T1X,]- areformed.143 On the basis of its vibrational spectra t,he cation [Me,Tl,py]f isbelieved to be T-shaped.14,Group IV.-Carbon. Thorium mono- and di-carbides give hydrogen,C,-C, alka,nes and unsaturated hydrocarbons with aqueous alkali.145 Inter-calation compounds of Li,Na,K have been obtained from graphite and thenaphthalene complexes of the alkali metals in tetrah~drofuran.14~ A phase-change in graphits nitrate has been recognised as being due to '' melting '' of atwo-dimensional layer.l4' The energetics of the polymerisation of dicyano-gen have been reviewed.l4*136 0. T. Beachley and G. E. Coates, J . Chem. SOC., 1965, 3241.137 R. S. Nyholm and K. Ulm, J . Chem. SOC., 1965, 4199.laeA.J. Carty and D. 0. Tuck, J . Chem. SOC., 1964, 6012.139 D. G. Tuck and E. J. Woodhouse, J . Chem. SOC., 1964, 6017; E. N. Deichman,G. V. Rodicheva, and P. A. Chel'tsov, RUSS. J . Inorg. Chem., 1965,10, 48; E. K. Deich-man and L. S. Krysina, ibid., p. 256.140 F. A. Cotton, B. F. G. Johnson, and R. M. Wing, Inorg. Chem., 1965, 4, 502.lol R. Hoppe and C. Hebecker, 2. amrg. Chem., 1966, 335, 85.142 T. G. Spiro, Inorg. Chem., 1965, 4, 731, 1290.14s G. B. Deacon, J. H. 8. Green, and R. S . Nyholm, J . Chern. Xoc., 1965, 3111.144 I. R. Beattie and P. A. Cocking, J . Chem. Xoc., 1965, 3860.M. J. Bradley, M. D. Pattengill, and L. M. Ferris, Inorg. Chern., 1965, 4, 1080.lo6 C. Stein, J. Poulenard, L. Bonnetain, and J. Go16, Compt. rend., 1965, 260, 4503.A.R. Ubbelohde, G. S. Parry, and D. Nixon, Nature, 1965, 206, 1352.148 H. J. Rodewald, Chem.-Ztg., 1965, 89, 522JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMERTSSiticon.145Simple and substituted silanes form clathrate compounds withurea and thiourea which may be useful for their ~eparati0n.l~~ Iodosioaneforms complexes with pyridine and alkylpyridines which are formulated as(L,SiH,)+I-, and a 1 : 1 adduct (Me,NSiH,)+I- with trimeth~1arnine.l~~On the basis of its vibrational spectra, P(SiH,),, like N(SiH,),, is at leastclose to planarity, the lone pair on the central atom contributing to 3pz-3dzbonding ;151a by contrast, p3t-dn bonding is not stereochemically significantin trigermyl phosphine 151b P(GeH,), 0rl51c in GeH,NCO.The similarity ofthe ultraviolet spectra of phenanthrene and silazarophenanthrene ( 14) alsosuggests the use of &orbitals by silicon.152 The stability of the silylcobaltcarbonyls R,SiCo(CO), formed in the reaction of Co,(CO), with eitherSiH,I(R = H)15Za or R,SiH(R = Cl,Ph)153b is ascribed (as for similarphosphine derivatives) to d,-d, bonding.153b Evidence for electron releaseto silicon is provided by the measurement of the dipole moments of alkylsilyl derivatives,154a the electronic 154b and proton magnetic resonancespectra 154c of phenylsilanes and their derivatives, and by the detailed inter-pretation 154d of the electron spin resonance spectra of biphenyl radical ions(Me3X*C6H,*C6H5)-, (x = Si,Ge). Again, germanium withdraws electronsless effectively than does s i 1 i ~ o n .l ~ ~ ~ Configuration is retained in the cleav-a’ge of a substituted disilane by lithium.155 The chemistry of organo-substituted cyclosilanes has been reviewed.lS6Many new silicon-nitrogen compounds have been made, and their usein further preparative reactions in~estigated.1~7, Particularly usefulreactions involve the elimination of either amines, e .g. ,I59a2R3SiNHR’ ---+ (R3Si)2NR’ + R’NH,,or of trimethylsilyl chlorides :15gbMe,SiNH*SiMe, + Me,SiCl, -+ Me,SiNH*SiMe,Cl + Me,SiCl.As with boron-nitrogen compounds, either linear or cyclic compounds can beprepared by transarninati~n.~~~~ The sodium derivative of hexamethyl-disilazane (Me,Si),NNa reacts with carbon dioxide and with carbon disul-phide togive the cyanamide derivative 160a Me,SiN:C:NSiMe,, and [ (RO),Si],N149 R.Muller and G. Meier, 2. anorg. Chem., 1964, 332, 81, -381; 1965, 337, 268.150 B. J. Aylett and R. A. Sinclair, Chena. and In&., 1965, 301.151 (a) G. Davidson, E. A. V. Ebsworth, and G. M. Sheldrick, Chem. Conzm., 1965,122; ( b ) S. Cradock, G. Davidson, E. A. V. Ebsworth, and L. A. Woodward, ibid.,p. 515; ( c ) J. E. Grfiths and A. L. Beach, ibid., p. 437.152 J. M. Gaidis and R. West, J. Amer. Chem. SOC., 1964, 86, 5699.153 (a) B. J. Aylett and J. M. Campbell, Chem. Comm., 1965, 217; ( b ) A. J. Chalkand J. F. Harrod, J . Amer. Chem. SOC., 1965, 87, 1113.154 (a) V. N. Krishnamurthy and S. Soundararajan, J . Inorg. Nuclear Chern., 1966,27, 2341; ( b ) L. Goodman, A.H. Konstam, and L.H. Sommer, J . Aqner. Chem. SOC., 1965,87, 1012; (c) R. Waack and M. A. Doran, Chem. and Ilnd., 1966, 563; ( d ) M. D. Curtisand A. L. Allred, J. Amer. Chem. Soc., 1965, 87, 2554.lS5 L. H. Sommer and R. Mason, J . Amer. Chem. Soc., 1965, 87, 1619.156 H. Gilman and G. L. Schwebke, Adv. Organonaetallic Chem., 1964, 1, 90.15’ E. W. Abel and D. A. Armitage, J . Chem. SOC., 1964, 5975.15*K. Ruhlmann, A. Reiche, and M. Becker, Chem. Ber., 1965, 98, 1814.159 (a) U. Wannagat, P. Geymeyer, and E. Bogusch, Xonatsh., 1966, 96, 585;( b ) J. Silbiger and J. Fuchs, Inorg. Chem., 1965, 4, 1371; ( c ) C. H. Yoder and J. J.Zuckerman, &id., p. 116.16* (a) U. Wannagat, H. Kuckertz, C. Kruger, and J. Pump, 2. anorg. Chem., 1964,333, 54; ( b ) U.Wannagat, K. Behmel, H. Wolf, and H. Burger, ibid., p. 62146 INORGANIC CHEMISTRYis obtained from [(RO),Si],NNa, by successive treatment with silicontetrachloride and the alcohol.ls@ Dichloro(phtha1ocyanino)silicon is con-veniently synthesised from SiC1, and either o-cyanobenzamide or 1,3-di - iminoisoindolineAlkylpolysiloxancs substituted by fluorine in the a- and /?-positions aresensitive to heat and alkali, whereas the y-derivatives are stable to both.162The reaction of aluminium chloride with dimethylsiloxanes leads to mole-cules in which the groups -Me,SiO- and -AlClO- alterr~ate,l~~ and hetero-ailoxanes of zinc, cadmium, mercury, and thallium(@ have been preparedfrom organometallic compounds and silanols or silanolates,l64 typicallyMe,SiONa + MeHgCl + Me,SiOHgMe + NaCl.The infrared spectra of a series of disiloxanes 165a shows that the partialp,-d, bonding is strongly dependent on the nature of the substituents.Asimple treatment 165b of the vibrational spectra of X,O, (X = Si,P,S,CI)molecules suggests that z-bonding is strongest in the silicon compounds.The force constants and interbond angles, taken as a sensitive measure ofppn-dra bridge bonding, have been discussed critically,165c and the importanceof polarising cations in increasing p n 4 , bonding and the XOX angle inX20, anions has been s t r e s ~ e d . l ~ ~ ~ , ~ Organosilyl sulphides are formed fromalkylchlorosilanes, typically according to the reactionMeSMgI + Me,SiCl ---+ MeSSiMe, + MgICl;the corresponding germyl compounds are better prepared from a germylhalide (e.g., Ph3GeBr) and a mercaptan in the presence of pyridine.166Polymeric Sip, is obtained by condensing at -196" the product of the re-action of silicon with SiF,; perfluorosilanes Si,$2n+2 (n = 1-14) are pro-duced by its destructive distillation, and the compounds SiF,( SiF,),BF,,(n = 1,2,3), have been isolated from the reaction of the monomer with borontrifluoride.l67 Polymeric SiCI,, also, is formed 168 in a reaction betweensilicon a,nd SiC1,.Calcium silicide CaSi, reacts with iodine monochloride to give169a thehighly-coloured, layer-structured, (SiCl),, in which the chlorine can bereplaced by methyl or alkoxy-groups. The aminopolysilanes 169b, arenon-stoicheiometric, and contain unpaired electrons.161 31.K. Lowery, A. J. Starshak, J. N. Esposito, P. C. Krueger, and M. E. Kenney,Inorg. Chem., 1965, 4, 128.162 T. N. Bell, R. N. Haszeldine, M. J. Kewlands, and J. B. Plumb, J. Chem. SOC.,1965, 2107; R. N. Haszeldine, M. J. Newlands, and J. B. Plumb, ibid., 2101.163 D. Cordischi, A. Mele, and A. Somogyi, J. Chem. Soc., 1964, 5281.164 F. Schindler, H. Schmidbaur, and U. Kriiger; H. Schmidbaur and F. Schindler,Arzgew. Chem., 1965, 77, 865.165 (a) G. Engelhardt and H. Kriegsmann, 2. anorg. Chem., 1965,336, 286; ( b ) R. J.Gillespie and E. A. Robinson, Canad. J. Chem., 1964, 42, 2496; (c) A. N. Lazarev,BUZZ. Acad. Sci. U.S.S.R., 1964, 218; ( d ) A. N. Lazarev and T. F. Tenisheva, ibid.,166 K. A. Hooton and A. L. Allred, Inorg.Chem., 1965, 4, 671.167 P. L. Timms, R. A. Kent, T. V. Ehlert, and J. L. Margrave, Nature, 1965, 207,187; P. L. Timms, T. C. Ehlert, J. L. Margrave, F. L. Brinckman, T. C. Farrar, andT. D. Coyle, J . Arner. Chem. SOC., 1965, 87, 3819.168 M.. Schmyisser and P. Voss, 2. anorg. C h . , 1964, 334, 50; P. W. Schenk andH. Blochmg, sbsd., p. 57.169 (a) E. Hengge and G. Scheffler, Monatsh., 1964, 95, 1461; (b) E. Hengge andU. Brychly, 2. anorg. Chem., 1965, 339, 120; (c) E. Hengge and G. Schemer, Monatsh.,1964, 95, 1450.p. 379JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 147Spectroscopic evidence supports the cisoctahedral codguration forSiF,,Z(amine) adducts7170a and the tram-configuration 170b for SiF4,2Ph,P0.Infrared spectroscopy and conductivity measurements suggest that the1 : 4 adducts, e.g., Si(C10,),,4Ph3PO, contain the cation [Si(Ph,PO)4]4+.Themethyl fluorosilicate ions (SiMe,F,-,)2-, (n = 1,2,3) have been synthesisedfrom Me4NF and the appropriate fl~orosi1ane.l~~Trichlorogermane, HGeCl,, is acidic, and can be used forthe preparation 1 7 2 of chlorogermanites MGeC1, (M = NH,,K,Rb,Cs) ; it canbe methylatedl73 with tetramethyltin to give methyldichlorogermaneMeGeC1,H. Thermally stable compounds R,GePPh2 and R,Ge(PPh,), areformed from the appropriate halide and lithium diphenylphosphide ; they arehydrolysed to the digermoxane (R,Ge) ,O and diphenylphosphine, andoxidised to R,Ge*O*P( O)Ph,. Germanes carrying more halogen atoms formwater-stable polymeric dipheny1pho~phinogermanes.l~~ A study by protonmagnetic resonance spectroscopy of the mobile equilibrium between Me2GeX,(X = C1,BrJ) and either Me,Ge(SMe), or (Me,GeS), has shown that theinterchange process is non-random; in the first system, mixed speciesMe,Ge(X)SMe predominate, and in the second, trimeric (Me,GeS), is themost abundant compound in a mixture of rings and chains.17j A new pre-parative method for the cyclic compound (GePh,), (from diphenylgermane)has been described.The ring is opened by iodine to give I(GePh,),I, whichforms the linear derivative Ph( GePh,) ,Ph with phenyl-lithium, and whichis hydrolysed to the cyclic ether (15). The cyclic compounds (GePh,) 5,6Germa.iLium.EtI \ Ph,Ge, ,GePh,0 (I 5 )Me2Sn /N\ SnMezi IEtN, ,NEtSnMe2 (16)have also been prepared.176 The tetrahdides of germanium, tin, and leadform 1 : 1 adducts with bipyridyl, with the exception of GeI,, which forms a1 : 2 ndduct formulated as (bi~y,GeI,)~+, 21-.Terpyridyl gives the ioniccomplexes (terpy,MI,)+I-, (M = Ge,Sn). All the cations contain the 6-co-ordinated metal; the 1 : 1 terpyridyl complexes with Ph,PbX, are undis-sociated.177Tin. The species Snl?,- and Sn,F,- predominate in the molten systemsMF-SnF, (M = Na,K,Rb,Ca), as they do in aqueous solution.178a Various170 (a) H. Burger, W. Sawodny, and F. Hofler, Monatsh., 1965, 96, 1437; ( b ) I. R.171 J. J. Moscony and A. G. MacDiarmid, Chem. Comm., 1965, 307.172 I. V. Tananaev, B. F. Dzurinskii, and Yu. N. Mikhailov, Russ. J . Inorg.Chem.,173 V. F. Mironovana and A. L. Kravchenko, J . @en. Chem. (U.S.S.R.), 1964, 34,174 E. H. Brooks, F. Glocking, and K. A. Hooton, J . Chem. SOC., 1965, 4283.175 K. Moedritzer and J. R. Van Wazer, J . Amer. Chem. Xoc., 1965, $7, 2360.176 W. P. Neumann and K. Kiihlein, Annalen, 1965, 683, 1.177 J. E. Fergusson, W. R. Roper, and C. J. Wilkins, J . Chem. SOC., 1965, 3716.17* ( a ) J. D. Donaldson, J. D. O'Donogue, and R. Oteng, J . Chena. SOC., 1965, 3876;Beattie and M. Webster, J . Chem. SOC., 1965, 3672.1964, 9, 862.1359.( b ) J. D. Donaldson and J. F. Knifton, ibid., 1964, 6107148 INORGANIC CHEMISTRYspecies have been found in solutions of complex tin formate~,17~~ but thesolids obtained are all derivatives of the triformatostannate(r) ionESn(CHO2) ,I-*Many of the reactions of compounds of tin(1v) depend on the cleavage of apola’r covalent bond from tin; organotin hydrides can act as either electro-philic 179a or nucleophilic 179b reagents. Aldehydes and ketones react withstannanes, to give alkoxytin compounds in good yield; e.g.,NN-Dialkylstannylamines are obtained similarly from trialkyltin hydridesand azomethines.lsO On the other hand, hydrogenolytic fission of Sn-Nbonds by dialkyl- or diaryl-tin hydrides gives a monohydride, e.g.,R,SnNPh*CHO + R’,SnH, + R,SnSnR‘,H + PhNHCHO.Linear tri-, tetra-, penta-, and hexa-tine derivatives have been prepared bysimilar reactions,181 and also from organotin hydrides and oxides,1S2 e.g.,2Bu,SnH + Bu,SnO + Bu[SnBu,],Bu + H20.Alkylstannanes are decomposed by hydrogen bromide to give hydrogen andpolytin derivatives; with arylstannanes the Sn-C bond is broken in prefer-en~e.18~ The preparation of several aryl- and perfluorophenyl-derivativesof Snxv has been reported;ls4 reaction of tetraphenyltin with fluorides ofboron or phosphorus is thought to yield salts of the Ph,Sn+ Distan-nazanes, like disilazanes, are formed in the elimination reaction2R,SnNHR’ + (R,Sn),NR’ + R’NH,,a.nd the cyclic trimer (16) has been synthesised by a method involving bothelimination and transamination.186 In contrast to related compounds ofsilicon, however, alkylthio-compounds of tin(Iv), R,SnSR’, R,Sn(SR’), andRSn(SR’), can be prepared in aqueous s01ution.l~~ Cyclic and spiro-derivatives have been obtained, as well as a sulphonium salt (Me,SnSMe,)+I-.Dipolar double bonds, (C:C, C:N, C:O, S:O, S:N) undergo addition reac-tions with stannylaminesl88a (e.g., Me,Sn-NMe,), stannylphosphines,188bPh,SnPPh, + CS, + Ph,Sn*S*CS*PPh,and with dibutyltin oxide.188c Tin( ~ v ) alkoxides add exothermally acrossthe carbonyl bond in aldehydes, and since the product is also a tin alkoxide,high polymers R’,Sn(OCHR),OR’ are eventually formed by an (‘ insertion ”mechanism .lS9R,CO + R’,SnH + R,CH.OSnR’,.179 ( a ) H.M. J. C. Creemers and J. G. Noltes, Rec. Tn7v. chim., 1965, 84, 500;180 W. P. Neumann and E. Heymann, Annalen, 1965, 683, 11, 24.lS1 H. M. J. C. Creemers and J. G. Noltes, Rex. Truv. chirn., 1965, 84, 382.lS2 A. K. Sawyer, J. Amer. Chem. SOC., 1965, 87, 537.183 G.Fritz and H. Scheer, 2. anorg. Chem., 1965, 338, 1.lS4 ( a ) R. D. Chambers and T. Chivers, J. Chem. SOC., 1964, 4782; ( b ) J. Burdon,lS5 D. W. A. Sharp and J. M. Winfield, J. Chem. SOC., 1965, 2278.lS6 K. Jones and M. F. Lappert, J. Chem. SOC., 1965, 1944.18’ E. W. Abel and D. B. Brady, J. Chem. SOC., 1965, 1192.lS8 (a) T. A. George, K. Jones, and M. F. Lappert, J. Chem. SOC., 1965, 2157; ( b ) H.Schumann, P. Jutzi, and M. Schmidt, Angew. Chem., 1965,77,912; ( c ) A. J. Bloodworthand A. G. Davies, Chena. and Ind. 1965, 900.1*9 A. G. Davies and W. R. Symes, Chem. Comn., 1965, 25.(b) A. J. Leusink and J. G. Noltes, ibid., p. 585.P. L. Coe, and M. Fulton, ibid., 1965, 2094JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 149Dimethyldichlorostannane reacts with carboxylic acids and phenols togive distannoxane~~~~ of the type (R’Me,Sn),O, (R’ = RCO,, PhO).Theoccurrence of 4-, 5- and 6-co-ordination in organotin compounds has beendiscussed on the basis of spectroscopic evidence.lg1 Five-co-ordinated tinappears to be present lg8 in the complexes R,Sn(Ox)X, (R = Me,Ph;Ox = 8-quinolinyl; X = C1,I). Several compounds of the type R,Sn(Ch),,where Ch is a chelating ligand, have been prepared,l93 and also salts of thethiocyanatomethylstannate ionslg4 [Me,Sn(SCN),-,],- (x = 1,2,3). In com-plexes of the type (R,SnL,), (R = Me,Ph; L is bidentate),195a and195b in[Me,Sn( 0H),l2-, spectroscopic results show that the C-Sn-C skeleton islinear, the s-orbital contribution being maximised in the bonds to carbon.Some disproportionation to a trimethyltin species occurs in aqueous solu-tionThe nitrate groups in tin(1v) nitrate are probably bidentate lg6 (on infraredevidence), as in [Co(N03)J2-, the metal being eight-co-ordinated, but theyare unidentate in the complex py2,Sn(N03),. The configuration of a numberof octahedral complexes of tin(rv) fluoride is cis where n-bonding with theligand is likely, ( Ph3P0, MeCN), but trans otherwise (tetrahydrofuran,Me3N).lg7 Stannic fluoride reacts with the fluoride ion to give the octa-hedral anions SnF,B-, provided the solvent (B) is a strong enough baseto prevent the formation of fluorine bridges.198 The existence of cis- andtrans-[SnF,( OH) ,I2- and [ SnF3( OH),]2- in labile and statistical equilibriumwith [SnF,OHI2- has been established by 19F nuclear magnetic resonancespectroscopy.199 Stannic chloride also forms both cis- and trans-di-adducts ;diethyl sulphicle complexes more strongly than diethyl ether.200a A trans-configuration has been found crystallographically2OOb in tetrachlorobis( tetra-hydrothiophen) tin( IV) .cis-Complexes are formed with chelating carboxylicanhydrides 201a and with carboxylic acids,201b in which the ligand is probablya half-opened acid dimer. The complexes Sn(Acac)(OMe)X, (X = Cl,Br,I)are dirneric, and possibly involve methoxy-bridges.202 The preparation ofthe oxyhalidea SnOX, (X = F,Cl,Br) and of SnF,CI, and S11F,(ON02), hasbeen described. O3The Pb2T ion forms weak Complexes with (preferentially) even Lead.l90 &I.Ohara, R. Okswara, and Y . Nakamura, Bull. Chem SOC. Japan, 1965, 38,lS1 R. Okawara, J . Chena. SOC. Japan, 1965, 88, 543.lS2 A. H. Westlake and D. F. Martin, J . Inorg. Nuclear Chena., 1965, 27, 1579.193 W. H. Nelson and D. F. Martin, J . Inorg. Nuclear Chem., 1965, 27, 89.lS4 A. Cassol, R. Portanova, and R. Barbieri, J . Inorg. Nuclear Cheni., 1965, 27,lS5 (a) M. M. McGrady and R. S. Tobias. J . Anaer. Chern. Soe., 1965, 87, 1909; ( b )lS6 C. C . Addison and W. B. Xinipson, J . Chern. SOC., 1965, 598.lS7 C. J. Wilkins and H. M. Haendler, J. Chem. SOC., 1965, 31i4.lS8 R. 0. Ragsdale and B. B. Stewart, Inorg. Chem., 1965, 4, 740.lS9 P. A. W. Dean and D. F. Evans, Proc. Chem. SOC., 1964, 407.* O 0 ( a ) I.R. Beattie and L. Rule, J . Chent. SOC., 1965, 2995; ( b ) I. R. Besttie, R.201 ( a ) P. Hunt and D. P. N. Satchell, J . Chena. SOC., 1964, 5437; (b) D. P. N. Satchel1202 Y. Kawasaki and R. Okawara, J . Inorg. Nuclear Chem., 1965, 27, 1168.go3 K. Dehnicke, Chent. Ber., 1965, 98, 280, 290.1379.2275.Re. S. Tobias and C. E. Freidline, Inorg. Chern., 1965, 4, 215,Hulme, and L. Rule, ibid., p. 1581.and J. L. Wardell, Tram. Paraday SOC., 1965, 61, 1132150 INORGANIC CHEMISTRYnumbers of chloride ions in aqueous solution.2w The triphenylplumbyl-methane derivatives CR,, CHR,, and CH2R2, (R = Ph,Pb), have beenobtained 205 from the appropriate chloromethane and LiPbPh,. The newcompounds Ph3(CGF,)Pb, Me,(C,F,)Pb, and (C,F',),Pb have been preparedfrom pentafluorophenyl magnesium halides and R,PbCl (R = Ph,Me) andPbC1, respectively.206Oxidation of ammonia by alkaline hypobromite 2 ~ 0 7 ~yields predominantly the bromo-amines NH,Br and NHBr, ; nitrogentribromide is formed preferentially at pH < 6.Di-imide N2H2 has beenidentified 207b as an intermediate in the alkaline decomposition of NH2C1,through its hydrogenating action on multiple bonds, and organic chloro-amines have been converted 207c into the corresponding azides R2N*N, andthiocyanates R,N(SCN)3-, (n = 0-2). The reaction between iodine andammonia has been re-investigated.20idFor steric reasons, the symmetry of (CF,) ,N*N( CF,), approximates toD2d, so enhancing z-bonding between the nitrogen atoms, and shorteningthe N-N bond.208 Methylation of the dilithio-derivative 209 of 1,2-bis(trime-thylsily1)hydraxine gives both the 1,2-dhethyl derivative and the isomeric(Me,Si),N*NMe,.Azidocarbodinitrile NCN.NCN has been prepared by the pyrolysis ofcyanogen azide, and may exhibit cis-trans-isomerism ;210 the vibrationalspectra of CF2N2 are interpreted 211 as evidence for the cyclic structure (17).Group V.-Nitrogen./c\F, N=N (17)On the basis of infrared spectra, co-ordination of the azides R3MN3(R = Me,Ph; M = Si,Ge,Sn) to Lewis acids 212 is believed to take placethrough the nitrogen atom attached t,o M.Nitramide has been prepared by the ammonolysis of nitrogen p e n t ~ x i d e .~ ~ ~Bis(trifluoromethy1)hydroxylamine has been oxidised 214 to the new, purple,gaseous radical bis( trifluoromethyl) nitroxide (CF,),NO, which is stable toalkalis.Dimerisation occurs on solidification. The adduct of diethylamine2 0 4 G. P. Haight, jun., and J. R. Peterson, Inorg. Chem., 1966, 4, 1073.205 L. C. Williamsens and G. J. M. Van der Kerk, Bec. Trau. chim., 1965, 84, 43.206 D. E. Fenton and A. G. Massey, J . Inorg. Nzcclear Chena., 1965, 27, 329.207 ( a ) H. Galal-Gorchev and J. C. Morris, Inorg. Chm., 1965, 4, 899; ( b ) E. Schmitz,R. Ohme, and Q. Ihzakiewicz, 2. anorg. Chem., 1965, 339, 44; (c) H. Bock and K.-L.Kompa, ibid., 1964, 332,238; E. Allenstein and E. Lattewitz, ibid., 333, 1; (d) J. Janderand U. Engelhardt, ibid., 1965, 339, -225.208 L. S. Bartell and H. K. Higgmbotham, Inorg. Chena., 1965, 4, 1346.209 R.E. Bailey and R. West, J . Arner. Chem. Xoc., 1964, 86, 5369.211 C. W. Bjork, N. C. Craig, R. A. Mitsch, and J. Overend, J . Amer. Chem. Soc.,212 J. S . Thayer and R. West, Inorg. Chem., 1965, 4, 114.213 P. Vast and J. Heubel, Compt. rend., 1965, 260, 5799.211 W. D. Blackley and R. R. Reinhard, J . Arner. Chem. SOC., 1965, 87, 802.F. D. Marsh and M. E. Hermcs, J . Amer. Chem. Soc., 1965, 87, 1819.1965. 87, 1186JOHNSON, PADDOCK AND M7ARE: THE TYPICAL ELEMENTS 151with nitric oxide decomposes in oxygen, the reaction being formulated as :215[Et2NH,]+[Et2N*N,0,]- + +02 -+ [Et2NH2]+N0,- + Et,N*NO.Nitrosonium nitrate NOSNO,- has been isolated by the oxidation of NO a t79*K, and it is concluded 216 that the stabilities of the isomers of N,O, de-crease in the order 0,N*N02 > NO+N03- > ONO*NO,.A detailed mole-cular-orbital study of O,N*NO suggests that the formation of the centralBond involves delocalisation of z-electrons from oxygen into an antibondingN-N 0rbital.21~ Dinitrogen tetroxide removes some of the water cleanlyand rapidly from salt hydrates;2l8 e.g., KAl(S0,),,12H20 loses 6H20. Theexistence of the complex HN0,,2HC1O4 has been confirmed by therma,l andX-ray analysi~.~1~The difluoramicle ion decomposes in alkaline solution :22*(ferric ions promote the formation of tetmfluorohydrazine N2P,). Similarly,the complexes formed 221 by difluoramine with alkali-metal fluorides ME'(M = K,Rb,Cs) decompose Z2Ia to difluorodiazine :2MF + 2HNF, --+ 2MHF, + N2F2.Fluorination of sodium azide gives a mixture of cis- and trans-difluoro-diazine;222u a good yield of the tmns-isomer is obtained by decomposition of3??,F, + 2AlC1, + 3N2F, + 3C1, + 2A1F3.cis-Difluorodiazine forms a 1 : 1 complex with ASP, which is formulated223aionically as the hexafluoroarsenate of the hitherto unrecognised cationN,F+ ; the trans-isomer does not react.cis-Difluorodiazine also bothdeoxygenates and fluorinates oxides and oxyflu~rides.~~~~ Chlorodifluora-mine ClMF, has been prepared by the chlorination of HNF, in the presenceof potassium or rubidium and by the combined action of fluorineand chlorine on sodium a ~ i d e . , , ~ ~ Arsenic triffuoridc is displaced by N2F4from its complex with SbF,, to form22z NE,,SbF,. The chemistry of thefluorides of nitrogen hams been reviewed.226Difluorophosphine has been prepared 227 by the reactionNF2- + F- 4- &N,F,N2F4 :22ZbPhosphorus.PF21 + HI + 2Hg + PF2H + Hg,I,.215 R.0. Ragsdale, B. R. Karstotter, and R. S. Drago, Inorg. Chem, 1965, 4, 420.216 L. Parts and J. T. Miller, jun., J . Chenz. Phys., 1965, 43, 136.217 R. D. Brown and R. D. Harcourt, Austral. J . Chem., 1965, 18, 1115.218 C. C. Addison and D. J. Chapman, J . Chem. Soc., 1965, 819.219 A. Potier, J. Potier, and D. Rousselet, Compt. rend., 1965, 261, 4115.220 K. J. Martin, J. Amer. Chem. SOC., 1965, 87, 394.221 (a) E. A. Lawton, D. Pilipovich, and R. D. Wilson, Inorg. Chem., 1965, 4, 118;(b) H. E. Dubb, R. C. Greenough, and E. C. Curtis, ibid., p. 648.222 (a) A. V. Pankratov, 0.M. Sokolov, and N. I. Savenkova, Rws. J . Inorg. Chem.,1964, 9, 1095; (b) G. L. Hurst and S. I. Khayat, J . Amer. Chem. SOC., 1965, 87, 1620.223 (a) D. Moy and A. R. Young, jun., J . Amer. Chem. SOC., 1965, 87, 1889; (b) M.Lugtig, Inorg. Chem., 1965, 4, 104.2 2 4 ( a ) 137. C. Firth, jun., Inorg. Chem., 1965, 4, 254; (b) A. V. Pankratov and 0. 0.Zherebina, Rws. J . Inorg. Chem., 1964, 9, 1096.225 J. K. Ruff, J . Amer. Chem. SOC., 1965, 87, 1140.226 C. B. Colburn, Endeavour, 1965, 24, '138.227 R. N. Rudolph and R. W. Parry, Inorg. Chem., 1965, 4, 1339152 IN 0 RC AN I C CH E MI S TRYOrganophosphines containing pentafluorophenyl groups have been syn-thesised ;120, 228 alkylphosphines carrying dialkylamidogroups are quarter-nised only a t phosphorus.229 Ligand exchange with PCl, takes place morerapidly with P(NCS), than with P(NCO),; exchange is much slower betweenthe corresponding oxy-~ompounds.~~0 Tetrachlorodiphosphine P,Cl, hasthe trans-structure in the solid, liquid, and vapour phases,231 in contrast toP21,, which is tmns in the solid, but gauche in solution.The latter compoundreacts with bromine and with BBr, to give PBrI, and P,I,,2BBr3 respec-ti~ely.~32 The diphosphines and diarsines R,(P,As), are cleaved to giveR ,( P,As)H by lithium aluminium h~dride,~33" and linear phosphines con-taining up to four phosphorus atoms are formed when the ring structure ofEt,P, is opened by an alkali metal or by phenyl-lifhi~m.~33b The crystalstructures of pentameric 234a and hexameric234b phosphobenzene (PhP),,( n = 5,6), have been determined, the molecules containing rings of five andsix phosphorus atoms respectively.Two more crystal modifications ofphosphobenzene are Phosphobenzene forms 1 : 1 and 1 : 2 com-plexes with cuprous halides 235a and the compounds 235b (PhP),(Mo,W)( CO),with the metal liexacarbonyls. The preparati0n,~~5c by the same method, of(PhP),M(CO),, (M = Cr,Mo,W) and the related compounds of arsenic,(PhAs),Mo(CO), and (PhAs),[Mo(CO),],, has been reported; cis-substitu-tion is indicated by their infrared spectra. Nickel carbonyl 235b gives(PhP),Ni(CO), ; ring expan~ion2~5b or contraction 2sQc may occur in the for-mation of some of these derivatives. The heats of reaction of arylphosphineswith diborane and the dipole moments of the boranes so formed are consistentwith some B-P pc- dn bonding.236 Dimeric and trimeric phosphinoborines(R,PBR',),,, (R = Et,Bu; R' = F,CI,Br,Pr) are formedz3' by eliminationof Me3SiR' from the borane adducts (Me,SiPR,)BR',. Halogens displacehydrogen from the BH, groups of P- hexaphenylcyclotriphosphinoborine.238The new phosphinoamines RN[P(CF,),],, (R = Me,H) have been pre-pared by condensation of (CF3),PC1 and (CF,),PNHR with trimethylamine.The sodium salt NaN[P(CF,),], is converted239 by (CF3),PC1 into the tertiaryphosphinoamine N[P(CF,) ,I3.The elements of hydrogen fluoride are easilyeliminated from compounds containing the > CF-PH- group, and reactionof the resulting phospha-alkene > C = P- or > COP- with (e.g.) ammonia228 M.Fild, 0. Glemser, and I. Hollenberg, Natzwuhs., 1965, 52, 590.22s 9. H. Cowley and R. P. Pinnell, J. Amer. Chent. SOC., 1965, 87, 4454; cf. A. €3.230 E. Fluck, F. L. Goldmann, and K. D. Rumpler, 2. anorg. Chern., 1965, 338, 5%;231 S. G. Frankiss and F. A. Miller, Spectrochim. Acta, 1965, 21, 1235.232 A. H. Cowley and S. T. Cohen, Inorg. Chern., 1965, 4, 1200, 1221.233 (a) K. Issleib, A. Tzchach, and R. Schwartzer, 2. anorg. Chenz., 1965, 338, 141;{b) E. Fluck and K. Issleib, ibid., 1965, 339, 274.234 (a) J. J. Daly, J . Chem. SOC., 1964, 6147; ( b ) ibid., 1965, 4789; (c) J. J. Daly andL. Maier, Nature, 1965, 208, 383.235 (a) D. G. Hicks and J. A. Dean, Chem. Comna., 1965, 171; (b) H. G. Ang, J. S.Shannon, and B.0. West, ibid., p. 10; (c) G. W. A. Fowles and D. I<. Jenkins, ibid.,p. 61.236 M. A. Frisch, H. G, Heal, H. Mackle, and I. 0. Madden, J . Chern. SOC., 1965, 899.23' H. Noth and W. Schragle, Chem. Ber., 1965, 98, 352.238 W. Gee, J. B. Holden, R. A. Shaw, and B. C. Smith, J . Chena. SOC., 1965 3171.23s A. B. Burg and J. Heners, J. Ainer. Chenz. SOC., 1965, 87, 3092.- +Burg and P. J. Slota, ibid., 1958, 80, 1107.E. Fluck, H. Binder, and F. L. Goldmann, ibid., p. 58JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 153affords a new route into phosphorus-nitrogen ~hemistry.~40niethy1)phosphinyl chloride has been prepared 241 by the reactionsBis( trifluoro-NO, Me,NH HCI(CF,),P + (CF,),PO -+ (CF,),PO*NMe, -+ (CF,),PO-CI.A bicyclic hydrazodiphosphine (18) has been prepared by the transamina-tion of tris(dimethy1amino)phosphine with 1,2-dimethylhydrazine hydro-chloride.242 Monophosphazenes RN:PPh(NHR) and some (PhP), a.reproduced in the pyrolysis of di( alkylamino)phenylph~sphines.~~~Aminosilanes and silazanes are useful in the synthesis of phosphorus-nitrogen compounds.The difunctional heptamethyldisilazane (Me,Si) ,NMegives the four-membered ring (19) with PCl,, whereas the trimeric and te-PhPh\ ,P=N,Jph 1NCLP-NMe1 1MeN-PCt(1 9)trameric compounds (EtN-PC1) ,, are obtained if N-ethylhexamethyldisi-lazane is used.244 A similar reaction with phosphorus pentafiuoride 24ij yieldsthe diazadiphosphetidine (MeN*PF,) ; the chlorine stoms in (PhN:PCI,)can be replaced successively by dialkylarnido-gr~ups.~~~ Several new com-pounds containing -N:PC13 groups, especially derivatives of hydrazine, havebeen obtained in Kirsanov reactions.247Silazanes have also been used248 in the preparation of phosphonitriles, e.g.,(Me,Si),NH CsFPh,PF, - [Ph,PF*NH], -+ [Ph,PN],.- HFThe pyrolysis of aminophosphoniuw salts is also an increasingly usefulsynthetic method.Dialkylchlorophosphines R ,PCl, (R = Me,Et,Bu,) reactwith a mixture of ammonia and chloramine to form the salts [R,P(NH,),]+Cl-,[R2P(NH2)*N*P(NH2)R2]+C1-, which give a mixture of alkylphosphonitriles(R2PN)3,4 on pyrolysis.249 Phenylphosphonitriles (NPPh2)3, are obtainedfrom a related P-N-P intermediate,250a from 250b [Ph2P(NH2)C1]+PC16-, andby heating dimethylhydrazinodiphenylphosphine.250c Reaction of sodium240 H.Goldwhite, R. N. Haszeldine, and D. G. Rowsell, Chem. Comm., 1965, 83.241A. B. Burg and A. J. Sarkis, J . Amer. Chem. SOC., 1965, 87, 238.212 D. S. Payne, H. Noth, and G. Henniger, Chem. Comm., 1965, 327.243 A. P. Lane and D. S . Payne, Proc. Chem. Soc., 1964, 403.244 E. W. Abel, D. A. Armitage, and G. R. Willey, J . Chem. SOC., 1965, 57.245 R. Schmutzler, Chem. Comm., 1965, 19.z4sV. Gutmann, C. Kemenater, and K. Utvary, Manatsh., 1965, 96, 836.247 M. Becke-Goehring, W. Hanbold, and H. P. Latscha, 2. anorg. Chem., 1964,333, 120; M. Becke-Goehring and W. Weber, ibid., p. 128; H.-P. Latscha, W. Hanbold,and M. Becke-Goehring, ibid., 1965, 339, 82; M. Becke-Goehring and W. Weber, ibid.,p. 281.24a R.Schmutzler, 2. Naturforsch., 1964, lob, 1101.249 H. H. Sisler and S. E. Frazier, Inorg. Chem., 1965, 4, 1204.250 ( a ) I. T. Gilson and H. H. Sisler, Inorg. Chem., 1965, 4, 273; (b) M. Becke-Goehring and W. Hanbold, 2. anorg. Chem., 1965, 338, 305; (c) M. Winyall and R. H.Sisler, Inorg. Chenz., 1965, 4, 655.154 INORGANIC CHEMISTRYazide with a mixture of Ph2PC1 and PhPC1, gives mainly the tetraphos-phonitrile (20, R = Cl); other derivatives (R = O€€,OEt,OPh) have beenreported, and diols give polymeric products.251 A mixture of chlorophos-phazenes is obtained 252 by the action of chlorine on phosphorus thionitrideThe rate of the reaction of hexachlorocyclotriphosphazene with piperidinefollows mixed second- and third-order kinetics, and is catalysed by tributy-lamine.253 A geminal substitution pattern has been established for thereaction with t - b u t ~ l a m i n e ; ~ ~ ~ with dimethylamine, both geminal and cis-and trans -non- g eminal subst it u tion occurs.255 Disubst i t u t ion of non- geminalmethylamino-groups occurs exclusively in the cis-orientation ; some of thegeminal derivative is also formed.256 The Friedel-Crafts phenylation ofN3P,C1, is accelerated if formation of the conjugate acid of the phenylderivative is prevented;257 unequal ring bond lengths have been found 258 in2,2-diphenyl-4,4,6,6-tetrachlorocyclotriphosphazatriene. Thephenylationofalkylaminophosphonitriles takes place n~n-geminally,~~~ and cis-truns-isomerisation of non-geminal chloroalkylamino- 259a and chlorophenyl259bderivatives is catalysed by AlCl,.NsP3Cl6-n (Oh),(h = Ph,p-BrC6Ha; n = 1-6) takes place non-geminally;260a,b the cis-cis-trans-configuration has been established260u for N,P,Cl,( OPh),.Thespiro-derivative tris-(o-pheny1enedioxy)phosphonitrile trimer forms crystal-line inclusion compounds with organic solvents.261 Replacement of some orall of the chlorine atoms in N3P3C16 by ally1amine,262u alkylamines,262balcohols,262C d i ~ l s , ~ ~ ~ ~ thiocyanate,262e and thiourea 262t has been reported.Hexachlorotriphosphazene forms complexes with pyridine and stannicchloride,263@ and with aminopho~phazenes.~6~b On spectroscopic evidence,264the planar structure of N,P,C16 in solution is distorted in the crystal, inagreement with the detailed structure determinations.Effects of the solventPNS),.Substitution in the series25lD. L. Herring and C. M. Douglas, Imrg. Chem., 1965, 4, 1012.252 S. N. Nabi, S . N. Nabi, and N. K. Das, J . Chem. Sac., 1965, 3857.26s B. Capon, K. Hills, and R. A. Shaw, J . Chem. SOC., 1965, 4059.264 S. K. Das, R. Keat, R. A. Shaw, and B. C. Smith, J . Chewa. SOC., 1965, 5032.266 H. Koopman, F. J. Spruit, F. Van Deursen and J. Bakker, Rec. Trav. chim.,256 C. T. Ford, F. E. Dickson, and I. I. Bezman, Inorg. Chem., 1965, 4, 890.257 E. T. McBee, K. Okuhara, and C. J. Morton, Inorg. Chem., 1965, 4, 1672.265 N. V. Mani, F. R. Ahmed, and W. H. Barnes, Acta Cryst., 1965, 19, 693.259 (a) R. Keat, R. A. Shaw, and C. Stratton, J . Chem. Soc., 1965, 2223; ( b ) B.Grushkin, M.G. Sanchez, M. V. Ernest, J. L. McClanahan, G. E. Ashby, and R. G.Rice, Inorcq. Chern., 1966, 4, 1538.260 (a) C. T. Ford, F. E. Dickson, and I. I. Bezman, Inorq. Chem., 1965, 4, 419;( b ) D. Dell, B. W. Fitzsimmons, and R. A. Shaw, J . Chem. SOC., 1965, 4070; (c) V. B.Tolstoguzov, V. V. Pisarcuko, and V. V. Kireev, Raw. J . Inorg. Chm., 1965, 10, 382.261H. R. Allcock and L. A. Siegel, J . Amer. Chem. SOC., 1964, 88, 5140.262 (a) H. R. Allcock, P. S . Forgone, and K. J. Valan, J . Org. Chem., 1966, 30,947; j b ) A. F. Nikolaev and Er-Ten Wan, J . Gen. Chem. (U.S.S.R.), 1964, 34, 1843;(c) ibzd., p. 1846; ( d ) S. M. Zhivukhin and V. V. Kireev, ibid., p. 3169; ( e ) N. I. Shvetsov,K. A. Nuridzanyan, A. Ya. Yakubovich, and F.F. Sukhov, ibid., p. 3874; (f) A. V.Babaeva and G. V. Derbisher, Rzcss. J . Inorg. Chm., 1965, 10, 156.2sa (a) S. M. Zhivukhin and V. V. Kireev, Rzcss. J. Inorg. Chem., 1964, 9, 1439;(b) S . K. Das, R. A. S h w , and B. C. Smith, Chm. Comm., 1965, 176.264 I. C. Hisatsune, Spectrochim. Acta, 1965, 21, 1899.1965, 84, 341; R. Keat and R. A. Shaw, J . Chem. Soc., 1965, 2215JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 156on the spectra of (NPCl,),,, have been determined,265 and new vapour-pressure results presented for crystals of these molecules and for 266 (NPBr2)3.There is little difference between the basicities of corresponding members ofthe two series ( PY ,) 3,4, (Y = OR,SR ; R = alkyl,aryl), though theteOramer is often the slightly stronger base.267Treatment of N,P,CI, with phenylmagnesium bromide results (in part)in ring contraction, the compound (21) being formed.268 Configurationsa’’ %ahave been assigned to three out of a possible four isomeric phenyl-N-dimethylaminotetraphosphonitriles.2~~ Decabromopentaphosphonitrile 270(NPBr,), and the medium-ring derivatives 271 (NPY,)5-8, (Y = OMe,OPh,OCH,CF3,NMe2) have been prepared, and features of their proton magneticresonance spectra discussed.The molecular structure of [NP(NMe2),16 hassome similarity to that of the tetrameric chloride, and large angles a t bothring and exocyclic nitrogen atoms suggest appreciable electron release tophosphor~s.~7~ The rate of exchange of s6C1- with the chlorophosphoni-triles (NPCI,),, (n = 3-45) is of the first order in each reactant; the re-activity, which decreases in the order n = 4 > 5 > 6 > 3, is not whollyexplicable in terms of ring flexibility.273 The tetrameric chloride is alsomore reactive than the trimer to substitution by a m i n e ~ .~ ~ ~ The heats ofpolymerisation of the chlorides (NPCl,) indicate that stability increaseswith ring size.274The six-membered rings in the trimetaphosphimate ion275a [NH-PO,],S-and in the related cyclotriphosphazane 275b [MeN*PO-OMe], are found to havechair, and slightly twisted boat forms respectively ; the tetrametaphosphi-mate ion [NlEcP02],4- is t ~ b - s h a p e d , ~ ~ ~ ~ with approximate 4 symmetry.Ring bond-lengths and the angles a t the ring nitrogen atoms in all threemolecules suggest the presence of n-bonding in the ring, arising from thedelocalisation of the nitrogen lone-pairs.266 N.B. Jurniski, C. C. Thompson, jun., and P. A. D. de Maine, J . Inorg. NucJear266 S. Cotson and K. A. Eodd, J. Inorg. NzlcZeur Chem., 1965, 27, 335.207 D. Fealrins, W. A. Last, N. Neemuchwala, and R. A. Shaw, J . Chem. SOC., 1965,268 M. Biddlcstone and R. A. Shaw, Chem. Comm., 1965, 205.269 J. H. Smalley, F. E. Dickson, and I. I. Beeman, Imrg. Cltem., 1964, 3,G. E. Coxon, D. B. Sowerby, and G. C . Tranter, J . Chem. SOC., 1965, 5697.271 G. Allen, D. J. Oldfield, N. L. Paddock, F. Rallo, J. Serregi, and S. M. Todd,87a A. J. Wagner and A. Vos, Rec. Trav. chim., 1965, 84, 603.273 D. B. Sowerby, J . Chem. Soc., 1965, 1396.w4 J.K. Jacques, M. F. Mole, and N. L. Paddock, J. Chem. SOC., 1965, 2112.*76 (a) R. Olthof, T. Migchelsen, and A. Vos, Actu Cqst., 1965, 19, 596; ( b ) G. B.Ansell and G. J. Bullen, Chem. Comm., 1965, 493; (c) T. Migchelsen, R. Olthof, and A.Vos, Acta Cryst., 1965, 19, 603.Ohm., 1965, 27, 1571.2804.1780.Chem. and Ind., 1965, 1032156 INORUANIC CHEMISTRYTriphenylphosphine oxide is reduced to the phosphine by organo-boranes ;276a the corresponding reaction with trichlorosilane is stereo-specifi~.~~6* The conditions for the effective preparation of the oxychloridesP,OZn- lC1,+ have been investigated,277 and the synthesis of oxide-halides,including those of phosphorus, has been reviewed.27s The structures ofP,O, and P,Og are derived from that of P,Ol, by the omission of terminaloxygen atoms.279The specific importance of the cation in determining the configurationof the anion in p-M2P207 (M = Mg,Zn) has been emphasised;280a in themagnesium salt, the anion is statistically linear280* above 68".A study,(by 31P magnetic resona.nce spectroscopy), of the interaction of cations withlinear and cyclic phosphates, favours electrostatic binding at fixed sites.281aThe stability of calcium complexes of polyphosphate ions increases withchain length up to about the heptaphosphate ;281b the hydrolysis of thepentaphosphate ion to trimetaphosphate and orthophosphate is catalysedby cupric chelate complexes.281c The cyclic trimetaphosphate ion (P309)3-is cleaved reversibly by ammonia, methylamine, or fluoride ion.282 Thehexametaphosphate ion (P6019)6-, which is resistant to hydrolysis,383a ischair-shaped, with C2h symmetry.283b The tetramethoxyphosphonium ionhas been isolated as its hexachloroantimonate.2s4 The configuration of thefive oxygen atoms bound to phosphorus in the penta-oxyphosphorane formedby the addition of phenanthrenequinone to tri-isopropyl phosphite isapproximately trigonal bip~ramidal.~~5Tetraphosphorus heptasulphide P,S7 loses sulphur preferentially from theterminal positions, with slight shortening of the P-P bond.2*6 The structureof tetraphosphorus triselenide287 is similar to that of P,S,.Nuclear mag-netic resonance studies288a of tetramethyldiphosphine disulphide Me4P,S sug-gest that the two phosphorus atoms are joined through sulphur, though a bandbelieved to correspond to P-P stretching has been found in a re-determinationof the Rainan spectrum of this, and related compounds.288b In the newthiotrifluoromethylphosphines (CF,),PSR, [R = H, Me, But, P(CF,),] and276 ( a ) R.Koster and Y. Morita, Angew. Chem., 1965, 77, 589; (b) L. Horner andW. D. Balzer, Tetrahedron Letters, 1965, 1157.277 (a) G. Muller-Schiedmayer and H. Harnisch, 2. anorg. Chem., 1964, 333, 260;(b) K. Dehnicke, Chem. Ber., 1965, 97, 3358.278K. Dehnicke, Angew. Chem., 1965, 77, 22.279 K. H. Jost, Ada Cryst., 1964, 17, 1593; D. Heinz, 2. anorg. Chem., 1965, 336,137.380 ( a ) C. Calvo, Canad. J . Chm., 1965, 43, 1139, 1147; (b) A. N. Lazarev and T. F.Tenisheva, Bull. Acad. Sci.U.S.S.R., 1964, 224; (cf. Refs. 165c, d.).281 (a) M. M. Crutchfield and R. R. Irani, J . Amer. Chem. SOC., 1965, 87, 2815.( b ) M. Miura and Y. bfonguchi, BUZZ. Chem. SOC. Japan, 1964, 37, 1522; (c) ibid., 1965,38, 678.282 W. Feldmann, 2. Chem., 1965, 5 , 26; 2. aiwrg. Chem., 1965, 338, 235.zs3 (a) E. J. Griffith and R. L. Buxton, ITnorg. Chem., 1965, 4, 549; (b) K. H. Jost,Acta Cryst., 1965, 19, 555.284 J. S. Cohen, Tetrahedron Letters, 1965, 3491.W. C. Hamilton, 8. J. La Placa, and F. Remirez, J . Anaer. Chm. Soc., 1965,87, 127.286 D. T. Dixon, F. W. B. Einstein, and B. R. Penfold, Acta Cryst., 1965, 18, 221.287 K. Irgolic, R. A. Zingaro, and M. Kudchdker, Inorg. Chem., 1965, 4, 1421.288 (a) R. K. Harris and R. Q. Hayter, Canad. J.Chem., 1964,42,2282; (b) H. Gerding,D. H. Zijp, F. N. Hoop, G. Blasse, and P. J. Christen, Rec. Truv. chim., 1965, 84,1274JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 157CF,P(SMe),, the electronegative CF, groups prevent the occurrence of theArbuzov rearrangement. Unlike the corresponding oxygen compound, thethiophosphinous acid (CF,)&'SH has some tendency to condense to[(CF,),PJ,S, a-bonds from phosphorus to sulphur being weaker than thoseto 0xygen.28~PCW, and of 290b CCl,*PF,X, (X = Cl,Br) hasbeen described. Axial P-F bonds are found 291a~* in the molecules PCl,F,PCl,F,, and PCIJ?,, and2Qb in MePF,; some n-character is suggested for theaxial bonds on the basis of fQF magnetic resonance spectra,2@la The vibra-tional spectra282 of the methyl chlmphosphoranes PMe,cI,, show thatthese cornpun& am phosphonhim dts (PMe,CI,,J+Cl- (la = 14).Alkyl- or axyl-di~la~ot~uorophosphoranw remange thus 99,2RPF8*NR't + WPF(NR',)J+ IRPFJ-,.The complexw formed by PF, with a number of donor molecules2" aresimilar to analogous compounds of BF3.Substitution of fluorine in PF6 byalkyl and asyl groups reduces acceptor strength drastically, although theRP'E5- ion his been identified.2s5 The 1 : 1 adduct of NOT and PhPF,reaots with secondary amines as follows:-NOF*PhPF, + ZR@ + RP-NO + JR&H,]+[PhPF5]-whioh auggesb an ionic formulation NO+PhPF,- for the initial adduct.296Ar8efik. The (new) alkoxybis( tfiuorornethy1)arsines 2@7 (CF,)&OR,(R = Me,But), do not undergo the Arbuzov rearrangement, owing to thelow basicity of arsenic; on the other hand, As-0 n-bonding is weak, andallows the formation of an adduct with BF,.The reaction of As20, withSiF, at high temperatures can be used2Q* to prepare AsF,. In contrast tothe reaction with PCl,, only two chlorine atoms in AsC1, am replaced byamin0silanet3.~~~ It has been shown by nuclear magnetio resonance apectro-scopy that reorganisation reactions in solutions of As203 in As(OMe), orAs(NMe,), occur rapidly; labile polymeric species AsC1S-n(NMe)nf2 areformed in the AsC1,-As,(NMe), s~~stem.~99bMixed crystals (As,P),O,, isostructural with As2O6, have been obtainedby evaporation of the mixed acids?O0 Thallous tetrameta-arsenate isisomorphous with the corresponding phosphate.301The anion of empirical composition ASFIO-, previously believed to beThe preparation of**BA.B. Burg and K. Gtosling, J . A ~ T . Chem. Soc., 1965, 87, 2113.*SO (a) R. P. Carter, jun., and R. R. Holmes, I m g . Chem., 1965, 4, 738; (b) J. F.Nixon, J . Inorg. Nuckmr Chm., 1965, 2'7, 1281.**a (a) R. R. Hohes, R. P. Carter, jun., and a. E. Peterson, Inmy. Cbm., 1964,8,1748; (b) R. R. Holmes andR. P. Cater, jun.,J. C k . Plqp., 1965,48,1645; (0) A. J.Downa and R. Schmutzler, 8pectpochim. A&, 1966, €31, 1927.n@a R. Baumgiirtner, W. Sawodny, aad J. Coubeau, 2. a w g . Ohm., 1964,888,171.a@*R. Schmutzler, J . Chm. Soc., 1966, 5630.a@41. K. Gregor, Chem. a d I d . , 1966, 385.E. L. Muetterties and W. Mahler, Inorg. Chem., 1965, 4, 119.**@R.Schrnutzler and (3. 8. M d y , I w g . Cham., 1965, 4, 191.2B7 A. B. Burg and J. Singh, J . Amr. Ohm. Soc., 1965, 87, 1213.**eK. 0. Chris& and A. E. Pavlath, J . C h . Soc., 1966, 827.a@B (a) K. Moedritzer and J. R. Van W~lzer, I w g . Cbm., 1965, 4, 893; (b) J. R.a*oA. Winkler and E. Thilo, 2. anmg. Cham., 1965, 889, 71.801 K. Dosbl and V. Kocman, 2. Chem., 1965, 5, 344.Van Wazer K. Moedritzer and M. D. Ransch, J . Chem. Phys., 1965, 42, 3302158 INORUANIO CHEMISTRYtrimeric, is now f0rmulated3~~ as a, h e r (22). Trimethyl arsenafe reactswith n-propylamine to give 303 the pentamethyl ester As(OMe),. The threenew compounds Ph3AsBr,, PhAsIBr,, and Ph3As13Br ionise as halogeno-triphenylarsonium trihalides in methyl ~yanide,~M and the formulation ofhF3C12 as [AsCl,]$-[AsE’,]- has been verified by vibrational spectroscopy.305Antimony and Bismuth.Antimony trichloride, which can be preparedsimply306 by heating Sb2S3 with anhydrous CuCl,, is a weaker acceptor toamines than are stannic or zinc chlorides.307Tetrameric imido-compounds (RNeSbY),, (Y = 1,OEt) of antimony(m)are obtainedSo8 by reaction of SbY, with alkylamines; aromatic amines givethe imides Sb,(NR),. A crystal structure determination shows that potas-sium antimony1 tartrate is a derivative of the antimonite ion [Sb(OH),]-, themetal being co-ordinated by four oxygen atoms at the corners of a deformedtrigonal bipyramid, one equatorial position being occupied by an unsharedpair of electrons.309a In ,8-Sb204, the SbIn atoms have a similar environ-ment, the SbV atoms being octahedrally co-ordinated.In conjunction with hydrogen fl~oride,~lO SbF, is a stronger acid thanBF,.Ligand exchange in the SbF,-SbCl, system is rapid, but the equili-brium is complicated by polymerisation and i ~ n i s a t i o n . ~ ~ ~ On the basis of itsRaman spectra, SbFCl, is found to have the trigonal bipyramidal shape insolution, but to be ionic, [SbCl,]+F-, in the crystal.31a Binuclear fluoroanti-monates [F,Sb(02)SbFJ2- [cf. (22)] and [F,SbOSbF,]- are formed bythermal condensation of hydroxyfl~oroantimonates.~~~ Alkali thiocyanato-bismuthates(m) containing the ions [Bi(SCN),]-, [Bi(SCN),I3- have beenprepared. 314The superoxide ion 0,- has been obtained by theelectrolytic reduction of 0 in aprotic solvents.316 Tetramethylammoniumsuperoxide has been ~repared.~le The single and double electron affinities ofthe oxygen molecule have been deduced from the heats of formation andlattice energies of alkali-metal superoxides and peroxides.The covalentbond energy in 022- is negative, (-95 kcal. mole-l), the crystal beingstabilised mainly by the lattice energ~.~17 Rubidium peroxide is completelydissociated318 into the ions Rbf, 022-, in solution in LiN03-KNOs. Theradical ion formulation [(HO),BO-O]-‘ is suggested, to account for theGroup VI.-Oxygen.L. Kolditz, B. Nussbucker, and M. Schrbnherr, 2. anorg. Chem., 1965, 335, 189.D. Hass, 2. unorg. Chem., 1966, 335, 297.SOPA. D. Beveridge and (3. S. Harris, J . Chem. SOC., 1964, 6076.J.Weidlein and I(. Dehnicke, 2. anorg. Chem., 1965, 337, 113.$06 M. H. Khundker and S. S. M. A. Khorasani, 2. unorg. Chem., 1965, 334, 329.a07 D. P. N. Satchell and J. R. Wardell, J . Chem. SOC., 1965, 739.so8D. Ham, 2. amrg, Chem., 1964, 332, 287.809 (a) D. Grdenio and B. Kamenar, Acta Cryat., 1965, 19, 197; (b) D. Rogers ands10 G. A. Olah, J . Amer. Chena. Soc., 1965, 87, 1103.sll N. E. Aubrey and J. R. Van Wazer, J . Inorg. Nuclear Chem., 1965, 27, 1761.s13 K. Dehnicke and J. Weidlein, Chm. Ber., 1965, 98, 1087.813 L. Kolditz and B, Nussbucker, 2. anorg. G?mn., 1965, 337, 191.8I4A. Cyg$nski, Rocznilcd C M . , 1965, 39, 193.81s M. E. Peover and B. S. White, Chem. Comm., 1965, 183; W. Slough, iba., p. 420.*l*A. D. McElroy and J. S. Hashman, I w g .Chem., 1964, 3, 1798.n7L. A. D’Orazio and R. H. Wood, J . Phys. Chem., 1965, 89, 2550, 2658.318 A. Chr6tien and P. Allarnagny, Cmpt en&., 1965, 260, 1425.A. C. Skapski, Proc. Chem. SOC., 1964, 400JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 159paramagnetic properties of certain pero~yborates.~l9 The visible spectraof all the oxygen fluorides a t present known, OnF2, (n = 1 4 ) , have beenreported.320Subphur. The S, molecules in monoclinic (#?)-sulphur are crown-shaped,as they are in the rhombic a-m0dification.3~1 So are (a) cyclo-heptasul-phur imide,522a S,KK, which is obtained in high yield in the reduction ofS4N4 or S4N3C1 by hydra~ine;3~2~ (b) cyclohexasulphur 1,3-di-imide, (pro-duced in the same reaction) ;322c and (c) the 1,4-i~omer.~,,~ Cyclopenta-thiotri-imine, S(N,H),, probably the 1,3,5-isorner, has been isolated,323 andNN’-dimethylcyclohexasulphur 1,5-di-imide, S,(NMe) ,, has been preparedfrom S 3Cl and methylamine .324Theproton chemical shifts of the sulphanes H,S,, (x = 1-6), are stronglydependent on chain length.326 Sulphanes react with olefhic compounds oftin, polysulphides such as (Ph,Sn),S,, (x = 3,4), being produced on pyro-l ~ s i s .~ ~ ’ Trithiocarbonates react with CSC1, to give polymeric C-S com-pounds ;328 bromine oxidises trithiocarbonic acid to the polymeric (CS*S z)n.Monothiophosphates M,+PS0,3- are produced either from sodium trithio-carbonate and sodium metaphosphate 32Qa or by alkaline hydrolysis32Qb ofPSCl,. They are oxidised by iod.h~e,~~~c or ferricyanide32Qd todisulphanediphosphonates M4+(P0,S,P0,)4-, from which cyclic thiotri-metaphosphates [containing the (P30,s3)3- ion] are formed by thermaldecomposition.329c The disulphanediphosphonates disproportionate to tri-sulphanediphosphonates in alkaline methanolic sol~tion.~29~ The prefer-ential attack of alkyl halides on the sulphur atoms of PS0,S- is attributed tothe comparative weakness of n-bonding between phosphorus and sulphur.330Umymmetrical disulphides (which disproportionate rapidly) have beenprepared by the displacement of sulphite ion from amino-Bunte ions, e.g.,NH2CH2CH2*SS03-, by rnercaptide~.~~~ The association of amines withelectron-poor disulphides has been studied spectrophotometrically.~32 InStrontium polysulphides (including SrS,) have been*Ip R.Bruce, J. 0. Edwards, D. Gris.com, R. A. Weeks, L. R. Dartee, W. DcEleine,880A. G. Streng and L. Streng, J . Phyg. Chm., 1966, 69, 1079.asrD. E. Sands, J. Amer. Chem. Soc., 1966, 87, 1395.388 (a) J. Weiss and H. S. Neubert, Acta: Cryat., 1965, 18, 815; (b) H. Garcia-Femmdez, C m p t . rend., 1965,260, 1183; (c) W., 261, 745; (d) J. C. Van de Grampeland A. Vos, Rec. Trav. china., 1965, 84, 599.and M. McCmthy, J . Amr. Chern. Soc., 1965, 87, 2057.H. Garcia-Fernandez, Compt. rend., 1965, 260, 6107.324 R. C. Brasted and J. S. Pond, Inorg. Chern., 1965, 4, 1163.a25 H. D. Lutz, 2. anorg. Chem., 1965, 339, 308.326 H. Schmidbaur, M. Schmidt, and W. Siebert, Chern. Ber., 1964, 97, 3374.327 W. T. Schwartz, jun., and H.W. Post, J. 0rganmetaWi.e Ohm., 1964, 2, 425.B. Krebs and G. Gattow, 2. a w g . Chem., 1965, 338, 225; cf. M. Schmidt, “ In-organic Polymers,” ed. F. Gs. A. Stone md W. A. G. Graham, Academio Press, 1962,p. 140.329 ( a ) A. Lamotte, M. Porthault, and J. C. Merlin, Bull. SOC. chim. France, 1965,915; ( b ) F. Feh6r and F. Vial, 2. anorg. Chem., 1965, 335, 113; (c) G. Lsdwig and E.‘Thilo, ibid., p. 126; (d) H. Kern-, I. Z. Steinberg, and E. Katchalski, J . Amer. Chem.Soc., 1965, 87, 3841; cf. Ann. Reports, 1964, 61, 145.380 S. Akerfeldt, Nature, 1965, 206, 505; cf. Ref. 289.s81 33. L. Klayman, J. D. White, and T. R. Sweeney, J. Org. Chm., 1964, 29,3737.**% F. Fischer and R. Gottfd, 2. Chm., 1965, 5, 226160 INORaANIC CHEMISTRYbasic conditions, disulphides are cleaved smoothly by elemental phosphorusto form thiophosphites :333P, + GRSSR -+ 4(RS),P.The boat configuration, which maximises n-interactions between carbonatoms in tetracyanodithiin ma (23a), is skewed in the thiobromide P,S,Br,(23b), so minimising steric repulsions between terminal and ring sulphurat0rns.33~~ The electron spin resonance spectrum of the dibenzothiophenradical ion shows no evidence for the participation of d-orbitals in the bondsto sulph~r.~~5have been prepared from the elements.Iodine reacts with CUBS to giveIBS, which has properties unlike those previously reported for this com-pound.336 The hydrogen dithiocyanate ion has been isolated as its tetra-phenylarsonium salt from the reaction of [Ph4As]+HC12- with KSCN insulphur di0xide.3,~ Caesium thioiodide CsSI has been prepared.338Sulphur dichloride forms 1 : 1 complexes with AlCl,, FeCI,, and SbCl,,which are formuhted as salts of the SC1+ cati0n.33~ The primary reaction inthe thermal decomposition of triarylsulphonium alkoxides 340a appears to bethe formation of the neutral radical Ar3S*, whereas for the halides340b therelative yields of the various RX species are more compatible with theformation of a 4-covalent sulphur intermediate.N-Fluoroformyliminosulphur difluoride SF,:N*COF has been preparedfrom SF, and the isocyanates of silicon, phosphorus and and therelated perfluoroisopropyl compounds RfN:SF*CF(CF,) 2, ( Rf = CF,, C2F5,C,F,), from R,N:SF, and perfluoropropane in the presence of casiumfluoride.342" Further fluorination of the perfluoroalkyl derivatives RfXSF,by N,F4 takes place in ultraviolet light.342b New cations of the typeSeveral ternary compounds in the general class (Cu,Ag) (B,P) (S,Se),,333 Chisung Wu, J .Amer. Chem. SOC., 1965, 87, 2522.384 (a) W. A. Dollase, J . Amer. Chem. SOC., 1965, 87, 979; ( b ) F. W. B. Einstein,336 R. Gerdil and E. A. C. Lucken, J . Amer. Chm. Soc., 1965, 87, 213.336 J. K. Kom, Ann. Ch;m. (France), 1964, 9, 179; cf. E. Wiberg and W. Sturn,337 31. F . A. Dove, Chem. Comm., 1965, 23.33BC. Dagron, Compt. rend., 1965, 260, 1422.3a9 S. N. Nabi and M. A. Khaleque, J . Chem. SOC., 1965, 3626.340 (a) J. W. Knapczyk, G. H. Wiegand, and W. E. McEwen, Tetrahedron Letters,341 A.F. Clifford and C. S. Kobayashi, I w g . Chem., 1965, 4, 571.342 (a) R. D. Dresdner, J. S. Johar, J. Merritt, and C. S. Patterson, Inorg. Chem.,B. R. Penfold, and Q. T. Tapsell, Inm-g. Chem., 1965, 4, 186.2. Naturforsch., 1955, lob, 108.1965, 2971; ( 6 ) G. H. Wiegand and W. E. McEwen, ibid., p. 2639.1965, 4, 678; (b) R. D. Dresdner, 5. Merritt, and J. P. Royal, {bid., p. 1228JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 161[R,S:NSR,]+ have been obtained by the reaction of NCI, with thioethersa3"and of sulphoxides with cyanogen halides :u3b2R,SO + *(CNX), -+ [R,S:N:SR,]+X- + C02.The ultraviolet spectrum and diamagnetism of S,N, are explicable only ifmolecular-orbital terms corresponding to S S cross-bonding are included.344Thiotrithiazyl halides S4N3X, (X = C1, Br) have been obtained by theammonolysis of the dihalogenodisulphanes, and other salts by metathesis .345The cation S4N,+ has a planar cyclic structure (24), in which the S-S andN-S lengths correspond to single and approximately double bonds respec-tively.3a6 Monomeric thiazyl fluoride NSF has been prepared 347 by thefluorination of S,N,, and other sulphur-nitrogen compounds by the actionof atomic nitrogen on compounds of bivalent s~lphur.3~~The chemistry of the lower oxides of sulphur has been re~iewed.~49The freezing points of solutions of sulphoxides in sulphuric acid correspondto the formation of the expected R,SOH+, in spite of the deep colours,which are attributed to charge transfer proce~ses.~5*~ Unlike sulphones,N-oxides, or phosphine oxides, sulphoxides exchange oxygen rapidly withsulphuric acid.350* 2-Thiaindane 2-oxide is dimeri~,5~l probably, on theevidence of its proton magnetic spectrum, through a double bridge (25).Dimethyl sulphoxide and alkylsulphinylcarboqlic acids RSO ,CH,CH,*CO,Hare reduced to the sulphides by tervalent phosphorus compounds 352a and byiodide ion.352b Halides of tervalent phosphorus 353a and triphenylphos-phine 353b react with sulphur dioxide to give a mixture of the phosphoryl andthiophosphoryl derivatives; if an excess of sulphur dioxide is used, thethiophosphoryl halides exchange sulphur for ~ x y g e n .~ ~ ~ a Trirnethylphos-phine reacts more vigorously, to give the oxide The crystalstructure of ammonium sulphite monohydrate has been determined ;354 thesulphite ion retains CQV symmetry in (NH,),[Hg(SO,),], and is thereforeco-ordinated through ~ulphur.~5~ Reaction of NF, with molten sulphur343 (a) R.Appel and G. Buchler, AnnaZen, 1965,684,112; (6) P . Y. Blanc, Experientia,344 P. S. Braterman, J . Chem. SOC., 1965, 2297.34ii M. Becke-Goehring and H. P. Latseha, 2. anorg. Chem., 1964, 333, 181.846 J. Weiss, 2. anorg. Chem., 1964, 333, 314; A. W. Cordes, R. F. Kruk, and E. K.847 B. Cohen, T. R. Cooper, D. Hugill, and R. D. Peacock, Nature, 1965, 20'7, 748.348 J. J. Smith and W. L. Jolly, Inorg. Chem., 1965, 4, 1006.349 P. W. Schenk and R. Steudel, Angew. Chem., 1965, 77, 437.350 (a) S. Oae, T. Kitao, and Y. Kitaoka, Bull. Chem. SOC. Japan, 1965, 38, 543;(b) S.Oae, T. Kitao, Y. Kitaoka, and S. Kawamura, ibid., p. 546.351 R. F. Watson and J. F. Eastham, J . Amer. Chem. SOC., 1965, 8'7, 664.354. (a) E. H. Amonoo-Neizer, S. K. Ray, R. A. Shaw, and B. C. Smith, J . Ohem.SOC., 1965, 4296; ( b ) S. Allenmark, Acta Chem. Scand., 1965, 19, 1.353 (a) E. Fluck and H. Binder, Angew. Chem., 1965, 17, 381; (b) B. C. Smith andG. H. Smith, J . Chem. Soc., 1965, 5516.354 L. F. Battell and K. N. Trueblood, Acta Cryst., 1965, 19, 531.1965, 21, 308 (cf. Ann. Reporta, 1964, $1, 145).Gordon, Inorg. Chern., 1965, 4, 681.J. J. Bullock and D. G. Tuck, J . Chem. SOC., 1965, 1877162 INORGANIC CHEMISTRYyields 356 both fhiothionyl fluoride SSF, and NSF; stretching constants havebeen determined 357 for both types of bond in SF,, and the valence problemsof SF, and SF,O considered the~retically.~~BThe main product of the reaction between dilute sulphur trioxide vapourand aqueous ammonia s9 is the nitrilosulphonate (NHaf),[N(SO,)!]3-; the1 : 3 complexes of SO, with oxygen bases are formulated 360 as six-co-or-dinated, e.g., (MeO),S(OH),.The complexes N205,nS03, (n = 2, 3, 4) arepresumably polys~lphates.~~~ Methyl polysulphates MeO(SO,),Me havebeen detected in equilibrium mixtures of sulphur trioxide and dimethyl~ulphate.~6~ Acids of the general formula H[SbF5-,(SO3I?),+,], (n = 0, 1,2,3) have been found in solutions of SbF, and related compounds in fluoro-sulphuric The protonation of weak bases in this solvent has beenstudied by nuclear magnetic resonance spectroscopy,364 and its behaviour asa reaction medium and fluorinating agent has been re~iewed.~6~ A con-venient method for the preparation of amidosulphuryl fluoride NH,SO,Ffrom sulphamide has been described.366a The terminal amido-groups inH,N*S02*NMe*S0,*NH2 and in H2N(S0,*NMe),S0,*NH, react with PCI,to give -N:PCl, derivatives, in which the chlorine atoms can be replaced byphenyl or phenoxy-gr~ups.~~~~ Fluorine reacts with sulphamide in aqueoussolution to form NN-difluorosulphamide NF,*SO,*NH,, which decomposesto NHF, onDisulphuryl fluoride is attacked by anionic nucleophiles thus :S,O,F, + X- ---+ FS0,X + S0,F-,(X = F, C1, N3), and the new compounds FSOa,, CF,SO,N, have beenreported.Disulphuryl chloride oxidises the nucleophile 367 to ClX.Di-(methylsulphuryl) peroxide368a (MeSO2),0, and bis( trifzuoromethylsd-phuryl) peroxide368b have been prepared electrolytically ; the latter compounddecomposes explosively. Tetrafluorohydrazine reacts quantitatively 369 withS2F10:NzFa + --+ 2mzSE’,and N:SF$Et, is obtained in a condensation reaction between thiazyltrifluoride NSF, and diethylamine.8703~ 0. Glemser, U. Biermann, J. Knaak, and A. Haas, Chm. Ber., 1965, 98, 446.~ ~ 5 7 Ed. G, K. Pillai, K. Ramaswamy, and R. Pkhai, Cam&. J . Chem., 1965, 43, 463.358 R. D. Willett, Theor. Chim. Acta, 1964, 2, 393.369 H.P. Lehmann, D. Beyer, and W. Scbeider, 2. amrg. Chem., 1965, 337, 22.3s0R. C. Pad, M. S. Bains, R. Kesh, S. S . Pam, and D. Shgh, Indian J. Ohm.,361B. Vandorpe and J.Heubel, Compt. rend., 1965, 860, 6619.J. R. Van Wazer, D. Grant, and C. H. Dungan, J . Amer. Chem. Soc., 1965, 87,s63 R. C. Thompson, J. Barr, R. J. Gillespie, J. B. Edilne, and R. A. Rothenbury,3a4T. Birchall and R. J. Gillespie, Canad. J . Chm., 1965, 43, 1045,se5A. Engelbrecht, Angew. Chem., 1965, 77, 695.s66 ( a ) L. K. Huber and H. C. Maadell, jun., Irwrg. Chm., 1965, 4, 919; (b) P. Nan-nelli, A. Failli, and T. Moeller, ibid., p. 558; (c) R. A. Wieaboeck and J. K. Ruff, ibid.,p. 123.367 J. K. Ruff, .Tn.org. Chern., 1965, 4, 567.388 (a) R. N. Hasmldine, R. B. Heslop, and J. W. Lethbridge, J . Chm. Soc., 1964,4901; ( b ) R. E. h’oftle and G. H. Cady, Inorg. Chem., 1965, 4, 1010.370 0. Glemser, H. Meyer, and A. Haas, Chern.Ber., 1965, 98, 2049.1965, 3, 239.3333.Inorg. Chm., 1965, 4, 1641.J. L. Boivin, Canad. J. Chem., 1964, 42, 2744JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 163Selelzium and Tellurium. Trimethylsilyl selenide (Me,Si),Se is formedfrom Me3SiC1 and PhSeNgBr, and the telluride analogously.lee Improvedmethods for the preparation of (CF,) 2Se,( CP,) 2Se2 (from selenium and silvertrifluoroa~etate)~~1~ and of alkylisoselenocyanates RNCSe (from seleniumand alkyl i s ~ c y a n i d e s ) ~ ~ ~ ~ have been described. Selenocyanates react withorganomercq compounds, e.g.,372Ph,Hg + Se(SeCN), --+ PhHgSeCN + PhSeCN + Se.Selenocarbonates and thioselenocarbonates containing the ions CSe,3-,CSe,S3- and CSeS,3- have been obtained from carbon disulphide or disel-enide.373 Dimethylselenium dihalides Me2SeX, form complexes with bothamines and boron trihalides; the former (X = C1)374a are unstable at roomtemperature, and the latter, (X = ClYBr),374b are salts (Rle,SX)+(BX,)-.The chemistry of the complexes of SeIV, TeIV has been re~iewed.87~ Thedimethylamido-derivatives Me&*SeOCl and (Me,N) ,SeO have been ob-tained from C1,SeO ; the bis( dimethylamido)-compound slowly loses oxygenat room Alkylselknio esters 376b RSe0,R' and the anhy-d~ide~7~c (26) have been prepared.The corresponding(27)acid forms anitrate378c [(CH,)2Se(OH),](N0,),, and selenious acid itself-is basic, forminga perchlorate in which the cation [Se(OH),]+ is pyramidal.376d Potassiumfluoroselenite KSe0,F has been prepared,376e and its properties comparedwith those of KS0,F.Crystalline selenium trioxide exists in stable and unstable forms, in whichthe cyclic tetrameric molecules have the symmetry 8, and D2d respec-t i ~ e l y ; ~ ~ 7 ~ the lengths of the ring bonds alternate in the 8,-modification 377bThe same structure persists in the vapour, in which the tetramer is inequilibrium with monomer units.377c The hydrogen atoms in silver amido-selenate AgSe0,NH , can themselves be substituted by silver ; triammine-diaquotrisilver amidoselenate 378 is formulated asAg(NH3 )SeO3"Ag 12,2=20( a ) H.J. Emeleus and M. J. Dunn, J . Inorg. Nuclear Chem., 1965, 27, 752;373 E. E. Aynsley, N. N. Greenwood, and M. J. Sprague, J . Chem. SOC., 1965, 2395.373 H. Seidel, Naturwisa., 1965, 52, 539.(a) K.J. Wynne and J. W. George, Inorg. Chem., 1965, 4, 256; ( b ) J . A w r .Chem. Soc., 1965, 87, 4750.376 D. I. Ryabchikov and I. I. Nazasenko, Rum. Chem. Rev., 1964, 33, 65.376 (a) R. Paetzold and E. Ronsch, 2. anorg. Chem., 1965, 338, 22; ( b ) ibid., p. 195;(c) R. Paetzold and D. Lienig, ibid., 1965, 335, 289; (d) R. Paetzold and M. Garsoff'ke,ibid., 1965, 336, 52; (e) R. Paetzold and K. Aurich, ibid., 1965, 335, 281.s7' (a) R. Paetzold and H. Amoulong, 2. arz.org. Chem., 1965, 337, 225; (b) F. C.Mijlhoff, Acta Cryst., 1965, 18, 795; (c) F. C. Mijlhoff, Rec. Trccu. chint., 1968, 84, 74.87a I(. DOf3thl and A. Rbzicka, 2. anorg. Chem., 1966, 337, 326.(b) W. J. Franklin and R. L. Werner, Tetrahedron Lettere, 1965, 3003164 INORGANIC CHEMISTRYThe preparation of iodoxyl selenates 379a (IO,),SeO,, IO,HSeO, and thenitrosyl selenates 379b NO-HSeO, and (NO),Se,O, has been described; theSe-O-Se grouping in the diselenate ion is bent.379c The chemical shifts ofa number of compounds relative to 77SeOC1, have been determined.380Bis(bipheny1ene)tellurium (27) has been prepared from TeCI, and 2,2’-dilithi~biphenyl.~~~ A new oxychloride of tellurium, Te6011C1, has beenobtained,382 and a paramagnetic oxide of composition Te,O, has been foundas an intermediate in the thermal decomposition of telluric a ~ i d .3 ~ ~ BariumtelIurate reacts in a more complicated way with fluorosulphuric acid thandoes barium ~elenate,~8~ to give the new pentafluorotellurium( VI) compoundsTeF,OH, TeF,OSO,F, TeF,OSO,H, and (TeF,O),SO,.Nitrous acid and some of its derivatives formstable solvates in hydrogen fluoride, which are useful fluorinating agents.385~So is benzoyl fluoride, (for oxygen-containing compounds of the non-metals),boric oxide being converted by it to boron trifluoride and octamethylcyclo-tetrasiloxane to dimethyldifl~orosilane.~85b The trifluoromethoxides of thelarger alkali metals MOCF,, (M = K, Rb, Cs), have been prepared fromcarbonyl fluoride and a suspension of the metal fluoride in acetonitrile.Theyare immediately hydrolysed by water.386 The effective electronegativitiesof several fluoroalkyl groups have been estimated from the ionisation con-stants of the fluoroalkylmercuric hydroxides RHgOH ;387u the stronginductive withdrawal of electrons by fluoroalkyl groups from the benzenering is partly counteracted by the interaction of the p-electrons of fluorinewith the aromatic n - ~ y s t e m .~ ~ ~ ~ As a consequence of ring strain and thehigh electronegativity of the CF, groups, the carbonyl group in hexafluoro-cyclobutanone is highly polar, and reacts readily with boron halides, silanesand phosphine~.~~~ The addition reactions of hexafluoroacetone (CF,),COwith methyl- and dimethyl-arsine 389* are initiated by nucleophilic attack atcarbon, whereas the adducts with Me,MH, (M = Si,Ge,Sn), are formed byeleetrophilic attack at oxygen.389b The fluoroxy-compounds SF,OF andCF,OF react with N,F, to give the oxydifluoroamines SF,ONF,, CF30NF2.The new compounds are colourless gases which do not react with glass ormercury ., OChlorine and Bromine.Chlorine trifluoride forms 1 : 1 adducts withPF,, BF,, AsF,, and SbF,, in order of increasing stability. They are ionic379 (a) G. Icempe and D. Robus, 2. Chem., 1965, 5 , 394; ( b ) K. Dosthl, A. Rbzifika,and P. Rumigek, 2. anorg. Clzem., 1965, 336, 219; (c) R. Paetzold, H. Amoulong, andA. RSziEka, ibid., p. 278.380 T. Birchall, R. J. Gillespie, and S. L. Vekris, Canad. J . Chem., 1965, 43, 1672.381 D. Hellwinkel and G. Fahrbach, Tetrahedron Letters, 1965, 1823.382 P. Khodadad, Bull. SOC. chiin. France, 1965, 468.383 J. Rosickf, J. Lout, and J. Pavel, 2. anorg. Chem., 1965, 334, 312.384 A. Engelbrecht and F. Sladky, Monatsh., 1965, 96, 159.385 (a) F.Seel, Angew. Chrn., 1965, 77, 689; (b) F. Seel, R. Budenz, and K. Gruner,386 M. E. Redwood and C. J. Willis, Canad. J . Chem., 1965, 43, 1893.887 (a) H. B. Powell and J. J. Lagowski, J . Chem. Soc., 1965, 1392; ( b ) W. A. Shep-388 G. W. Parshall, Inorg. Chem., 1965, 4, 52.389 (a) W. R. Cullen and G. E. Styan, J . OrganmnetuZZk Chem., 1965, 4, 151; (6)390 W. H. Hale, jun., and S . AT. Williamson, Inorg. Chenz., 1965, 4, 1342.Group VII.-FZuurine.Annalen, 1965, 684, 1.pard, J . Amer. Chem. SOC., 1965, 87, 2410.Inorg. Chem., 1965, 4, 1437JOHNSON, PADDOCK AND WARE: THE TYPICAL ELEMENTS 165in the solid and in solution; the ClF,+ ion is bent,3,1a whereas the difluoro-chlorate(1) ion C1P2-, found in the 1 : 1 complex NO+ClF,- of nitrosylfluoride and chlorine monofluoride, is linear.39lb The equilibria of brominewith bromide ions on an anion-exchange resinss2 involve the polybromideions Br3- and Br5-, Lithium bromife LiBrO, has been prepared by thedry reaction between lithium bromide and lithium b r ~ m a t e .~ ~ ~Iodine. The iodine fluorosulphates ISO,F and 13S03F have been pre-pared from iodine and peroxydisulphuryl fluoride S 2O ,F , which is regardedas a pseudo-halogen. The iodine is bound covalently in the solid, but I+and 13+ have been identiiied spectroscopically in solution.394 Iodinedissolves in a solution of iodic acid in sulphuric acid. Measurement ofconductivities and freezing points show that the resulting cation I+ firstdisproportionates to I,+ + IO+; on further addition of iodine, the iodylcation also is reduced to 13+.Similar experiments with IC1 and IBr provideevidence 395 for 12Cl+, I,Br+, and ICI,+. The rapid exchange of iodine iniodide/iodate melt,s Sg6 is attributed to a, reversible redox reaction involvingI I or IIn. The electronic spectrum of the hypoiodite ion has been correlatedwith the photochemical sensitivity of hypohalites.397The hydrogen diiodide ion HI2- has been isolated as its tetra-n-butyl-ammonium ~ a l t ; ~ ~ 8 anion-exchange resins carrying C1-, I-, or SCN- holdiodine strongly 39s as 12C1-, 13-, or 12SCN-. The anion in Bun413 is linear,with equal bond-lengths.4OO Measurements of the temperature coefficientsof conductivity of tetramethylammonium salts containing the 13-, 15-, andI,- ions show that the conductivity is determined mainly by the shortestdistance between polyiodide ions. Polyiodides of the larger 10-methyl-acridinium cation have smaller conductivities, because of the reducedorbital overlap.401Iodine pentoxide reacts with peroxydisulphuryl fluoride to give iodylfluorosulphate in good yield :4021,05 + S20,FF, -+ 2102S0,F + 402.Iodyl fluoride accepts a fluoride ion from KF, to form K+I0,F2-, butgives the hexafluoroarsenate IO,+AsE”,- with arsenic pentafl~oride.~~~The periodate ion dimerises in alkaline solution. The monomer-dimerequilibrium has been measured spectrophotometrically, and the results used391 (a) K.0. Christe and A. E. Pavlath, 2. anorg. Chena., 1965, 335, 210; (a) K. 0.392 H. Irving and P.D. Wilson, J . Inorg. NucJear Chesn., 1964, 26, 2233.393P. Hagenmuller and B. Tanguy, Compt. rend., 1965, 260, 3974.394F. Anbke and G. H. Cady, I w g . Chem., 1965, 4, 269.396 R. A. Garrett, R. J. Giflespie, and J. B. Senior, Inorg. Chem., 1965, 4, 563.3s6 Yu. Ya. Fialkov, V. S. Slonina, and RI. S. ICartavov, Rzcss. J. Inorg. Chem.,397 0. Haimovich and A. Treinin, Nature, 1965, 207, 185.398 K. M. Harmon, S. D. Alderman, K. E. Benker, D. J. Diestler, andP. A. Gebauer,390 C. Barraqu6 and B. Trkmillon, Bull. SOC. ckim. France, 1965, 1674, 1680.400 S. G. W. Ginn and J. L. Wood, Chem. Comm., 1965, 262.401 S. Kawai, R. Kiriyama, M. Uchida, S. Kurabayashi, and H. Milkawa, BUZZ.402F. Aubke, G. H. Cady, and C. H. L. Kennard, Inorg. Chem., 1964, 3, 1799.403 J.J. Pitts, S. Kongpricha, and A. W. Jache, Inorg. Chem., 1965, 4, 257.Christe and J. P. Guertin, Isaorg. Chem., 1965, 4, 905.1964, 9, 116.J . Amer. Chem. Soc., 1965, 87, 1700.Chem. SOC. Japan, 1965, 38, 799; S. Kurabayashi and H. Mikawa, ibid., p. 1410166 INORGANIC CEEMISTRYto calculate a new value of the second dissociation constant of the acid.4wTwo 10, octahedra share an edge 405 in the mesoperiodate anion of thepotassium salt K,[H,12010],8H,0. Further thermogravimetric studies ofthe thermal decomposition of periodates have been reported,408 and aparamagnetic salt BaIO,,H,O obtained, which may contain IyI. Vibra-tional 407 and nuclear magnetic resonance spectra 408a are compatible with thesymmetry Call for IOF,, but the 19F spectra 408a#b give no detailed structuralinformation about the shape of IF,.404 G.J. %&t and J. D. Lewis, Chem. Comm., 1965, 66.405 A. Ferrari, A. Braibauti, and A. Tiripicchio, Acta Cryst., 1966, 19, 629.406 31. Drtitovskf, 2. anorg. Chem., 1964, 334, 169; cf. Ann. Reports, 1964, 61, 147,407 D. F. Smith and 0. M. Begun, J. Chem. Phys., 1965, 43, 2001.408 (a) N. Bartlett, 8. Beaton, L. W. Reeves, and E. J. Wells, C a d . J . Chm.,1964, 4&, 2531; (b) R. J. Gillespie and J. W. Quail, ibid., p. 26713. THE TRANSITION ELEMENTSBy F. E. Mabbs and Q. J. mchh(Chemistry Department, Tits University, Munchester, 13)Fo LL o w IN G previous practices, the advances in transition-metal chemistrywill be reviewed by dividing the elements into groups and then mentioningcompounds generally in order of increasing oxidation state.Papers dealingwith elements from a number of groups will normally only be mentionedonce.All papers dealing with kinetic studies have been omitted; and becauseof lack of space much of the work on solvent extraction and general solutionstudies has had to be omitted. General reviews which have appeared havedealt with transition-metal oxides,l reactions of metal acetylacetonates,2reactions of metal halides with amines and alkyl cyanides, complexes ofsulphur, selenium, and tellurium donors, the Mossbauer effect, polarographicstudies, fused-salt spectrophotometry,4 and magnetic proper tie^.^Scandim and the Lanthanides.-Doubt has been cast on the existenceof lower chlorides of scandium and some new oxides MIScO, (MI = alkalimetal) have been prepared.' A method of preparing high-purity holmiumhas been described,s and vacuum distillation proposed as a means of puri-fying lanthanide chlorides.9 E.s.r.studies lo of europium dissolved in liquidammonia suggest that the species present are EuII and solvated electrons.The crystal structures11 of the oxide hydroxides (MOOH) of holmium-,erbium-, and ytterbium-( m) are based on a trigonal prismatic co-ordination.Phase studies12 of the Gd-GdC1, system led to the isolation of GdC1,.,while the corresponding iodide system yields a metallic, ferromagneticphase GdIpo4.The co-ordination chemistry of the lanthanides has been reviewed ;13the possibility of fhding laser materials seems to be stimulating interest inthis field.A co-ordination number of ten has been established14 for thecompound La(H,O), (edta),SH,O and a number of eight-co-ordinate tropo-Bull. SOC. c h h . Prance, 1965, 1051-1215.J. P. Coleman, Angew. Chem. Internat. Edn., 1965, 4, 132.G. W. A. Fowles, Progr. Inorg. Chem., 1964, 6, 1.J. F. Duncan and R. M. Golding, Quart. Rev., 1965, 19, 36; D. R. Crow and3. V. Westwood, ibid., p. 57; R. A. Walton, ibid., p. 126; D. M. Gruen, ibid., p. 349;S. E. Livingstone, ibid., p. 386.B. N. Fig& and J. Lewis, Progr. Inorg. Chem., 1964, 6, 37.13 J. D. Corbett and B. N. Ramsey, Inorg. Clzern., 1965, 4, 260.7 R. Hoppe, B. Schapers, H.-J. Rohrborn, and E. Vielhaber, 2. anorg. Chem.* K. T. Faler, J . Imrg. Nuclear Chem., 1966, 27, 25.* G. SchBmacher, Compt. rend., 1965, 260,182.1965, 339, 130.lo M. J. Blandamer, L. Shields, and M. C. R. Symons, J . Chem. SOC., 1965, 3759.I1A. N. Christensen, Acta Chern. Scad., 1965, 19, 1391.la J. E. Mee and J. D. Corbett, Inorg. Chem., 1965, 4, 88.l3 T. Hoeller, D. F. Ifartin, L. C. Thompson, R. Ferrtk, C;. R. Feistel, and W. J.14M. D. Lind, B. Lee, and J. L. Hoard, J . Amer. Chern. Soc., 1965, 87, 1611.Randall, Chm. Rev., 1965, 65, 1168 INORGANIC CHEMISTRYlone, propanedione, and 4-picoline N-oxide complexes are kn0wn.15 It isoften possible to prepare both six- and eight-co-ordinate complexes with@-diketone ligands.l6 Complexes with 1 ,lo-phenanthroline, act’-bipyridyldimethylacetamide, and salicylaldehyde have been described .17A preparation of cerium(rv) fluoride has been described.lsThe Actinides.-Element 104 has been reportiedl9 but no details are ayet available; presumably this the first member of the fourth transitionseries. Potential methods for preparing new elements have been reviewed.20The separation of americium, curium, berkelium, and californium ;21 and ofprotactinium from monazite sand has been described.22Small traces of tungsten, from the electrodes used in arc-melting uraniumdicarbide, have been shown markedly to affect 23 the nature of the hydrolysisproducts of the carbide; and this may affect the results published by otherworkers 24 on uranium and thorium carbides. Plutonium borides have beenidentified 25 up to PuB12.Many ternary oxides of these elements have beencharacterised.26 Attempts to repeat the preparation of UN, have alwaysyielded 27 UN,.,.A number of halide complexes have been described, e.g., thorium( m)iodide and 01- and /%forms of the di-iodide;28 Cs3PuCI,,2€€,0 is known 29 andcompounds R1,MI, (MIv = Th or U) have also been prepared.30 Uraniumpentafluoride has been characterised and a semi-continuous preparationde~cribed.~~ Single crystals of alkali-metal salts MUF, have been prepared.32Potassium heptafluoroprotactinate(v) is nine-co-ordinated 33 while lithiumoc t a,fluoropr ot a ct ina t e ( v ) is presumably eight - co- ordinat ed , 34 Thoriumoxyiodide has been prepared from Tho, and ThI,, and is said 35 not to be al6 E.L. Meutterties and C. M.Wright, J . Amer. Chem. Soc., 1966,87,4706; J. Blancand D. L. Ross, J . Chem. Phys., 1965, 43, 1286; N. J. Rose and E. Abramson, ibid.,1965, 42, 1849.16 L. R. Melby, N. J. Rose, E. Abramson, and J. C. Caris, J . Amer. Chem. SOC.,1964,86, 5117; H. Bauer, J. Blanc, and D. L. Ross, ibid., p. 6125; S . M. Lee and L. J.Nugent, J. Inorg. Nuclear Chem., 1964, 26, 2304.1’ F. A. Hart and F. P. Laming, J . Inorg. Nuclear Chem., 1965, 27, 1605, 1826;T. woeller and G. Vincentini, ibid., p. 1477; R. G. Charles, ibid., 1964, 26, 2298.i* W. J. Asher and A. W. Wylie, Austral. J. Chem., 1965, 18, 959.19 Nuclear Science Abstracts, 1965, 19, Abstract no. 3233.20 C. Keller, Angew. Chem. Internat. Edn., 1965, 4, 903.21 J. Kooi, R. Boden, and J. Wijtra, J. Inorg.Nuclear Chem., 1964, 26, 2300.22 T. N. V. Pillai, J. Indian Chem. SOC., 1965, 42, 32.23 33. J. Bradley and L. M. Ferns, Inorg. Chem., 1965, 4, 597.Z 4 See e.g., L. M. Ferris and M. J. Bradley, J . Amer. Chem. SOC., 1965, 87, 1710;M. J. Bradley, M. D. Pattengill, and L. M. Ferris, Inorg. Chem., 1965,4,1080; S . Evered,M. J. Moreton-Smith, and R. G. Sowden, J. Inorg. Nuclear Chem., 1965, 27, 1867;J. Besson, P. Blum, and B. del Litto, Compt. r e d . , 1965, 261, 1859.25 H. A. Eick, Inorg. Chem., 1965, 4, 1237.26 C. Keller, L. Koch, and K. H. Walter, J . Inorg. Nuclear Chem., 1965,27,1205-53.27 C. E. Price and I. H. Warren, Inorg. Chem., 1965, 4, 115.28 D. E. Scaife and A. W. Wylie, J. Chem. SOC., 1964, 6450.2 9 R . E. Stevens, J. Irtorg. Nuclear Chem., 1965, 27, 1873.30 K.W. Bagnall, D. Brown, P. J. Jones, and J. G. H. du Preez, J. Chem. SOC.,3lA. S. Wolf, J. C. Posey, and K. E. Rapp, Inorg. Chem., 1965, 4, 751.32 G. D. Sturgeon, R. A. Penneman, F. H. Kruse, and L. B. Asprey, Inorg. Chem.,33 D. Brown and A. J. Smith, Chem. Corm., 1965, 554.a 4 D. Brown and J. E. Easey, Nature, 1965, 205, 589.3 5 D . E. Scaife, A. G. Turnbull, and A. W. Wylie, J. Chem. Soc., 1965, 1432.1965, 350.1965, 4, 748MABBS AKD MACHIN: THE TRANSITION ELEMENTS 169'' thoryl " compound. A number of thiocyanate complexes of uranium(rv)and thorium(m) with up to eight ions co-ordinated have been rep~rted.~eTricyclopentadienyl complexes of uranium, thorium, and plutonium arerep~rted.~' Among other complexes described are : uranium(rv) tetracar-b ~ x y l a t e s , ~ ~ amide complexes of uranium(m) and thorium(m) iodides 39 ando-phenanthroline and triphenylphosphine complexes of thorium( IV) chl0ride.4~An unusually large shift in the P=O stretching frequency has been noted 41in the complexes UCl,R,PO (R = Ph or C8H1,).Titanium, Zirconium, and Hahiuxn.-The monoxides of these elementshave been studied by heating the dioxide to above 2500" and quenching inan argon or neon matrix.42 A preparation for zirconium(n) chloride has beendescribed.43 Attempts 44 to repeat the preparation of dicyclopentadienyl-titanium led to the product (C5H,),TiC1.Zirconium(m) fluoride has been prepared45 from the hydride and anH,-HF mixture ; the product is ferromagnetic.The binuclear cyclopenta-ciiene complex [ (C,H5)zTiC1], has magnetic properties similar to those ofcopper(=) acetate 46 and its structure is discussed on this basis.Complexesof p-diketones with titanium-(In) and -(Iv) and zirconium(II1) have beencharacterised fully.47 Adducts of titanium(=) chloride with a wide rangeof ligands continue to attract attention 48 and similar work on vanadium andmolybdenum compounds has been reported. The complex TiCl,( bipyridyl)has been shown 49 to be an electrolyte [TiCl,(bipyridyl),]Cl.Many anhydrous metal chlorides may be obtained5* by treating theoxide with boiling octachlorocyclopentene. In some cases (e.g., MoV1 andWvl oxides) an oxychloride is formed. Chlorine azide has been shown 51 toreact with TiC1, and VOCI, yielding TiCl,N, and VOCl,N, which decomposeto the nitrides TiClN and VON.Hexanitrato-complexes of zirconium- andV. I. Belova, Ya. K. Syrkin, and E. N. Traggeim, Russ. J . Inorg. Chem., 1964,9, 1551; A. K. Molodkin and G. A. Skotnikova, ibid., p. 32.37 F. Baumgartner, E. 0. Fischer, B. Kanellakopulos, and P. Laubereau, Angew.Chem. Internat. Edn., 1965,4, 878; G. L. Ter Haar and iST. Dubeck, Inorg. Chem., 1964,3, 1648.38 R. C. Paul, J. S. Ghota, and M. S. Bains, J . Inorg. Nuclear Chem., 1965, 27,265.39 K. W. Begnall, D. Brown, P. J. Jones, and J. G. H. du Preez, J . Chem. Soc.,1965, 3594.40 B. W. Fitzsimmons, P. Gans, B. C. Smith, and M. A. Wasseff, Chem. and Id.,1965, 1698.K. W. Bagnall, D. Brown, and J. G. H. du Preez, J . Chem.SOC., 1965, 5217.4 2 W. Weltner and D. McLeod, J . Phys. Chem., 1965, 69, 3488.4 3 B. Swaroop and S. N. Flengas, Canad. J . Chem., 1965, 43, 2115.G. W. Watt and L. J. Baye, J . Irwrg. Nuclear Chem., 1964, 26, 2099.45 P. Ehrlich and G. Kaupa, 2. anorg. Chem., 1964, 333, 209.46 R. L. Martin and G. Winter, J . Chern. SOC., 1965, 4709.4 7 M. Cox, J. Lewis, and R. S. Nyholm, J . Chem. SOC., 1964, 6113; 1965,2840.48 G. W. A. Fowles and R. A. Walton, J . Chem. SOC., 1964, 4953; G. W. A. Fow~~s,R. A. Moodless, and R. A. Walton, J . Inorg. Nuclear Chem., 1965,27,391; D. A. Edwards,G. W. A. Fowles, and R. A. Walton, ibid., p. 1999.4 9 M. T. Siddiqui, N. Ahmad, and S. M. F. Rahman, 2. anorg. Chem., 1965, 336,110.A. B. Bardamil, F. N. Collier, and S.Y. Tyree, J . Less Common Metals, 1965,9, 20.s1 K. Dehnicke, J . Inorg. Nuclear Chem., 1965, 27, 809170 INORGANIC CHEMISTRYhafnium(1v) have been prepared 52 and a wide range of peroxy-complexesof early transition-group elements characterised.53Eight- co-ordinate complexes of zirconium- and hafnium-(rv) and niobium-and tantalum-(v) with tropolone have been ~tudied,~4 but o-phenylenebis-diethylarsine only forms sis-co-ordinate complexes with titanium(rv)chloride or bromide and vanadium(Iv) chloride, unlike the correspondingbi~dimethylarsine.~~ NN'-Dialkyldithiocarbamate complexes M( S ,CNR,),,[M = Ti, Zr, HfIY] and M(S,CNR,)5, [M = V, Nb, TaV] can be prepared 56from the corresponding complex &l(NR,), in carbon disulphide solution. Itis suggested that the titanium and zirconium compounds are eight-co-ordinate. The oxidation of titanium, vanadium, or chromium metal byhalogens in acetonitrile solution leads 57 to a variety of products dependingon the halogen used.As with titanium(m), solvent adducts of titanium(rv)continue to receive attention,58 a wide variety of donors being employed.The compound (Me,N),(TiCl,O) has been prepared, and is said59 to befive-co-ordinate. Dicyclopentadienyltitanium dichloride reacts 60 withammonia or methylamine at -37" breaking only one Ti-C1 bond but a troom temperature, the Ti-C,H, bonds are broken.Vanadium, Niobium, and TantaIum.-The chemistry of oxovanadium(rv)has been reviewed, and so have vanadium-oxygen systems.61 Very littlework on vanadium(@ systems has been reported.Acetylacetone and pico-linic acid complexes have been studied in solution G2 and a series of bivalentmetal tetrachloroaluminates [M( MU,) 2] prepared for all first-row transitionelements except titanium.63 The e.8.r. spectrum of vanadiurn(n) in a cad-mium chloride lattice has been studied.64Studies of metal clusters have been extended to niobium and tantalumhalides: compounds M&,, have been prepared for M = Nb or Ta andX = C1, Br, or I; usually by reduction of the pentahalide with a metal in ittemperature-gradient. The crystal structures of ??b6C1,, and Ta61,, arebased on octahedral arrays of metal atoms. 65 Similar preparative procedures6 1 K. W. Bagnall, D. Brown, and J. G. H. du Preez, J. Chem. SOC., 196415523.53 W.P. Griffith, J. Chem. SOC., 1964, 5248.54 E. L. Muetterties and C. M. Wright, J. Amer. Chem. Soc., 1965, 87, 4706.55 R. J. H. ClBrk, J . Chem. Soc., 1965, 5699.56 D. C. Bradley and M. H. Gitlitz, Chem. Comm., 1965, 289.67 B. J. Hathaway and D. G. Holah, J. Chem. SOC., 1965, 537.68 K. Baker and G. W. A. Fowles, J . Less Common Metah, 1965,8,47; V. Krishnanand C. C. Patel, J . Inorg. Nuclear Chem., 1964, 26, 2201; A. D. Westland and L. West-land, Canad. J . Chem., 1965, 43, 426; D. I. Tsekhovol'skaya, Russ. J . Inorg. Chem.,1964, 9, 755.6a A. Feltz, 2. anorg. Chem., 1965, 838, 147.6o A. Anamostopoulos and D. Nicholls, J. Inorg. Nuclear Chem., 1965, 27, -339.8, 1.61 J. Selbin, Chem. Rev., 1965, 65, 163; J. Stringer, J .Less Common Metals, 1965,6% W. I?. Sohaefer, I w g . Chem., 1965, 4, 642; R. C. Mercier, M. Bonnet, and M. R.63 R. F. Belt and H. Scott, Inorg. Chem., 1964, 3, 1785.64 I. Y. Chm, D. C. Doetschman, C. A. Hutchison, B. E. Kohler, and J. W. Stout,J . Chem. Php., 1965, 42, 1048.66 A. Simon, H. G. Schnering, H. Wohrle, and H. Schafer, 2. anorg. Chem., 1966,339, 165; D. Bauer, H. G. Schnering, and H. Schiifer, J . Less Common Metals, 1966,8, 388; R. J. Allen and J. C. Sheldon, AecstraE. J . Chem., 1965, 18, 277.Pgris, Bull. SOC. chirn. Fvame, 1965, 2926; Compt. rend., 1965, 260, 3092MABBS AND MACHIN: THE TRANSITION ELEMENTS 171have resulted g6 in the isolation of Nb6F15, Ta,XI6 (X = C1 or Br), andTa,Br,,. It has been shown 67 that these M6C1122+ systems readily undergoa two-electron oxidation, and their spectra have been interpreted.68Potassium hexafluorovanadate( m) may be prepared from vanadiummetal and KHF, and purified by sublimati~n.~~ Vanadium- and cluomium-(m) chlorides have been shown to act as chloride donors to e.g., SbCl,,SnC1, ; the hexachloro-species being formed.Trisdithioglyoxal complexes ofvanadium, molybdenum, tungsten, and rhenium(m) have been prepared 71and may have a triganal prismatic co-ordination [see under rhenium(m)].Tantalum(m) chloride forms M,TaCl, in alkali-metal halide melts,72 but theco-ordination number is not discussed.Vanadium(rv) chloro-complexes M,IVCl, can be prepared 73 from thecorresponding [VOC1,]2- salt in thionyl chloride. The same species may beprepared from VC1, in liquid HCl.In complexes of the types [VS,C,R6]Z,(R = CF3, x = 2- or I - ; R = Ph, x = 2-, 1-, or 0) and [V(S,C,H,X),]2-(X = H or Me,), the unpaired electron has been shown 74 to be predominantlyin ligand orbitals for all species with x = 2 (and z = 0 when R = Ph); itis thus not surprising that these complexes oxidise readily. A number ofsix-co-ordinate adducts of vanadium( IV) chloride have been prepared, 75however, some sulphur, phosphorus, and arsenic ligands lead to reduction tovanadium( m) . Some polymeric nitrosyl complexes [V(NO) 3C12]n have beenprepared.76 A number of vanadyl(Iv) species have been studied. Thecomplex VOL (L = quadridentate /3-keto-imine) has been partially re-solved. 7 7 A new method of synthesising maleonitriledithiolate complexeshas been devised 78 in which sodium dithiocyanoformate is reacted withvanadyl sulphate.Thermodynamic studies of ligand addition to the sixthco-ordination site of VO(acetylacetone), reveal 79 a wide range of equilibriumconstants. E.s.r. measurements on vanadyl phthalocyanine confirm 80that the unpaired electron is in a 3d, orbital. Niobium(rv) fluoride andiodide and tantalum(rv) chloride and bromide have been prepared;81 NbF,saH. Schizfer, H. G. Schnering, H.-J. Niehues, and H. G. Nieder-Vahrenholz,J . Less Comrnon Metals, 1965, 9, 95; P. J. Kuhn and R. E. McCarley, Inorg. Chem.,1965, 4, 1482; R. E. MoCarley and J. C. Boatman, ibid., p. 1486; EI. ScMfer, R. Gerken,and H. Scholx, 2. anorg. Chem., 1965, 335, 96.67 R.E. McCarley, B. G. Hughes, F. A. Cotton, and R. Zimmerman, Inorg. Chem.,1965, 4, 1491.68M. B. Robin and N. A. Kuebler, Jnorg. Chem., 1965, 4, 978.69 B. M. Wanklyn, J . Inorg. Nuclear Chem., 1965, 27, 481.70V. Gutrann, G. Hampel, and W. Lux, Mon&h., 1965, 96, 533.71 G. N. Schrauzer, V. P. Mayweg, and W. Heinrich,Chem.and Ind., 1965, 1464.m V. V. Safanov, €3. C. Korshunov, Z . N. Shevatova, and S. I. Bakum, Rum.13P. A. Kilty and D. Nicholls, J . Chem. Soc., 1965, 4915.A. Davison, N. Edelshin, R. H. Holm, and A. H. Maki, Inorg. Ohm., 1965,4,55.76 B. E. Bridgland, G. W. A. Fowles, and R. A. Walton, J. Incwg. Nuclear Ohm.,l6 W. Beck, K. Lottes, and K. Schmidtner, Angew. Chem. Internat. Edn., 1965,7 7 K. Ramaiah and D. I?.Martin, J. Inorg. Nucbar Ohm., 1965, 27, 1663. '* N. M. Atherton, J. Locke, and J. A. McCleverty, Chem. and Id., 1965, 1300.R. L. Carlin and F. A. Walker, J . Amer. Chem. SOC., 1965, 87, 2128.O0 J. M. ASSOUP, J. Goldmacher, and S. E. Harrison, J . Chem. Phys., 1965, 43, 169.F. P. Gortsema and R. Didchenko, Inorg. Chem., 1965, 4, 182; P. W. Seabaughand J. D. Corbett, ibid., p. 176; V. V. Sofonov, B. G. Korshunov, Z. N. Shevstova, andJ. Inorg. Ohm., 1964, 9, 914.1965, 27, 383.4, 161172 INORGANIC CHEMISTRYdisproportionates a t 350" in VMUO yielding NbF, and NbF,; however NbI,melts incongruently at 503" forming Nb,I,.Studies of niobium(v) and tantalum(v) halides have been continued.NbCl, or TaCl, will abstract an oxygen atom from triphenyl-phosphine or-arsine oxide yielding 82 the oxytrichloride, and Ph,Cl,P or Ph,Cl,As.Ithas been estimated that niobium(v) and tantalum(v) fluorides are less thanone per cent ionised in the molten state and shown that niobium(v) chlorideremains a dimer in dry, oxygen-free carbon tetrachloride or nitromethanebut that in acetonitrile a monomer NbCl,CH,CN is formed.83 A number ofaddition compounds of the pentahalides have been isolated. 84 The structuresof some fluoro-peroxy-complexes of niobium, tantalum, molybdenum, andtungsten have been deduced from lgF.n.m.r. studies.85 The reaction ofo-phenylenebisdimethylarsine (diars) with niobium(v) or tantalum(v) chlorideor bromide in a non-hydroxyllic solvent yields seven-co-ordinate speciesMX,(diars), but if an excess of diarsine is heated in a sealed tube withNbX,, NbX,, or NbOX, (X = C1, Br, or I) an eight-co-ordinate speciesNbX,(diars) 2, isomorphous with TiCl ,(diars), results.86Chromium, Molybdenum, and Tungsten.-Apart from the carboiiyl de-rivatives dealt with elsewhere, a number of zero-valent compounds have beenprepared.Nitrosyl chloride reacts 87 with molybdenum and tungstenhexacarbonyls yielding the dinitrosyl dichloro-complex. These readily formcomplexes M(NO),C12L, with amines and phosphines. Phosphorus tri-fluoride reacts 88 with tungsten hexachloride to form the complex W(PF,),but CoI, only yields HCo( PF,),. A maleonitriledithiolate (MNT) complexPh,P[Mo(NO),(MNT),] has been reported,sg and the constrained phosphiteester, 4-methyl-2,6,7-trioxa-l-phosphabicyclo[2,2,2, ]octane has been shown 90to form mono- and di-substituted complexes with chromium, molybdenum,tungsten, iron, and nickel carbonyls.It has been reported that phosphoro-benzene [(PhP),] undergoes ring expansion to the pentamer when reactedwith molybdenum or tungsten carbonyl yielding (PhP) 5(Mo,W)(CO) 5 , how-ever, this has been disputed by other workers.91 Electron-diffractionstudies 92 of dibenzenechromium show that the complex has DGh symmetryand that C-C bond lengths do not differ by more than 0.02 8.L. G. Shadrova, Russ. J . Inorg. Chem., 1965, 10, 359; S. S. Berdonosov and A. V.Lapitskii, ibid., p. 152.82 D. B. Copley, F. Fairbrother, and A. Thompson, J . Less Common Metals, 1065,8, 2567.83 F. Fairbrother, K.H. Grundy, and A. Thompson, J . Chem. SOC., 1965, 761;D. L. Keppert, and R. S. Nyholm, ibid., 2871.84 F. Fairbrother, K. H. Grundy, and A. Thompson, J . Chem. SOC., 1965, 765;K. Feenan and G. W. A. Fowles, ibid., p. 2449; J. Desnoyers and R. Rivest, Cunad. J .Chem., 1965, 43, 1879.85 D. F. Evans, W. P. Griffith, and L. Pratt, J . Chem. SOC., 1965, 2182; J . E.Guerchais, B. Spinner, and R. Rohmer, Bull. SOC. chim. France, 1965, 55.86 R. J. H. Clark, D. L. Keppert, andR. S. Nyholm, J . Chem. SOC., 1965, 2865, 2877.8 7 F. A. Cotton and €3. F. G. Johnson, Inorg. Chern., 1964, 3, 1609.88 Th. Kruck, W. Lang, and A. Engelmann, Angew. Chem. Internat. Edn., 1965,4,148.8s J. Locke and J. A. McCleverty, Chem. Comm., 1965, 102.90 J. G. Verkade, R.E. McCarley, D. G. Hendricker, and R. W. King, Inorg.91 H. G. Ang. J. S. Shannon, and B. 0. West, Chem. Comm., 1965, 11; C. W. A.9 2 A. Haaland, Acta Chern. Scand., 1965, 19, 41.Chem., 1965, 4, 228.Fowles and D. K. Jenkins, ibid., p. 61MABBS AND MACHIN: THE TRANSITION ELEMENTS 173The wetting of chromium, molybdenum, and tungsten by molten sodiumhas been studied.93 The reaction of molten sodium with molybdenum(rv) ortungsten(1v) oxide fields the metal, or an oxide Na,(Mo,W),06 dependingon temperature, while Cr03 yields the chromium(rv) compound Na,Cr0,.94Chromium(n) compounds are receiving greater attention this year. Inthe alkali-metal halide-chromium(r1) chloride systems both MICrCl, andM2CrC1, can be prepared when MI is Cs, Rb, or K, but when M = Na onlyNa,CrCl, is said to exi~t.~5 Na,CrF, has been prepared and shown 96 to beair-stable but NaCrF, could not be obtained.Mass-spectrometric studies 97have shown that the monofluoride CrF is formed when CrF, and chromiummetal are heated together. A number of chromium(n) complexes, mainlywith nitrogen donors, have been prepared 98 and magnetic and spectralstudies g9 of these, and other complexes have been reported. The magneticproperties of a number of phthalocyanine complexes have been investi-gated.loO The structure of molybdenum(n) acetate, which was discussed inlast year's report, has now been elucidated:lol it is a dimer, similar tocopper(I1) acetate but with an exceptionally short Mo-Mo distance of2-11 A (cf. expected value of about 2.9 A).The low-frequency infrared spectra of many complexes of the transitionelements have been assigned.lo2 The ion [Mo,C1,I4+ forms lo3 addition com-pounds with many ligands, e.g., [Mo&1&6]4+, [Mo,Cl,,L,] etc.The speciesK6M03C1,,, (NH,),Mo3Cl1,,H,O and cs6MO&11, have also been prepared.lwIn the MCl-CrC1, systerns,lO5 both M3CrC16 and M3Cr2C19 species areformed when M = Rb or Cs, but only the monomer exists when M = Li, Na,or K. The magnetic properties of molybdenum(II1) chloride have been inter-preted106 on a trimeric model. The ligand-field parameter, Dp, for thenitrogen end of cyanide ligands has been estimatedlo7 to lie between 950and 1010 cm.--l from studies of KFeCr(CN), and KCrFe(CN),: it is suggestedthat the former contains the unit FeII-NrC-CrIII.The compound pre-viously formulated as Cr3(MeC02),(OH),C1,8H,0 has been shown lo* to beCr,(MeCO ,) ,0.C1,5H20.83 C. C. Addison and E. Iberson, J . Chem. SOC., 1965, 1437.s4 C. C. Addison, M. G. Barker, and R. J. Pulham, J . Chem. SOC., 1965, 4483;95 H.-J. Seifert and K. Klatyk, 2. anorg. Chem., 1964, 334, 113.D6 A. J. Deyrup, Inorg. Chem., 1964, 3, 1645.O 7 R. A. Kent and J. L. Margrave, J. Amer. Chem. SOC., 1965, 87, 3582.D8 R. L. Pecsok, R. A. Garber, and L. D. Shields, Inorg. Chem., 1965, 4, 447; D. G.Holah and J. P. Fackler, ibid., p. 1112.g e A. Earnshaw, L. F. Larkworthy, and K. S. Patel, Chem. and Ind., 1965, 1521;J . Chem. SOC., 1965, 3267; 2. a w g . Chem., 1964, 334, 163; J. P. Fackler and D.G.Holah, Inorg. Chem., 1965, 4, 954.C. C. Addison and M. G. Barker, &id., p. 5534.looA. B. P. Lever, J. Chem. SOC., 1965, 1821.lolD. Lawton and R. Mason, J. Amer. Chem. SOC., 1965, 87, 921.lo2 J. Lewis, R. S. Nyholm, and G. A. Rodley, J . Chem. SOC., 1965, 1483; R. J. H.Clark and C. S. Williams, Imrg. Chem., 1966, 4, 350.lo3 F. A. Cotton and N. F. Curtis, Inorg. Chem., 1965, 4, 241.lo4 I. R. Anderson and J. C. Sheldon, AustraE. J. Chem., 1965, 18, 271.lob I. V. Vasil'kova, A. I. Efimov, and B. 2. Pitirimov, Russ. J. Inorg. Chem.,lo* R. Colton and R. L. Martin, Nature, 1965, 207, 141.lo7 D. F. Shiver, S. A. Shiver, and S. E. Anderson, Imrg. Chem., 1965, 4, 725.lo8 B. N. Figgis and G. B. Robertson, Nature, 1965, 205, 694.1964, 9, 493174 INORGANIC CHEMISTRYComplexes of amines and amine oxides 109 with first-row transition ele-ments have been described.It has been suggested 110 that a perchlorate ionis co-ordinated in solutions of chromium(m) ions in 12~-HC10,. The mag-netic properties of a range of polynuclear chromium(m) complexes havebeen reported.lll Unlike some other trihalides, molybdenum(m) halidesreact with urea and thiourea to form complexes MX,L, rather than the[MLJ3+ species.l12 Sulphur-bridged polymers may be prepared by reactionof Li,MoCl, with chelating sulphur ligends.l13Adducts of the type MoCl,L, are readily prepared 114 from molybdenum-(IV) chloride. The photolysis of the [Mo(CN)J4- ion in aqueous solutionyields HsM~(CN)4(OH),,H,0 as the final product, not K,Mo(CN)~(OH), aspreviously reported.l15 At high temperature, molecular hydrogen reduce8K,Mo(CN), to a molybdenum(n) species K4Mo(CN) 6.Extraction of thisproduct with methanol, in air, yields K,Mo(CN),. The tungsten analoguebehaves similarly.l16 New methods for preparing molybdenum and tungstenoxyhalides, and addition reactions of these compounds have been des-cribed .llNew molybdenum and tungsten bronzes have been described.ll* Amethod for growing single crystals of salts of heteropoly-acids has beendevised 119 and applied to ammonium 12-molybdophosphate. The reductionof molybdic acid with diphenylcarbazide has been studied;120 dimericspecies are produced. Several polytwgstate systems have been studied.121Manganese, Technetium, and Rhenium.-The chemistry of technetiumand rhenium; and the analytical chemistry of technetium have been re-viewed.lZ2A five-co-ordinate structure has been established 123 for the compounds(Ph2MeAs0),M(C1O,),; [MI1 = Mn+Zn]; the fifth position in a tetragonallo@ J.H. Bright, R. S. Drago, D. M. Hart, and S. K. Madan, Inorg. Chem., 1965,4,18 ; R. Longhi and R. S. Drago, ibid., p. 11 ; R. S. Drago, J. T. Donoghue, and D. W.Herlocker, &id., p. 836; S. K. Madan and W. E. Bull, J . Inmg. Nuclear Chem., 1964,26, 2211.1l0 K. M. Jones and J. Bjerrum, Acta Chem. Scund., 1965, 19, 974.111T. Morishita, K. Hori, E. Kyuno, and R. Tsuchiya, Bull. Chem. Soc. Japan,1965, 38, 1276; H. Kobayashi, T. Haseda, and M. Mori, ibid., p. 1455.112 T. Komorita, S.Miki, and S. Yamada, Bull. Chem. SOC. Japan, 1965, 38, 123;V. I. Spitsyn, I. D. Kolli, and T’am Wen-hsai, Rws. J. Inorg. Chem., 1964, 9, 51; A. I.Grigor’ev, T’am Wen-hsai, I. D. Kolli, and V. I. Spitsyn, ibid., p. 1397.113 L. F. Lindry, S. E. Livingstone, and T. N. Lockyer, Austral. J. Chem., 1966,18, 1549.1l4 E. A. Allen, K. Feenan, and G. W. A. Fowles, J. Chem. Soc., 1965, 1636.llaA. W. Adamson and J. R. Perumareddi, Inorg. Chem., 1965, 4, 247.116 J. S. Yoo, E. Griswold, and J. meinberg, Inorg. Cheem., 1965, 4, 365.117 R. Colton and I. B. Tomkins, Austral. J . Chem., 1965, 18, 447; K. Feenan andG. W. A. Fowles, Inorg. Chem., 1965, 4, 310; D. A. Edwards, J . Inorg. Nwlear Chem.,1965, 27, 303.P.-H. Hubert, Compt. rend., 1965, 260, 3677; L.E. Conroy and T. Yokokawa,Inorg. Chem., 1965, 4, 994.ll0 J. van R. Smit, J. Inorg. Nuclear Chem., 1966, 27, 227.lao A. Paigankar and B. C. Haldar, J. Indian Chem. Soc., 1965, 42, 25.H. R. Craig and S. Y. Tyree, Inorg. Chem., 1965, 4, 997; W. N. Lipscomb, ibid.,p. 132; 0. Glemser, W. Holzangel, W. Holtje, and E. SchwarzIIltLM, 2. Nuturforah.,1965, 20b, 725.la2 R. Colton, “ The Chemistry of Rhenium and Technetium,” J. Wiley, New York,1965; A. A. Pozdnyakov, Russ. Chem. Rev., 1965, 84, 129.13* J. Lewis, R. S. Nyholm, and G. A. Rodley, Nature, 1965, 207, 72MABBS AND MACHIN: THE TRANSITION ELEMENTS 175pyramidal arrangement being occupied by a perchlorate group. DimericN-methylsalicylaldimine complexes of manganese-, cobalt-, and zinc-(n)have also been shown to be five-co-ordinate.124 The nitrate ligands aresaid 125 to be bidentatre in complexes [M(C,H,NO),(NO,),]; MI1 = Mn, Co,Ni, or Cu; this is supported by infrared and visible spectroscopic evidence.The infrared spectra of complexes [M(NC0)J2-; MI1 = Mn-+Zn can beassigned by assuming Td symmetry (except for M = Cu), implying a linearM-N-C-0 system; ions M(NCS)42-, MI1 = Mn or Fe are said to be tetrahe-dral and nitrogen-bonded.126 The ligand-field strength of 4,4',4",4"' -tetrasulphophthalocyanine co-ordinated to manganese-, iron-, cobalt-,nickel-, or copper-(=) has been found127 to be equal to that of cyanide.Azido-complexes (Et4N)2Mn(N3)4 and (Ph4As)Pd(N3), have been pre-pared.128 The preparation, far-infrared spectra, and thermal decompositionof Complexes of manganese, iron, cobalt, nickel, copper, and zinc with aminesand other nitrogen donors have beenCalorimetric studies of nitriloacetic acid complexes of divalent ions man-ganese to zinc show that the considerable differences in stability are due toentropy effects, the entropy of formation of the copper complex being par-ticularly large.Similar measurements of bipyridyl and tetraethylene-pentarnine complexes of these elements have also been reported.lS0One of the most interesting structural studies reported has established 131for the first time a trigonal prismatic co-ordination in tris(ck-1,Z-diphenyl-ethene-l,2-dithiolato)rl~enium(m). It has been suggested that, by analogywith this compound, supported by magnetic e.s.r., and polarographic studies,the complexes ML,- M = Cry Mo, W; L = toluene-3,4-dithiol, S,C,Ph,, orS,C,(CF,),] and [L = toluene-3,4-dithiol, S2CzPh2, or maleonitriledithiolate] also have this form of six-~o-ordination.~~~The oxidation of ReBr, in concentrated HBr leads 133 to a variety ofproducts depending on the cation present, e.g., Cs[ReOBr,], (Ph4As),ReBr,.Thiourea, acetylacetone, and mixed phosphine acetylacetone complexes ofrhenium( DI) have also been described.134 A number of complex technetiumoxides have been prepared 135 containing technetium in all oxidation statesfrom (m) to (VII).Compounds containing [Re2C1J2- and [Re2Br,l2- ions have been preparedla4P. L.Orioli, M. DiVaha, and L. Sacconi, Chm. Comm., 1965, 103.126 R.L. Carlin and M. J. Baker, J . Ohm. SOC., 1964, 5008.126 D. Forster and D. M. L. Goodgame, J . Chem. SOC., 1965, 263, 268.la8 W. Beck, K. Feldl, and E. Schuierer, Angew. Chem. Internat. Edrt., 1965, 4,439.la0 I. S. Ahuya, D. H. Brown, R. H. Nuttall, and D. W. A. Sharp, J . Inorg. NuclearOh., 1965, 27, 1105, 1625; J. R. Allen, D. H. Brown, R. H. Nuttall, and D. W. A.Sharp, ibzd., pp. 1305, 1865.130 J. A. Hull, R. H. Davies, and L. A. K. Staveley, J. Chem. SOC., 1964, 5422;R. L. Davies and K. W. Dunning, ibid., 1965, 4168; P. Paoletti and A. Vacca, ibid.,1964, 6051.Is1 R. Eisenberg and J. A. Ibers, J . AwAr. Clzern. SOC., 1965, 87, 3776.E. I. Stiefel and H. B. Gray, J . Amer. Chem. SOC., 1965, 81, 4012.lS3F. A. Cotton and S. J. Lippard, Inorg.Chem., 1965, 4, 1621.lS4 L. I. Evteev, Rws. J. Inorg. Chem., 1964, 9, 336; D. E. Grove, N. P. Johnson,lS5 C. Keller and B. Kanellakopulos, J . Inorg. Nuclear Cbm., 1965, 27, 787.J. H. Weber and D. H. Busch, Inorg. Chem., 1965, 4, 469.C. 5. L. Locke, and G. Wilkinson, J . Chem. SOC., 1965, 490176 INORGANIC CHEMISTRPand shown to have the structure (I). Each rhenium is surrounded by asquare-planar array of cholorines, the dimer being formed by a rhenium-rhenium bond (Re-Re = 2.24 A in the chloride). The chlorines are in theeclipsed configuration; and this is said to be necessitated by the formation ofa S-bond between the rhenium atoms. This is perhaps the best evidencepresented to date for the existence of &bonds. (NH,),Tc,C18 is virtuallyisostructural with the rhenium analogue.136 The trimeric species [Re3Xl2I3-;[Re3Xll]2- (X = C1 or Br), and [Re,Br,,]- are well established, and additioncompounds, e.g., Re3XgL, for many unidentate ligands L, Re,Cl,(acety-lacetone),, Re,Cl,(SCN),(dithiocarbamate), etc., have been ~repared.13~ The[Re3Brl1l2- ion has been shown to have a structure similar to that of thech10ride.l~~ Compounds of empirical formula M,IRe,Br, ca,n be prepared 139but it has been shown that crystals contain Re,Br, and [ReBr612- units.Bonding in these clusters has been discussed 140 and the magnet,ic and massspectrometric properties of rhenium(1rr) chloride ~0nsidered.l~~It has been suggested that rhenium(1v) chloride is trimeric, based on itsmagnetic properties; on the other hand technetium(1v) chloride is an octahe-dral polymer, (Tc-Tc = 3.59 A).l42 When pyridine (py) is reacted 143 withrhenium(1v) iodide some Re1,py is formed as well as ReI,py2; the former isdiamagnetic and is formulated as Re,I,py,.In the same system, bipyridylforms Re,I, (bipyridyl),.Re205 and Cd,Re207 have been prepared.144 Following the prepara-tion 145 of ions [ReX,O]- (X = C1, Br, I) it is suggested that earlier formu-lations [ReBr,(H,O,)]- and [ReBr,]- are wrong. Cs2ReOC15 can be made 146F. A. Cotton, N. F. Curtis, B. F. G. Johnson, and W. R. Robinson, Inorg. Chem.,1965,4,326; F. A. Cotton and C. B. Harris, ibid., p. 330; F. A. Cotton and W. K. Bratton,J . Amr. C h m . SOC., 1965, 87, 21.13' B. H. Robinson and J. E.Ferguson, J . Chem. SOC., 1964, 5683; F. A. Cotton,S. J. Lippard, and J. T. Mague, Imrg. Chem. 1965, 4, 508.138 M. Elder and B. R. Penfold, Nature, 1965, 205, 276.13* F. A. Cotton and S. J. Lippard, Inorg. Chem., 1965, 4, 69.14O J. E. Fergusson, B. R. Penfold, M. Elder, and B. H. Robinson, J . Chem. Soc.,141 D. Brown and R. Colton, Austral. J . Chem., 1965, 18, 441; K. Rinke and H.142 R. Colton and R. L. Martin, Nature, 1965, 205,239; M. Elder and B. R. Penfold,ld4 S. Tribalat, D. Delafosse, and C. Piolet, Compt. rend., 1965, 261, 1008; P. C.Donohue, J. M. Longo, R. D. Rosenstein, and L. Katz, Inorg. Chem., 1965, 4, 1152.1osF. A. Cotton and S. J. Lippard, Chm. Comm., 1965, 245.146 R. Colton, Austral. J . Chem., 1965, 18, 435.1965, 5500; F. A.Cotton, Imrg. Chm., 1965, 4, 334.Schiifer, Angew. Chem. Internat. Edn., 1965, 4, 148.Chem. Comrn., 1965, 308.C. Furhi and G. CiulIo, J . Imrg. Nuclear Chem., 1965, 27, 1167MABBS AND MACHIN: THE TRANSITION ELEMENTS 177from rhenium(v) chloride in ~ZM-HCI; it oxidises in air to Cs,ReOCI,. Somerhenium( v) amine and biguanide complexes have been synthesised.l*7Only three of the five predicted infrared frequencies but all of the Ramanfrequencies were observed in a study148 of rhenium(vn) fluoride. Thestructures of a number of mixed oxides containing rhenium(m) have beendetermined,l*D their general formula, being A,nRe2V11M1102. Alkali- andalkaline-earth metal salts of penta- and hexa-oxorhenate(m) have also beenprepared.l5oIron, Ruthenium, aad Osmium.-A review of the chemistry of osmiuma,nd its compounds has appeared during this year.151In the course of the reaction between Fe(CO), and amines, a t room tem-perature, the following three species were observed to appear successivelyin time ; >NH+-CO-Fe( CO),-, HFe( CO),- and >NH-Pe( C0)4.152 Withthe constrained phosphite ester, 4-methyl-2,6,7-trioxa-l-phosphabicyclo-[2,2,2]octane, mono- and di-substituted complexes of Fe(CO)6 have beenobtained.153 The reduction of RuCl,(CO) 2(Ph3P)2 with zinc in dimethyl-formamide, under a pressure of carbon monoxide, gave Ru(CO),(Ph,P)This latter compound can then undergo a series of oxidative additions, withreagents such as iodine, with the loss of one carbon monoxide group.15Q Anew series of hydride-aryl complexes typified by cis-[RuH( C1 ,,H,) ,( PP)2](where PP = Me,PCH,CH,PMe,), has been reported.155 Pyrolysis of thesecompounds can give [Ru(PP),], the physical properties of which are con-sistent with hydride transfer, from an alkyl side-chain of the ligand, to themetal atom.The Mossbauer spectra of Na[Fe,(CO),,Hj and Fe,(CO),, showthat in each compound only two of the iron atoms are eq~iva1ent.l~~ Whencoupled with X-ray data, these spectra suggest that the compounds havebridged triangular structures.Complexes with the general formula FeL,X,, (where L = 2,2'-bi-2-imidazoline, Ph3As0, Ph,PO, or quinoline, and X = halide), have beenprepared. Similar complexes of Con, NiII, and Cu' have also been reportedwith 2,2'-bi-2-imidazoline and spectral measurements used to show that thisligand occupies about the same position as NH, in the spectrochemicalseries.157 The iron-Ph3P0 and -Ph,AsO complexes are isomorphous withthe corresponding cobalt compounds, which are known to be tetrahedral.With 8-aminoquinoline as ligand, complexes of the types MLCl,, (whenM = FeII, Cu'I, CdII, or Znrr) and ML,X2, (when M = CoTr, Nil1, Curr,147 J.H. Beard, J. Casey, and R. K. Murmann, I.norg. Chem., 1965, 4, 797; M. M.14* H. R. Claassen and H. Selig, J . Chern. Phys., 1965, 43, 103.J. M. Longo, L. Katz, and R. Ward, Imrg. Chern., 1965, 4, 235.lS0 R. Scholder and K. L. Huppert, 2. amrg. Ch., 1964, 334, 209.161 W. P. Griffith, Quart. Rev., 1965, 19, 254.W. F. Edgell, M. T. Yang, B. J. Bulkin, R.Bayer, and N. Koizumi, J . Amer.lSs J. G. Verkade, R. E. McCarley, D. 0. Hendricker, and R. W. King, Inorg.16* J. P. Collman and W. R. Roper, J . Amer. Chem. Soc., 1965, 87, 4008.16b J. Chatt and J. M. Davidson, J. CJLem. SOC., 1965, 843.lssN. E. Erickson and A. W. Fairhall, I m g . Chern., 1965, 4, 1320.117 D. Forster and D. M. L. Goodgame, J . Chem. SOC., 1965, 454; J. C. Wang andRay, J . Imrg. Nuclear Chem., 1965, 27, 2193.Chem. SOC., 1965, 87, 3080.Chem., 1965, 4, 228.J. E. Bauman, jun., I w g . Chem., 1965, 4, 1613178 INORGANIU CHEMISTRYCdn, or Znn and X = C1-, Br- C10,- or NO,-) have been obtained.158 Thefirst example of tetrahedral iron(=) with the metal bonded to four oxygenatoms has been reported to occur in bis( dipivaloylmethanido)iron(n) .I59The measurement of the magnetic moment of (Fe salen)NO, (where salen =NN'-bis-salicylidene-ethylenediamine), over a temperature range, indicatesthe existence of a spin-free-spin-paired equilibrium.laO Nitrosyl thio-cyanates, aryl and alkyl mercaptides of iron(=) and cobalt(=) have beenisolated and then treated with tertiary phosphines or stibines to give thecomplexes M(NO),LR, (where L = phosphine or stibine and R = NCS-,C,H,S-, or C,H5S-).1a1In [Fe(CN),NOI2- the electronic structure is reported to be dominatedby the strong FeNO bond and the order of the energy levels should bezz,yx < xy < n*NO < xz - y2 < z2.16, For [Fe(CN),N0J3- the measure-ment of the e.8.r.14N hyperbe coupling tensor leads to the conclusion thatthe unpaired electron is mainly associated with the dzl orbital, the Fe-N-0direction being the a ax is.^^^ The iron( II) complex of 4,4',4",4"'-tetrasul-phophthalocyanine has been shown t o be a reversible oxygen-carrier in thesolid state.In solution, at neutral pH, it was not oxidised to ~ o D ( I T I ) . ~ ~ ~The preparation of RuPcClz and IrPcCl,, (where Pc = phthalocyanine),and a general discussion of the spectra of transition-metal phthalocyanineshas also been given.lg5 An investigation, over a temperature range, of therelative intensities of the C-N stretching vibration in the complexesFe(phen) ,( SCN) and Fe( bipy) 2( SCN) 2, show that they follow similar curvesto the magnetic moments. However, the infrared spectral evidence tendsto rule out the previous suggestion of a polymeric structure, with both ionicand co-ordinated thiocyanate g r 0 ~ p s .l ~ ~ The infrared spectra of the com-pounds Fe(C0)&3g2X, are reported to indicate that they consist of mono-meric ch-Fe( CO),( HgX) 2, in which there are two Pe-Hg bonds.ls7 Reactionof ruthenium and platinum salts with stannous chloride gave complexm ofthe type [MClz(SnC13)2]2-, in which SnC1,- behaves in a similar manner to achloride ion.168The compound Fe(NO,)P,O, has been prepared and formulated as(NO+)[Fe(NO,)&. When it is sublimed in vaxuo, there appears to be astructural change, probably to (NO,+)Fe(NO,),]-. The vapour-phasereaction between Fe(CO), and NO2 is reported to give [Fe(NO,)]O.l69168 J. C. Fanning and L.T. Taylor, J. Inorg. N&ar Chem., 1965, 27, 2217.158 J. P. Fackler, D. G. Holah, D. A. Buclhgham, and J. T. Henry, Inorg. Chem.,16oA. Earnshaw, E. A. King, and L. F. Larkworthy, Chem. C m . , 1965, 180.161 W. Hieber, J. Bauer, and 0. Neumair, 2. anorg. Chem., 1966, 335, 250.168 P. T. Manoharan and H. B. Gray, J . Amer. Chem. SOC., 1966, 87, 3340; H. B.168 D. A. C. McNeil, J. B. Raynor, rand M. C. R. Symons, J . Chem. SOC., 1965, 410.164 J. H. Weber and D. H. Busch, Inorg. Chern., 1965, 4, 469; D. Vonderschmitt,165 B. D. Berezh and G. V. Sennikova, Dokludy A M . Nauk S.S.S.R., 1964, 159,166 W. A. Baker and (3. T. Long, Chem. Cmm., 1965, 368.167 D. M. Adams, D. J. Cook, and R. D. W. Kemmitt, Nature, 1966, 205, 689.168 J. F. Young, R.D. Gillaxd, and 0. W m o n , J. Chem. SOC., 1964, 6176.16eC. C. Addison, B. F. G. Johnson, and N. Logan, J. Chm. rSoc., 1965, 4490;1966, 4, 920.Gray, P. T. Manoharan, J. Pearha, and R. F. Riley, Chmn. Convna., 1965, 62.I(. Bernauer, and S. Fallab, Helv. Chim. Ada, 1965, 48, 961.1127.C. C. Addison, P. M. Boorman, and N. Logan, ibid., p. 4978MABBS AND MAUHIN: THE TRANSITION ELEMENTS 179Complexes of NN-dimethylethylenedamine N-oxide with iron(m) and otherbi- and ter-valent transition-metal ions have been reported.lT0 The mag-netic properties of (Fe salen),O and (Fe salen)X, (where X = Cl- or Br-)have been investigated and the behaviour of the " oxide " interpreted onthe basis of spin-spin interaction in a binuclear c0rnp1ex.l~~ A series ofnitrosylruthenium(m) complexes containing nitrato- or aquo-groups hasbeen de~cribed.l7~ The main product of the reaction between rutheniumor osmium chlorides and 1,2-dicyanobenzene, at -280" c, was found tobe PcMCI[C,H,(CN),].~~~ In the complexes MCl,(Et,S), (where M = Ru,Rh, or Ir), the stability of the M-S bond is reported to be in the orderRh > Ir > Ru.In this same work the compound [RuCl,(Et,S),], waaisolated and its room-temperature magnetic moment found to be 0-95 B.M.174Pure u- and p-RuCl, have been prepared from ruthenium metal and0hl0rine.175 The preparation of a number of osmium nitrido-complexes hasbeen reported and their infrared spectra used to suggest possible s t r u c t ~ r e s . ~ ~ ~Cobalt, Rhodium, and Iridium.-The reaction of rhodium trichloridewith triphenylphosphine, in non-alcoholic oxygen-containing solvents, suchas dimethylformamide, has been shown to give [ RhC1( CO)( PPh,) Thisreaction is similar to that which occurs in alcohols.Contrary to this,(Ph,P),RhCl has been prepared from RhCl,, using ethyl alcohol as a sol-vent.178 Complexes containing silicon hydride residues have been reportedto be produced in the reaction between SiH,I and [Co(CO),]- and between[ (Ph,P),Ir(CO)Cl] and silicon hydride~.l7~A large number of complexes of the type CoLnX2 (where L = amine,X = halide or pseudo-halide), have been isolated and their structures dis-cussed on the basis of infrared, ultraviolet, and visible spectra and magnetioproperties.lsO Cobalt(=) complexes with Schif€ bases have also been inves-tigated and their structures discussed.Depending on the Schif€ base used,octahedral, tetrahedral, or five-co-ordinate Complexes can be obtained.181Recent investigations32 have ruled out a previous suggestion that the170 J. T. Summers and 5. V. Quagliano, Inorg. Ohm,. 1964, 3, 1767.171 J. Lewis, F. E. Mabbs, and A. Richards, Nature, 1965, 207, 865.17$ D. Scargill, C. E. Lyon, N. R. Large, and J. M. Fletcher, J . Inorg. NuchrChem., 1965, 27, 161; J. M. Fletcher and J. L. Woodhead, ibid., p. 1517.17aI. M. Keen and B. W. Mderbi, J . Inorg. Nuclear Ohem., 1965, 27, 1311.17c J. E. Fergusson, J. D. Karran, and S. Seevaratnam, J. Chm. SOC., 1965, 2627.171i K. R. Hyde, E. W. Hooper, J. Waters, and J. M. Fletcher, J.Less C n176 W. P. GrSth, J. Chem. SOC., 1966, 3694; G. W. Watt and W. C. McMordie, jun.,177 A. Rusina and A. A. VlEek, Nature, 1965, 208, 295.178M. A. Bennett and P. A. Longstaff, C i ~ m . Comm., 1965, 846.179 A. J. Chalk and J. F. Harrod, J . Amer. Chem. SOC., 1965, 87, 16; B. J. Aylettand J. M. Campbell, C M . Conzm., 1965, 217.180 N. H. Agnew and L. F. Larkworthy, J . Chem. SOC., 1965, 4669; H. C. A. King,E. Koros, and S. M. Nelson, W., 1964,4833; S. M. Nelson and T. M. Shephard, J. Inorg.N w k w Chem., 1965, 27, 2123; J. R. Allan, D. H. Brown, R. H. Nuttall and D. W. A.Sharp, ibicl., p. 1305; I. S. Ahuja, D. H. Brown, R. EL. Nuttall, and D. W. A. sharp, as., p. 1625; W. R. McWhinnie, ibid., p. 1619; D. P. Graddon and E. C. Watton, Austral.J .Chem., 1965, 18, 507; D. B. Fox, J. R. Hall, and R. A. Plowman, &id., p. 691.lS1 L. Srtccloni, M. Ciampolini, and G. P. Speroni, Inorg. Chern., 1965, 4, 1116;R. W. Oehmke and J. C. Bailar, jun., J . Inorg. NzccEeccr Chem., 1965,27,2199; H. Nishi-kwa and S. Yamada, Bull. Chem. SOC. Japan, 1965,3$, 1506; L. Sacconi, M. Ciampolini,and G. P. Speroni, J . A m p . Chern. SOC., 1965, 87, 3102.Met&, 1965, 8, 428.J . Imrg. Nuckar Chem., 1965, 27, 2013180 INORGANIC CHEMISTRYcobalt(@ complex with NN'-bis-salicylidene-ethylenediamine contains anaquo-bridge. The infrared spectra of the mono-nitric oxide adducts of thiscomplex, and some substituted derivatives, indicate that a conjugatedsystem can extend from the substituent to the NO molecule, v i a the metal.1s2X-Ray crystallographic studies, on bis- (2,5-dithiahexane)cobalt(n) perchlor-ate, have shown the perchlorate groups to be co-ordinated to the cobalt.183Infrared studies on the compounds CoL,(NO,), (where L = or-picoline,quinoline, isoquinoline, or pyridine N - ~ x i d e ) , ~ ~ ~ and on (NO+)[CO(NO,)~]-,~~~indicate that the nitrate group is acting as a bidentate ligand.Measurementof the room-temperature magnetic moment of 4,4',4'',4"'-tetrasulpho-phthalocyaninecobalt(n), a t different field strengths, indicates that there isconsiderable intermolecular interaction present.186 However, in aqueoussolution the magnetic moment was found to be 1.88 B.M., leading to theconclusion that, here, the cobalt is simply spin-paired. The effect of addingdonor ligands was reported to only slightly reduce the magnetic moment.The e.s.r.spectra of or- and #l-coba.lt phthalocyanine, diluted in the corre-sponding zinc and nickel derivatives, have been investigatedP87The first example of a six-co-ordinate cobalt@) complex containing onlymonodentate sulphur ligands has been isolated as the hexa-NN'-dicyclo-hexylthioureacobalt(rr) ion.18* Complexes of the cationic ligands, #l-amino-ethyltrimethylammonium and y-aminopropyltrimethylammonium, of thetype [ML6](C10J8 (where M = ColI or Nil1), have been reported.l89 Avariety of physical measurements on the compounds [ CoLJClO,) , (whereL = trimethylamine N-oxide or tetramethylguanidine), indicate that thecobalt is tetrahedrally co-ordinated.lgO A series of cobalt(11)-8-hydroxy-quinoline complexes has been isolated, in which the ligand can occuras either a neutral and/or a protonated bidentate chelating or bridgingThe effect of a variety of substituents, on the optical rotatory dispersionof some CoII, Nil1, and CuII Schiff base complexes has been reported.19zOptical rotatory dispersion and circular dichroism have been used to charac-terise, and in some cases determine the absolute configuration of, ColI1ammine and amino-acid complexes.193 The first amino-acid complexes ofrhodium(m), namely p-( +)- and #l-( -)-tris-[~( +)-alaninato]rhodiumO,group .l 91leap.C. Hemlett and L. F. Larkworthy, J. Chem. Soc., 1965, 882; A. Emhaw,183 F. A. Cotton and D. L. Weaver, J. Amer. Chem.SOC., 1965, 87, 4189.184 R. L. Carlin and M. J. Baker, J. Chem. SOC., 1964, 5008; A. B. P. Lever, Inorg.186 J. H. Weber and D. H. Busch, I w g . Chem., 1965, 4, 469, 472.187 J. M. Assour and W. K. Kahn, J . Amer. Chem. SOC., 1965, 87, 207.188 G. Yagupsky and R. Levitus, Inorg. Chem., 1965, 4, 1589.J. V. Quagliano, J. T. Summers, S. Kida, 8nd L. M. Vallerho, Imrg. Chem.,1964, 8, 1557.190 R. Longhi and R. 8. Drago, Inorg. Chem., 1965,4,11; R. S . Drago, J. T. Donoghue,and D. W. Herlocker, ibid., p. 836.191S. Lenzer, J. Chem. Soc., 1964, 5768.1 9 1 A. P. Terent'ev, G. V. Panova, and E. G. Rukhadze, J. Gen. Chem. (U.S.S.R.),1964, 84, 3049, 3055, 3060.A. M. Sargeson and G. H. Searle, Inorg. Chem., 1965, 4, 45; B. E. Dough andS. Yamada, ibid., p.1561; K. Garbett and R. D. Gillard, J. Chem. Soc., 1966, 6084.P. C. HewIett and L. F. Larkworthy, ibid., p. 4718.Ohm., 1965, 4, 1042.C. C. Addison and D. Sutton, J. Chem. SOC., 1964, 5563MABBS AND MACHIN: THE TRANSITION ELEMENTS 181have also been reported.194 The circular dichroism spectra of a number ofcobalt(rn) amine complexes have been measured and discussed in terms ofthe properties of the ligands and the symmetry of the ligand field>95However, low-temperature single-crystal spectral studies on the complex(-J-)[Co en,]Cl,NaCl,GH,O have raised some doubts as to the applicabilityof the above interpretations.lgsThe ultraviolet irradiation of [Co(diam),]Cl, (where diam = ethylene-diamine, propylenediamine, or butylenediamine), in aqueous solution, hasbeen shown to give mainly cobalt(=), ammonia, an aldehyde, and thediamine.197 Complexes of the type L,X,Rh-HgY, (where L = Ph,AsMe;X = C1 or Br, Y = F, C1, Br, or I), containing an Rh-Hg bond, havebeen prepared by the reaction of L,X,Rh-H with mercuric, mercurous,or organo-mercury compounds.Similarly ( Ph,P) 2(CO)C1,1r-HgCl wasprepared from (Ph,P),(CO)CIIr and HgC1,.Ig8 The reaction of rhodium oriridium salts with SnC1, gave the binuclear complexes [Rh2C1,(SnCl,),]4- and[ Ir2Cl6( SnCl,)4]4-. Neutral complexes containing (SnCI,) - together withPh,P, Ph,As, or diolefins can also be prepared.168(where X = C1, Br, I), [Rh,(CO),X,I2- (where X = C1, Br) and [Rh(CO)14]-,have been isolated. On the basis of infrared spectral evidence, the RhIcomplex was assigned a cis-square-planar structure, whilst the binuclearcomplex is thought to contain halogen bridges.lg9 The two isomers ofcis-[Rhpy4Br,]Br,6H,0, reported previously, have now been shown tobe trans-[ RhPy4Br,]Br,6H ,O (yellow) and trans-[ Rhpy,Br ,I( H 5O JBr,(orange).200 The formation of a hydridic species, by the reduction of thetrans-dichlorotetrapyridinerhodium( m) ion with borohydride or hypophos-phorous acid, has been reported.201 The reaction of triphenylstibine withK31rBr6 has led to the isolation of the following complexes: K[IrBr,L,],IrBr3L2, IrBr3L3, H[IrBr,L,], and I~HBI-,L,.~O~ The magnetic moment ofCs,RhCl, has been measured over the temperature range 78-300 O c andthe results interpreted in terms of an electron delocalisation parameterK = 0.7 and a spin-orbit coupling constant of 990 ~m.-l.~O~ The preparationand magnetic behaviour of RhF,, IrF5, and the previously unknownCsRhF, have been reported.204Nickel, Palladium, and Platinum.-The preparation of complexes of thetype Ni(PF,), and Ni(CO),(PF,),, (where 0 < x < 4), using a number oflg4 J.H. Dunlop and R. D. Gillard, J . Chem. Soc., 1965, 6531.lg6 R. A. D. Wentworth and T. S. Piper, Inorg. Chem., 1965, 4, 202; S. F. Masonand B. J. Norman, Chem. Comm., 1965, 48, 73; A. J. McCaffrey, S. F. Mason and B. J.Norman, &id., pp. 49, 132.lg6 R. Dingle, Chem. Cornm., 1965, 304.lD7 D. Klein and C. W. Moeller, Inorg. Chem., 1965, 4, 394; W. C. Taylor and C. W.Moeller, &id., p.398.lD8 R. S. Nyholm and K. Vrieze, J . Chem. Soc., 1965, 5331, 5337.ls9 L. M. Vallerino, Inorg. Chem., 1965, 4, 161.%O0 D. Dollimore, R. D. Gillard, and E. D. McKenzie, J . Chem. SOC., 1965, 4479.%OlB. N. Figgis, R. D. Gillard, R. S. Nyholm, and G. Wilkinson, J. Chem. Soc.,A new series of halogenocarbonyl anions with formulations [Rh( CO)1964, 5189.A. Araneo and S. Martinengo, Cfazzettu, 1965, 95, 825.I. Feldman, R. S. Nyholm, and E. Wakton, J . Chem. SOC., 1965, 4724.=04 N. Bartlett and P. R. Rao, Chem. Comm., 1966, 252; J . H. Holloway, P. R.Rao, and N. Bartlett, ibid., p. 306182 INORGANIC CHEMISTRYMerent methods, has been described.205 Using radioactive phosphorus,the reaction :Ni( PCI,), + 4PF, + Ni( PF& + 4PC1,has been shown to proceed wia ligand- rather than halogen-exchange.206In the reaction between P2CI, and Ni(CO), a t Ooc, a variety of compoundsis formed, depending on the ratios of the reactants.In the compoundsproduced? P2CJ4 can act as either a mono- or bi-dentate ligand.207 With aconstrained phosphite ester, substitution products of Ni(CO),, of the typeN~P(OCH2),C?Me],(CO),,, (where x = 1, 2, 3, or 4), have been preparedand characterised. Trialkyl phosphite derivatives of NiO, of the typeNi[P(OR)&, have been obtained by the reduction of the correspondingNin complexes with graphite-potassium.208 The reduction of K,Ni(CN),with molecular hydrogen is reported to give K4Ni2(CN), and hydrogencyanide.209A number of five-co-ordinate NiII complexes containing quadridentatephosphorus or arsenic ligands have been prepared and assigned trigonalbipyramidal structures,210 whilst some five-co-ordinate Schiff base complexeswe reported to have distorted square pyramidal structures.211 The structuresof other nickel(=) SchifF base complexes have been deduced from spectraland magnetic measurements, and the structures discussed in terms of thecomposition of the ligands.212 When dilute solid solutions of bis- (N-methyl-salicylaldiminato)nickel(n) in, the corresponding zinc(n) complex are formed,the nickel complex assumes the penta-co-ordinate stereochemistry of thehost lattice.213 The occurrence of monomeric or polymeric /Miketonecomplexes of nickel(=) has been shown to depend on the nature of the sub-stituents on the #?-diket~ne.~l~ The position of the square planar + tetra-hedral equilibrium in the complexes Ni[ R,COCH(NHR)R,] 2, was also foundto be dependent on the nature of both Ry and R,,a15 As in the case ofcobalt@), there have been a number of reports of the preparation and assign-ment of the structures of compounds of the type NiL,X, (where L is ana05 R.J. Clark and E. 0. Brimm, Inorg. Chem., 1965, 4, 651; J. R. Olechowaki,C. G. McAlister, and R. F. Clark, ibid., p. 246; T. Kruck and I(. Baur, Chm. Ber.,1965, 98, 3070.ao6 R. J. Clark, P. I. Hoberman, and E. 0. Brimm, J. Inorg. Nuclear Chm., 1965,27, 2109.a07 C. B. Lindahl and W. L. Jolly, Inorg. Chem., 1964, 3, 1634.ao8 K. A. Jensen, B. Nygaard, G. Elisson, and D. H. Nielsen, Acta Chm.Stand.,1965, 19, 768.2oQ Jin Sun Yoo, E. Griswold, and J. Kleinberg, Imrg. Chem., 1965, 4, 366.210 G. Dyer, J. G. Hartley, and L. M. Ventmzi, J. Chem. Soc., 1965, 1293; G. Dyerand L. M. Venanzi, ibid., p. 2771; G. Dyer and D. W. Meek, Inorg. Chem., 1965, 4,1398; G. S. Benner, W. E. Hatfield, and D. W. Meek, ibid., 1964, 3, 1544.211 L. Sacconi, P. Nannelli, N. Nardi, and U. Campigli, Inorg. Chm., 1965, 4, 943.21a N. F. Curtis and D. A. House, J . Chem. Soc., 1965, 6502; A. Chakravorty, J. P.Fennesey, and R. H. Holm, Inorg. Chem., 1966, 4, 26; A. Chahavorty, {bid., p. 127;L. Sacconi, P. Nannelli, and U. Campigli, ib;d., p. 818; A. K. Majumdar and B. C.Bhattacharyya, J . Inorg. Nuclear Chem., 1965, 27, 143; E. J. Olszewaki and D. T.Martin, ibid., p.345; B. Kirson and F. Kassirer, Bull. Soo. chim. France, 1966, 673;E. G. Jkiger, 2. anorg. Chem., 1965, 337, 80.a13 L. Sacconi, M. Ciampolini, and G. P. Speroni, J . Amer. Chm. ~ o c . , 1966, 87,3102.a14 L. Wolf and E. Butter, 2. anorg. Chm., 1965, 339, 191.a16G. W. Everett, jun., and R. H. Holm, J . Amer. Chem. Soc., 1965, 87, 2117MABBS AND MACHIN: THE TRANSITION ELEMENTS 183amine, n can be 1, 1.5, 2, 3, 4, or 6 and X = halide or pseudohalide)?16Co-ordinated perchlorate, tetrafluoroborate, and borohydride anions havebeen reported to occur in the complexes Ni(diamine)B(C10,)2, NiPy,X,(where X = ClO,- or BF,-), and NiA(BH4)S (where A = tetradentateamiae or Schif€ base). Also infrared spectra indicate the presence of biden-tate nitrito-groups in Ki[Me2N(CH,)2NMe](N0,)2 and mono- or bi-dentatenitrate in Ni en2(N03), and [Ni en,N03]C10,.217The nuclear magnetic resonance contact shifts observed for the com-pounds Ni(Ph,P)2X2 (where X = halide), and NiL1L2 (where L, and L,are different aminotroponeimine ligands), have been interpreted in terms ofmetal-to-ligand n-bonding.21* The preparation of the bis( ct-di$hiodiketone)-,bis( dithioglyoxa1)-, and bis( dimercaptoethy1ene)-nickel@) complexes andsome of their chemical and physical properties have been reported.219 Theultraviolet and infrared spectra of nickel(n) ions, in KE'-KCN mixtures,have been interpreted in terms of the presence of Ni(CN),2- and Ni(CN)53-.No evidence was found for the formation of [Ni(CN)5F14- or [Ni(CN)6]4-.220The polarised electrqnic absorption spectra of crystals containing the[Ni(CN),I2- ion have been interpreted on the basis of a square-planar con-figuration in the ground state and a distorted tetrahedral configuration inthe excited state.221 The two forms of bis( benzoylmethylglyoxime)nickel(n)have been shown to be respectively, a crystalline and a disordered species,22anot cis- and &am-isomers as previously reported.A series of nitrile-nickel( 11) halide and perchlorate complexes, and mixed aquo-nitrile- andamine-nitrile-nickel( n) halides, have been isolated. The bis- and tetra-methylcyanidenickel(11) perchlorates have been s h ~ t m by infrared spectralstudies to contain co-ordinated perchlorate ions.223 The reaction between[M(CN0),I2- (where M = NPI, PdII, or Ptxl) and the phosphinee PR,(where R = Et, c6Hll, or Ph), gives the complexes (PR,),M(CNO),.Thesecomplexes have been assigned tram-square-planar structures on the basisof magnetic and dipole-moment rneasurements.224216 S. M. Nelson and T. M. Shepherd, J . Chem. SOC., 1965,3276; D. M. L. Go-odgame,M. Goodgame, and M. J. Weeks, ibid., 1964, 5194; A. B. P. Lever, S. M. Nelson, andT. M. Shepherd, Imrg. Chem., 1965, 4, 810; S. M. Nelson and T. M. Shepherd, ibid.,p. 813; L. M. Vallerino, W. E. Hill, and J. V. Quagliano, ibid., p. 1598; W. E. Bulland L. E. Moore, J. Inorg. Nuclear Chem., 1965, 27, 1341; A. B. P. Lever, ibid., p. 149;E. Uhlig and K. Staiger, 2. anorg. Chem., 1965, 336, 42, 179.N. F. Curtis, J. Chem.SOC., 1965, 924; D. M. L. Goodgame and M. A. Hitchman,Imorg. Chem., 1965, 4, 721; N. F. Curtis and Y. M. Curtis, ibid., p. 804; M. R. Rosenthaland R. S. Drago, ibid., p. 840; S. F. Pavkovic and D. W. Meek, ibid., p. 1091.21e D. It. Eaton and W. D. Phillips, J. Chem. Phys., 1966, 43, 392; E. A. Lalancetteand D. R. Eaton, J. Amer. Chenz. SOC., 1964, 86, 5145.G. N. Schrauzer and V. P. iXayweg, J. Amer. Chem. SOC., 1965, 8'9, 1483; 3585;G. N. Schrawer, V. P. Mayweg, and W. Heinrich, Inorg. Chent., 1965,4,1616; E. Hoyer,Chem. and Ind., 1965, 652.220 J. S. Coleman, H. Petersen, jun., and R. A. Penneman, Imrg. Chem., 1966,4, 135.221 C. J. Ballhausen, N. Bjerrum, R. Dingle, K. Eriks, and C. R. Hare, Inorg. Chena.,1965, 4, 514.222 K. A. Jensen, B.Nygaard, and R. B. Jensen, Acta Chem. Scand., 1965, 19,770.22% A. E. Wickenden and R. A. Krause, Inorg. Chern., 1965, 4, 404; A. V. Babaevaand Kh. U. Ikramov, RUM. J. Inorg. Chem., 1964, 9, 327, 330.224 W. Beck and E. Schwierer, C7xm. Ber., 1965, 98, 298154 INORGANIC CHEMISTRYWhen tetraphenylarsonium chloride was added to a methanolic-hydrochloric acid solution of palladium and tin in the ratio 1 :5,[Ph,As],[PdCl(SnCl,),] was precipitated.22j The reaction of [Pt(SnC1,),]3-with hydrogen, under pressure, gave [HPt(SnC1,),I3-. The compound isbelieved to be the first example of an anionic platinum hydride. Also,X-ray data on [Pt(SnC13),-J3- compounds have shown this anion to betrigonal bipyramidal, with all five tin atoms co-ordinated to the platinum.226Compounds of the type (R3P)2M(GePh3)2 (where M = PdII or PtII), havebeen prepared and the breaking of the &--M bond, with reagents such asiodine, hydrogen chloride, methyl iodide etc., The isolation oftrans-(Ph,P),PtCl,, by the addition of an acetone solution of mercuricchloride to a benzene-acetone solution of trans-bis( tripheny1phosphine)-platinum(=) hydrochloride, a t 0 OC, has been described.228 If the temperatureof the reaction mixture is allowed to rise, only the ck-isomer is obtained.A structural determination of platinum@) chloride has shown it tocontain Pt&1,2 units, with the chlorine atoms situated above the edges ofan octahedron of platinum atoms.229 The electronic absorption spectra ofMagnus's green salt and some of its anologues have been interpreted in termsof metal-metal interactions within the crystals.230 However, other authorsbelieve that the visible spectra arise from the ligand-field transitions of theani~ns.~~l From a study of the infrared spectra of the cis- and trans-isomersof Pt(NH,),CI, and Pt(ND,),Cl, it has been concluded that ligand-ligandinteraction occurs via a filled d-orbital of the platin~m.~3~The preparations of the acetate, benzoate, trifluoroacetate, and penta-fluoroproprionate complexes of palladium(=) have been described.Thefluorocarboxylate complexes were found to be monomeric and the othercomplexes trimeric in solution. The reaction of these complexes with amines,Ph,P or Ph,As gave tran~-Pd(0COR),L,.~~~ In the complexes MX,L[where M = PdII or PtII, X = C1-, Br-, or I- and L = (a-Me2NC6H,),PPhor (a-Me,NC,H,),P], it has been shown that only the phosphorus and oneof the nitrogen atoms of the ligands are bound to the metal ions, to givesquare-planar stereochemistry.234Complexes of nickel(m) of the type NiBr,(dp) and [NiX,(dp),]X, (wheredp = Me2PC2H,PMe, and X = halide), have been is0lated.2~~ Polaro-graphic and electron spin resonance measurements on complexes of thef 2 6 M .A. Khattak and R. J. Magee, Chem. Comm., 1965, 400.226 R. D. Cramer, R. V. Lindsey, jun., C. T. Prewitt, and U. G. Stolberg, J . Amer.227 R. J. Cross and F. Glocking, J. Chem. SOC., 1965, 5422; E. H. Brooks and F.228 A. D. Allen and M. C. Baird, Chem. and I n d . , 1965, 139.419 K.Brodersen, G. Theile, and H. G. Schnering, 2. anorg. Chem., 1965, 337, 120.230 J. R. Miller, J. Chem. Soc., 1965, 713.231 P. Day, A. F. Orchard, A. J. Thornson, and R. J. P. Williams, J . Chem. Phys.,252 K. Nakamoto, P. J. McCarthy, J. Fujita, R. A. Condrate, and G. T. Behnke,f S 3 T. A. Stephenson, S. M. Morehouse, A. R. Powell, J. P. Heffer, and G. Wilkinson,234 H. P. Fritz, 3. R. Gordon, K. E. Schwarzhaus, and L. M. Venanzi, J . Chem. SOC.,235 G. Booth and J. Chatt, J . Chem. SOC., 1965, 3238.Chem. Soc., 1965, 87, 658.Glocking, Chem. Comm., 1965, 610.1965, 42, 1973.I w g . Chem., 1966, 4, 36.J . Chem. SOC., 1965, 3632.1965, 5210MABBS AND MACHIN: T H E TRANSITION ELEMENTS 185type N~(O-SC,H,NH)~ (where n = 0, 1-, or 2-), indicate that the varyingvalues of n are best described in terms of changes in the oxidation states ofthe ligands, rather than of the metal The infrared spectra of somemixed cyano-amine complexes of palladium(=), and the first mixed cyano-complex of rhodium(=), i.e., Rhpy,(CN),C1,2H20, have been used to suggesttheir structures.The rhodium complex is thought to be polymeric with bothterminal and bridging cyanideThe preparation of [PtX,YZen] (where X = halide, Y = halide, OH-,CN-, Z = CN-, NO,, NO,, or OH-), has been described. Also the reactionof [PtX,(CN),en] with silver nitrate gives ([PtX,(CN),en],Ag}NO, it is re-p0rted.23~ The preparations have also been described of [Pd(NH,),Cl,]Cl,([Pd(NH,),]C1,[Pd(NH3)4Br,]Br,) ,239 and Pt(glyc),Cl (where glyc = theglycinate anion) .240Copper, Silver, and Gold.-The reaction between Ph,PAuCl and sodiumborohydride, in ethanol, resulted in the isolation of Au,(Ph3P),C1,3-5H20,which could then be converted into Au,(Ph3P),C1,4CH,0H in methanol.Both of these complexes are thought to contain four gold(0) and one gold(1)atoms, the diamagnetism being explained in terms of interaction between thegold(0) atomsS24l The complexes (triars)M-Mn(CO),, [(triars)M],Fe(CO),,and (triars)M-Co(CO), (where triars = a tri-tertiary arsine and M = Cu orAg) have been isolated.242 The preparation of the complexes LAu-Mn(CO),[where L = (PhO),P, (p-MeOC6H4),P, ( P - M ~ C ~ H ~ ) ~ ~ , Ph,As, or Ph,Sb],and Ph,PAu-Mn(CO),L1 (where L1 = Ph3P, Ph,As, (PhO),P, or pyridine),has been described and the force constants for the carbonyl groups in LAu-Mn(CO), have been calculated from the infrared spectra.243 (Ph,P),CuBH,has been prepared and reacted with HX (where X = ClO,, NO,, or BF,) togive (Ph,P),CuX, in which X is co-ordinated to the copper atom.Thereaction of (Ph,P),CuBH, with anhydrous hydrogen chloride, in benzene,gave Cu2C1,(Ph,P), as one of the products.244 Molecular-weight measure-ments on 1,3-dimethylfriazenocopper(1), in benzene solution, indicate that itis a tetramer, and two possible cyclic structures have been prop0sed.2~5Infrared spectral measurements on the complexes (Xpy) ,MC10, (whereX = 2-, 3-, or 4-cyano and M = CuI, AgI, AuI), have been used to show thatin the 3- and 4-cyano-pyridine derivatives, the metal is bound to the pyri-dine nitrogen, whilst in the 2-cyanopyridine derivative it is bound to the236 E.J. Stiefel, J. H. Waters, E. Billig, and H. B. Gray, J. Amer. Chem. SOC.,1966, 87, 3016.237 R. D. Gillard, J. Inorg. Nuclear Chem., 1966, 27, 1321.238 I. I. Chernyaev, N. N. Zheligovskaya, Lieh-T’i-k’eng and D. V. Kurganovic,Russ. J . Inorg. Chern., 1964,9,312; I. I. Chernyaev, A. V. Babkov, and N. N. Zheligov-skaya, ibid., p. 319.238 A. V. Babaeva and E. Ya. Khananova, Doklady Akad. Nauk S.S.S.R., 1964,159, 1209.240 A. A. Grinberg and Y. Kan, Doklady Akad. Nauk S.S.S.R., 1964, 154, 8.241 L. Malatesta, L. Naldini, G. Simonetta, and F. Cariati, Chem. Co?nm., 1965, 212.242 A. S. Kasenally, R. S. Nyholm, and M. H. B. Stiddard, J. Chem. SOC., 1966,243 A.S. Kasenally, J. Lewis, A. R. Manning, J. R. Miller, R. S. Nyholm, and244 F. Coriati and L. Naldini, Gazzetta, 1965, 95, 201; J. M. Davidson, Chem. and245 F. E. Brinckman, H. S. Haiss, and R. A. Robb, Inorg. Chem., 1965, 4, 936.5343.M. H. B. Stiddard, J. Chem. SOC., 1965, 3407.Ind., 1964, 2021.186 INORGANIC CHEMISTRYnitrile nitrogen.246 Similar measurements on some 2-aminopyridine deriva-tives of silver nitrate have shown that the ring nitrogen of Z-methylamino-pyridine is bound to the silver atom, whereas with 2-aminopyridine and2-amino-6-methylpyridine the metal is bound to both the ring and amino-nitrogen^.^^'The formation of binuclear or more highly polymeric copper(r1) carboxy-late compounds has been correlated with the p&-values and steric proper-ties of the carboxylic The magnetic properties of coppes(r1) ben-zoate, nitrobenzoate, and some adducts of these complexes have beenmeasured over the temperature range 80-300 The magnetic proper-ties of the anhydrous complexes seem to depend on the methods of prepara-tion, this phenomenon being interpreted in terms of the existence of bothbi- and poly-nuclear structures. A reinvestigation of the absorption spec-trum of single crystals of copper(I1) acetate monohydrate has revealed apreviously unreported band a t about 11,000 cm.-1 The assignment of thespectrum is discussed.250 Using a weakly coupled clmomophore model, asuccessful explanation of the absorption spectrum of copper(I1) acetatemonohydrate has been rep0rted.~51 Magnetic measurements on complexesof the type CuLX, (where X = C1 or Br and L = pyridine N-oxide or 4-substituted pyridine N-oxide), have been interpreted in terms of a bicuclearstructure, in which there is considerable magnetic exchange between thecopper atoms.252 On the basis of magnetic, visible, and infrared spectra,and molecular-weight measurements, binuclear structures have been pro-posed for the copper@) salts of acrylic, vinylacetic, and allylacetic acids,253for complexes of the type [ (ampy),Cu( OR)NOJ2 (where ampy = 2-aminopyri-dine, R = H, Me, Et, Prn, n-pentyl) 254 and CU,(M~CO,),(OCH,CH,NR,),.~~~Also, using the same criteria, highly polymeric structures have been postu-lated for Cu( OMe),, Cu( OMe)CI, and Cu( OEt)C1.256The magnetic moments of complexes of the type (CuX,)2- (whereX = GI, Br, and NCS) and [C~(tetramethylguanidine)~](CIO~)~ have beenreported and discussed in terms of departures from tetrahedral stereo-chemistry.257 The electron spin resonance spectrum of the (CUCI,)~- ionhas also been considered in detail5$ The preparations of complexes of the2a6F.Farha, jun., and R. T. Iwamoto, Inorg. Chern., 1965, 4, 844.Z47 E. Uhlig and 31. Bladler, 2. anorg. Chem., 1965, 338, 199.248 J. Lewis, Y. C. Lin, L. K. Royston, and R. C. Thompson, J . Chem. SOC., 1965,6464.249 J. Lewis and F. E. Mabbs, J. Chem. Soc., 1965, 3894; C . S. Fountain and W. E.Hatfield, Inorg. Chem., 1966, 4, 1368; A. Earnshaw and K. S. Patel, J . Inorg. NuclearChem., 1965,27,1805; V.V. Zelentsov, M. N. Volkov, V. M. Allenov, and T. G. Aminov,Russ. J. Inorg. Chem., 1965, 10, 306.250 C. W. Reimann, G. F. Kokoszka, and G. Gordon, Inorg. Chm., 1965, 4, 1082.261A. E. Hansen and C. J. Ballhausen, Trans. Furuday SOC., 1965, 61, 631.262 W. E. Hatfield, Y. Muto, R. B. Jonasson, and J. S. Paschal, Inorg. Chem.,1965, 4, 97; H. R. Schafer, J. C. Morrow, and El. M. Smith, J. Chem. Phys., 1965, 42,504.268 B. J. Edmondson and A. B. P. Lever, Inorg. Chem., 1966, 4, 1608.254 W. R. McWhinnie, J. Inorg. Nuclear Chern., 1965, 27, 1063.2 5 5 F. Hein and W. Ludwig, 2. unorg. Chem., 1965, 338, 63.2 5 6 C. H. Brubaker, jun., and M. Wicholm, J. Inorg. Nuclear Chem., 1965, 27, 59.Z57 R. Longhi and R. S. Drago, Inorg. Chem., 1965, 4, 11; L.Sacconi, M. CiampolmiZ 6 * M. Sharnoff, J . Chem. Phw., 1965, 42, 3383.and V. Ciampigli, ibid., p. 407; D. Forster and D. M. L. Goodgame, ibid., p. 823MABBS AND MACHIN: THE TRANSITION ELEMENTS 187type CuX2L, CuX2L2,nH20, CuXL2C104,nH,0 (where L = 4,6,4’,6’-tetra-methyl-Z,Z‘bipyridyl), Cu(bipyam) ,X2 (where bipyam = 2,2’-bipyridyla-mine) and copper( n) complexes of the tridentate ligand, pyridine-2-carboxy-aldehyde - 2 ’ - p yridylhy drazone , have been described. The structures ofthese compounds are discussed in terms of possible four-, five-, or six-co-ordination.259 Gold phthalocyanine 260 and ( Bun4N) 2[ Au(mnt) 2] 261 havebeen reported and their formulations based on the presence of gold(=).The silver(m) complex, Na5H2Ag(IO6),,16H,O, has been prepared bytwo methods.262 The ligand field spectra of [Cu(OH),]- and the ethylene-bisbiguanide complex of AgIII, in both the solid state and solution, have beenreported and discussed.263 The formation of the complexes [Au( CN) %X,]-(where X = C1, Br, or I), [Au(CN),Cl]- [Au(CN),]-, and HAu(CN),,2H,Ohas been described, and their infrared and Rarnan spectra used to suggestpossible structures.264 The electronic spectrum of the complex Au( dto) 2,(where dto = dithio-oxalate), has been assigned on the basis of the energylevels derived for [ N i ( d t ~ ) ~ ] ~ - - .~ ~ ~Zinc, Cadmium, and Mercury.-The preparation of the 2 : 1 amine : metal-halide complexes of both zinc and cadmium have been reported. The zinccompounds are considered to be neutral tetrahedral species, whilst thecadmium complexes seem to be best described as [Cd( amine),][CdX,].266The pyrazine adducts of zinc, cadmium, and mercury halides, of the typeMX, pyrazine, have been isolated and polymeric structures suggested.267Polymers with molecular weights in excess of 10,000 have been reported forthe dibutylphosphinate and dioctylphosphinate derivatives of zinc( n).268The Raman spectra of the monoiodide, monobromide, and monochloridecomplexes of mercury(I1) have been observed in aqueous solutions with highratios of Hg: halide.Some evidence for the formation of [Hg-l-Hg]3+was also found.269 Infrared spectra have been used to demonstrate theco-ordination, through sulphur, of the sulphite group to mercury.270 Thepreparation of mercuricarbamates has been reported.These complexes wereshown to be less susceptible to hydrolysis than the corresponding stannyl-carbamates.271)Kg W. R. McWhinnie, J . Chem. SOC., 1964, 6165; J. F. Geldard and F. Lions, Imrg.Chem., 1965, 4, 414; J. R. Hall, M. R. Litzow, and R. A. Plowman, Austral. J . Chew.,1965, 18, 1331.260 A. MacCragh and W. S. Koslii, J . Amer. Chem. SOC., 1965, 87, 2496.261 J. H. Waters and H. B. Gray, J . Amer. Chem. SOC., 1965, 87, 3534.2 6 z G. L. Cohen and G. Atkinson, Inorg. Chem., 1964, 3, 1741,263 R. S. Banerjee and S. Basu, J . Inorg. Nuclear Chem., 1965, 27, 363.2 6 4 J. M. Smith, L. H. Jones, I. K. Kressin, and R. A. Penneman, Imrg. Chem.,265 A. R. Latham, V. C. Hascall, and H. B. Gray, Inorg.Chem., 1965, 4, 788.*66 M. Goldstein and E. F. Mooney, J. Inorg. Chem., 1965, 27, 1601.267 H. D. Stidham and J. A. Chandler, J . Inorg. Nuclear Chem., 1965, 27, 397.26sV. Cresceni, V. Giancotti, and A. Ripamonti, J . Amer. C h m . SOC., 1965, 87,J. H. R. Clarke and L A. Woodward, Trans. Furday Soc., 1965, 61, 207.870 J. I. Bullock and D. ‘ x . Tuck, J . Chem. SOC., 1965, 1877.a71A. G. Davies and G. J. D. Peddle, Chem. Comm., 1965, 96.1966, 4, 369; L. H. Jones, ibid., 1964, 3, 1681.392; S. H. Rose and B. P. Blcyk, ibid., p. 20764. TRANSITION-METAL CARBONYLS ANDRELATED COMPOUNDSBy F. J. Kohl and J. Lewis(Department of Chemistry, The University, Manchester)Structure.-Reviews on the alkali-metal derivatives of the carbonyls 1 andthe r81e of organometallic compounds in co-ordination chemistry havebeen published.The infrared spectra of osmium dodecacarbonyl,3 rheniumand manganese decacarbony14 have been analysed by using the techniquediscussed by Cotton and Kraihanzel.5 The use of the overtone and com-bination bands in frequency assignment of metal carbonyls has beene~aluated.~, The infrared spectra of a variety of phosphine-substitutediron carbonyl compounds have been reported,' and the R'aman and infraredspectra of Ni(CO),[P(Ph),] have been interpreted.8 The infrared spectraof the molecules Ni(C180),, Ni(C180)3(C160) have been used to determinethe force constants in nickel carbonyl.9 The mass spectra of chromium,molybdenum, tungsten,lO manganese, and cobalt 11 carbonyls are reported.Loss of CO groups occurs in a stepwise manner and a major positive ionin the spectra of manganese decacarbonyl and cobalt octacarbonyl are thedimetallic ions Mn,+ and Co,+ respectively.The mass spectra of sub-stituted cyclopentadienyl carbonyls of cobalt, manganese, and vanadium l2also of cyclopentadienylmolybdenum nitrosyl carbonyl l3 have been deter-mined.A polymeric platinum carbonyl [Pt(CO),], has Been isolated as a purplecolloidal precipitate by the action of carbon monoxide and water on abenzene solution of [PtCI,(CO),] or as a brown crystalline solid from carbonmonoxide with dilute ethanolic solution of sodium chloroplatinite. Thecompound is unstable in air. A series of stable trimeric platinum clustershave been prepared by reaction of the carbonyl with phosphines.14 A newformulation has been suggested for Co,(CO)12 in which the cobalt atomsform a tetrahedral array;15 each cobalt atom has two terminal and twobridging CO groups and forms a direct metal-metal bond to another cobalt1 R.B. King, Adv. Organometallic Chem., 1964, 2, 157.2 F . G. A. Stone, Pure Appl. Chern., 1965, 10, 37.D. K. Huggins, N. Flitcroft, and H. D. Kaesz, Inorg. Chena., 1965, 4, 166.F. A. Cotton and R. M. Wing, Inorg. Chem., 1965, 4, 1328.F. A. Cotton and C. S . Kraihanzel, J . Amer. Chem. Soc., 1962, 84, 4432; Inorg.Chem., 1963, 2, 633.J. Lewis. A. R. Manning. 5. R. Miller, M. Ware, and F. Nyman, Nature, 1966, Y . 20'7, 142.7 A. Reckziegel and M. Bigorgne, J. Organometallic Chem., 1965, 3, 341.8 W.F. Edgell and M. P. Dunkle, Inorg. Chem., 1965, 4, 1629.@G. Bouquet and M. Bigorgne, Compt. rend., 1965, 261, 2865.10R. E. Winters and R. W. Kiser, Inorg. Chem., 1965, 4, 157.IIR. E. Winters and R. W. Kiaer, J . Phys. Chem., 1965, 69, 1618.12 R. E. Winters and R. W. Kiser, J. Organometallic Chem., 1965, 4, 190.13 R. E. Winters and R. W. Kiser, J . Phys. Chern., 1965, 69, 3198.l4 G. Booth, J. Chatt, and P. Chini, Chem. Comrn., 1965, 639.1 5 D. L. Smith, J. Chem. Phys., 1965, 42, 1460KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 189atom. The monomeric compound Co(CO), has been identified by e.s.r.measurements.lBased on the structure of the ion [Fe3(CO),1H]-, Fe,(CO),, is formulatedas a triangular metal cluster in which one bridging group of the Fe2(CO)gsystem is replaced by an Fe(CO), gr0up.l' The structures of the carbonyland the ion [Fe,(CO),,H]- are then in agreement with expectations fromthe Mossbauer spectra.l* A new polymeric carbonyl [Re(CO)& has beenisolated by reaction of rhenium sulphide with copper in the presence ofcarbon monoxide :I9 the infrared spectrum indicates the absence of bridgingCO groups.The oxygen of the [Re(CO),]+ has been shown to be liableto 1 8 0 exchange with HZ80 whereas no exchange was observed withmolybdenum.20 The metal-metal distance and angular displacement ofd0 groups from the equatorial plane in manganese decacarbonyl has beendiscussed in terms of variation of d / p character to the bonds.21 It hasbeen suggested that the inert-gas configuration is exceeded in a manganesecarbonyl derivative which is formulated as a seven-co-ordinate complex[Mn(CO)5(NHMe)(NH2Me)].22 The crystal structure of cis-(diethylenetria-mine)molybdenum tricarbonyl has been determined and a bond-order-bond-length relationship deduced for metal-carbon bonds.23 The n-bondingin the M(CO), group has been discussed 24 and an attempt made to estimatethe n-acceptor ability of CO in the Group VIB ~arbonyls.~~ The X-raystructure of the compound [Fe2(C5H5),(CO),CNPh] confirms the pre-sence of a bridging isonitrile group.26 The structures of the compounds(CO),M*(PhCOMe) (M = Cr, W) are consistent with the formulation asmetal-carbene derivatives.27Photochemical Reactions.-A series of complexes W( CO) 5L, where L isaromatic or heterocyclic group is formed by photochemical reaction withtungsten carbonyl and the ligand.Infrared spectra indicate a symmetricalbonding to the arene and not to a fixed double bond.28 Photochemicalreaction of chromium and tungsten carbonyls with a variety of sulphidesand sulphoxides to give the compounds M(CO),L has been studied.29Irradiation of iron carbonyl with light or 6oCo y-rays in nitrobenzene yieldsa diamagnetic compound [ (CO) ,FeC,H,NO] in which iron-oxygen-nitrogen-metal bridges are p~stulated.~~ Photochemical substitution reac-tions of manganese decacarbonyl, to yield Mn,(CO),L (L = alkyl andaryl nitrile, pyridine, triphenylphosphine) and with butadiene to givel6 H. J. Keller and H. Wawersik, 2. Naturforsch., 1965, 20b, 938.l7 L.F. Dahl and J. F. Blount, Inorg. Chem., 1965, 4, 1373.lsN. E. Erickson and W. Fairhall, Inorg. Chem., 1965, 4, 1320.lS A. G. Osborne and M. H. B. Stiddard, J . Organometallic Chem., 1965, 3, 340.zo E. L. Muetterties, Inorg. Chem., 1965, 4, 1841.21 M. J. Bennett and R. Mason, Nature, 1965, 205, 760.z2 R. J. Angelici, Chem. Comm., 1965, 486.24 S. F. A. Kettle, Inorg. Chem., 1965, 4, 1661.25 G. R. Dobson, Inorg. Chem., 1965, 4, 1673.26 K. K. Joshi, 0. S. Mills, P. L. Pauson, B. W. Shaw, and W. H. Stubbs, Chem.2 7 0. S. Mills and A. D. Redhouse, Angew. Chem., 1965, 77, 1142.28 I. W. Stolz, H. Haas, and R. K. Sheline, J . Amer. Chem. SOC., 1965, 87, 716.2s W. Strohmeier, J. F. Guttenberger, and G. Popp, Chem. Bey., 1965, 98, 2248.30 E.Koerner v. Gustorf and M. J. Jun, 2. Naturforsch., 1965, Nb, 521.F. A. Cotton and R. M. Wing, Inorg. Chem., 1965, 4, 314.Comm., 1965, 181190 INORGANIC CHEMISTRYC,H,(CO) ,Mn-Mn(CO) 5y have been studied.3l Manganese decacarbonylpolymerises monoepoxides in U.V. light ;32 manganese and rhenium carbonyl,and phosphine-substituted rhenium carbonyls have been used as poly-merisation catalysts in carbon tetrachloride solution.33Nitrogen, Phosphopus, and Arsenic Derivatives.-Tetrakis(dimethy1-amino)-titanium, -zirconium, or -hafnium interact with nickel, iron, andmolybdenum carbonyls to give 1 : 2 adducts of the type Ti(NMe2),,2Ni(C0),.34The reaction of tetraphenylcyclotetraphosphine and arsine with nickel, iron,chromium, molybdenum, and tungsten carbonyl have been reported.35With molybdenum and tungsten ring expansion occurs to give the (PhP),ring system.Terpyridyl (terpy) reacts as a bidentate with chromium,molybdenum, and tungsten carbonyl to give M(CO),(terpy) ;36 the potentialtridentate arsine, tris-l,l,l-(dimethylarsinomethy1)ethane (vr-trias) alsobehaves as a bidentate in the compounds [W(CO),(v-trias)] and[Re( CO) 3C1( v-trias)] .37 A series of bisphosphinetricarbonylmanganese anionshave been prepared; their interaction with alkyl and acyl halides and thecorresponding fluorinated derivatives have been in~estigated.~S Thephosphine derivative of rhenium carbonyl, Re( CO) ,(PPh,) ,, is monomeric,paramagnetic and the zero dipole moment indicates a trans-bipyramidalstructure whereas the corresponding diethylphenylphosphine compound,[Re(CO),(PEt,Ph),],, is diamagnetic in the solid and presumably dimeric,but is paramagnetic in solution.39 Reaction of iron carbonyl with n-butyl-amine or piperidine gives complexes of the type Ph-NH*CO*Fe(C0),.4°The complex Fe(CO),(PPh,), has been obtained from Fe(CO),(PPh3),Br2with sodium amalgam.41 The infrared spectrum and dipole moment indicate&-equatorial positions for the carbonyl groups.The preparation of theruthenium carbonyl phosphine or arsine compounds Ru(C0) ,( MPh,) ,(M = P, As) is reported; oxidation of the phosphine compound gives aseries of octahedral complexes, Ru(CO),[P(Ph),],XP (X = Y = I, Br,CF,*CO,; X = H; Y = C1, Br).42 The photochemical reaction of thebridged dimethylphosphino-carbonyls of iron and molybdenum withphosphines has been reported.43 The details of the structure of the oxygencarrier described last year, IrO ,C1( CO)( PPh,) , have been given." Thedipole moments of the compounds NiCO[PhP( o-C,H,-PEt,) ,] and31 M.Ziegler, H. Haas, and R. K. Sheline, Chem. Ber., 1965, 98, 2454.3a W. Strohmeier, and P. Hartmann, 2. Natwfwsch., 1965, 20b, 613.33 C. H. Bamford, J. Hobbs, and R. P. Wayne, Chem. Comm., 1965, 469; C. H.Bamford, G. C. Eastmond, and K. Hargreaves, Nature, 1965, 205, 385; C. H. Barnford,G. C. Eastmond, and W. R. Maltman, Trans. Faraday Soc., 1965, 61, 267.34D. C. Bradley, J. Charalambous, and S. Jain, Chem. and Ind., 1965, 1730.35 H. G. Ang, J. S . Shannon, and B.0. West, Chem. Comm., 1965, 10; G. W. A.36M. C. Ganorkar and M. H. B. Stiddard, J . Chem. Soc., 1965, 5346.37 R. S. Nyholm, M. R. Snow, and M. H. B. Stiddard, J . Chem. SOC., 1965, 6564.38 W. Hieber, J. Muschi, and H. Duchatsch, Chem. Ber., 1966,98,3924; W. Hieber,39F. Nyman, Chern. and Ind., 1966, 604.40 W. F. Edgell, M. T. Yang, B. J. Bulkin, R. Bayer, and N. Koizumi, J. Amer.4 1 W. Hieber and J. Muschi, Chem. Ber., 1965, 98, 3931.43 J. P. Collman and W. R. Roper, J . Amer. Chem. Soc., 1965, 87, 4008.D. T. Thompson, J . Organometallio Chem., 1965, 4, 74.44 S. J. La Placa and J. A. Ibers, J . Amer. Chem. SOC., 1965, 87, 2581.Fowles and D. K. Jenkins, ibid., p. 61.M. Hofler, and J. Muschi, ibid., p. 311.Chem. SOC., 1965, 87, 3080KOEL AND LEWIS TRAWSITIOX-METAL CARBONYLS 191NiCO[MeC(CH,*PPh,),] have been reporfed 45 and discussed in terms of theNi-C bond order.The nickel complexes (1) and (2; R = Et, Ph) of bis-(phosphin0)-o-carboranes have been prepared.48 New preparative methods('1 (2)for mixed carbonyl fluoro-phosphine adducts of nickel, iron, manganese,chromium, molybdenum, and tungsten have been reported.47 All the pos-sible compounds and isomers of the series M O ( C O ) ~ ( P F ~ ) ~ - ~ (x = 0-5) havebeen prepared and isolated.48Nphm Derivatives.-Interaction of 1,4-dithian(dt) with molybdenumand tungsten carbonyls give dimeric species [M(CO),dt], (M = Mo, W).49Reaction of sulphur-tin complexes, e.g. (MeS) ,SnMe2, with manganese andrhenium carbony150 provides a new method for forming sulphur-metalcarbonyl complexes, and provides a new trinuclear metal cluster :XM(CO), + (MeS),SnMe ---+ [MeS*M(CO),], (M = Mn, Re; X = Br, CI).Similar compounds may be prepared for rhenium and the metalcarbonyl halide.The interaction of penfafluorophenyl mercaptan andrhenium hydride has been investigated.51 Thiophentricarbonylchromium,C4H,SCr(CO),, has been formulated as a n-complex on the basis of X-raydata.52 The structure of [SFe(C0)J2 has been determined and contains adisulphide group symmetrically bonded to two tricarbonyl iron fragmentscontaining a '' bent " iron-iron bond.53 A related compound, [S,Fe,(CO)J,has been shown t o be the product of reaction of 2-mercaptobenzothiazoleand iron carbonyl.54 Derivatives of substituted lY4-dithiins and ironcarbonyl have been isolated.55 With 2,5-diphenyl-l ,Q-dithiin the productis formulated as (3).Ph H' C = c'4 5 J.Chatt and F. A. Hart, J . Chem. SOC., 1965, 812.O6 F. Rohrscheid and R. H. Holm. J . Organonzetallic Chem., 1965, 4, 335.47 J. G. Verka.de, R. 33. McCarley, D. G. Hendricker, and R. W. King, .ln.org. Chem.,1965, 4, 228: T. k c k and K. Baur, Chem. Ber., 1965, 98, 3070: A. Loutellier andM. Bigergne, BuU. SOC. chim. France, 1965, 3186: A. S. Basenally, 3%. S. Nyholm,D. J. Parker, Ed. B. Stiddard, 0. J. R. Hodder, and H. M. Powell, Chern. and Ind.,1965, 2097.48R. J. Clark and R. I. Wobermaa, Inorg. Chem., 1965, 4, 1771.OS H. C. E. McFarlane and W. McParlane, J. Inorg. Nuclear Chem., 1965, 27, 1059.50 E.W. Abel, €3. C . Crosse, and D. B. Brady, J. Amer. Chem. Soc., 1965, 87, 4397.alA. G. Osborne and F. G. A. Stone, Chem. Corn., 1965, 361.a z M . F. Bailey and L. F. Dahl, Inorg. Ohem., 1965, 4, 1306.5s C. H. Wei and L. F. Dahl, Inmg. C h i . , 1965, 4, 1.54 R. Havlin and G. R. Knox, J. Organometallic Chern., 1965, 4, 247.5 5 C. W. Bird and E. M. Hollins, J . Orp~aometallic Chern., 1966, 4, 245192 INORGANIC CHEMISTRYHalogen Derivatives.-Oxidation of the anions [M(CO)I],- to [M(C0)413J-(M = Mo, W), reported last year 56 has been extended to yield the seven-co-ordinated mixed halogeno-compounds [M(CO),XY,]- (M = Mo, W;X = Br, I; Y = Br, I); the stability of the anions is very dependent onthe cation used.57 Oxidation of a series of tridentate arsenic chelate com-plexes of molybdenum and tungsten carbonyls also leads to seven- co-ordinatecomplexes [M(CO),(trias)X]X and [M(CO),(trias)X,] [M = Mo, W;X = Br, I ; trias = methylbis(dimethylarsino-3-propyl)arsine, v.Trias =bis(o-dimethylarsinopheny1)methylarsine (TTAs)] .58 With the diphosphine,1,Z-bisdiphenylphosphinoethane (diphos) complexes, oxidation of the tetra-carbonyl derivatives [M( CO),( diphos)] yields similar seven-ca-ordinatespecies W(CO),(diphos)X,] (M = Mo, W; X = Br, I), but with theclicarbonyl complexes, [M(CO),(diphos) ,I, paramagnetic six-co-ordinatederivatives of molybdenum and tungsten(1) are obtained.59 Oxidation ofthe diphos complexes or the triphenylphosphine-substituted carbonyls withexcess of halogen leads to phosphine oxide derivatives of molybdenum andtungsten(v and VI).~* The use of antimony pentachloride as a controlledchlorinating agent for arene carbonyls of tungsten has been established, togive [( arene)W( CO),C1]SbC16.61Manganese carbonyl bromide and iodide interact with diphos to yield[Mn(CO),(diphos)X] (X = Br, I) but with the chloride the cation[Mn(CO),(diphos) is obtainede6, The reaction of thiocyanogen chloridewith sodium manganese carbonyl gives [Mn(CO),CNS].The compound issulphur-bonded in the solid state, and nitrogen-bonded in acetonitrile.63In chlorinated solvents an equilibrium exists between the two forms ofbonding. Bromination of triphenylphosphine tetracarbonyl compounds ofmanganese and rhenium give mixtures of cis- and trans-M(CO),(PPh,)(Br) .64Oxidation of Re( CO)( diars) 2X (diars = o-phenylenebisdimethylarsine) givesthe seven-co-ordinate compounds of rhenium(m), [Re(CO)(diars)X,]Y(X = Br, I; Y = Br,, I,, ClOJ.65 Five-co-ordinate derivatives of cobalt(r),Co(CO),LX [X = C1, I; L = P(Ph,), P(OPh),; X = Br, L = PPh,], havebeen obtained by oxidation of the sodium salt Na [Co( CO) ,L] with phosphorusoxychloride, perfluoromethyl iodide, or N - bromosuccinimide. The chlorideand bromides readily decompose to give Co(CO),L2X derivatives. Thecompounds Co(CO),L2C1 react with carbon monoxide in the presence ofaluminium chloride to give [Co(CO) ,L2][A1Cl4].The acyl derivativesC,H,COCo(CO),L (L = PPh,, P(OPh),) have also been described.66 Deriva-5 6 D. Nicholls, Ann.Reports, 1964, 61, 170.5 7 M. C. Ganorkar and M. H. B. Stiddard, J . Chem. Soc., 1965, 3494.5~ C. D. Cook, R. S. Nyholrn, andM. L. Tobe,J. Chem.Soc., 1965,4194; R. S . Nyholm,M. R. Snow, and M. H. B. Stiddard, ibid., p. 6570.69 J. Lewis and R. Whyman, Chem. Comm., 1965, 159; J . Chem. Soc., 1965,5486.J. Lewis and R. Whyman, J . Chem. Soc., 1965, 6027.61M. R. Snow and M. H. B. Stiddard, Chem. Comm., 1965, 580.62A. G. Osborne and M. H. B. Stiddard, J . Chem. SOC., 1965, 700.63 M. F. Farona and A. Wojcicki, Inorg. Chem., 1965, 4, 857.64 P. W. Jolly and F. G. A. Stone, J . Chem. SOC., 1965, 5259.6 5 W. J. Kirkham, A. G. Osborne, R. S. Nyholm, and M. H. B. Stiddard, J . Chem.66 W. Hieber and H. Duchatsch, Chern. Ber., 1965, 98, 1744.SOC., 1965, 550KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 193tives of C,H,Co(CO)X, (X = C1, Br, I) have been prepared.s7 The phosphinecarbonyl chlorides of rhodium have been prepared from the rhodium(1n)chloride with phosphine in a series of non-alcoholic oxygen-containingsolvents and by decarbonylation of aldehydes with RhC1( PPh3)3.68 A seriesof bridged compounds [Rh(CO),X], (X = carbonyl, NO3, CNS, S,O,) andmononuclear compounds RhX(am)(CO), (am = pyridine, NH,, C6H,NH2,MeC6H5NH2, cc-picoline, bipyridyl) have been ~repared.6~ The preparationof anions [Rh(CO),X,]- (X = C1, Br, I), [Rh(CO),X,]- (X = C1, Br, I),[R8h,(CO)2X,]2- (X = Br, I), and [Rh(CO)I,]- has been reported.70 A newcarbonyl halide Pd2( CO) ,C1 has been isolated ; the complex is diarnagneti~.~~Miscellaneous.-Silicon-metal bonded derivatives have been isolated byreaction of Ir(PPh,),COCl with substituted silicon hydrides 7, and cobalt-silicon bonded complexes are postulated as intermediates in the hydrosilationof olefins catalysed by cobalt octacarbonyl.73 The silicon cobalt carbonylderivatives R’R,S~CO(CO)~ (R’ = R = C1, Et, Ph, H ; R’ = Ph; R = C1) havebeen prepared.74 The formation of carbonyl-cyanide ions [Ni(CN)(CO),]-and [Fe( CO),CN]- occurs in the reaction of substituted silylsodamides withmetal ~arbonyls,~~ e.g., Fe(CO), + NaN(SiR,), = Na[Fe(CO)&’N] + O(SiR,),.Hydrides .-T he structure of h ydrido c hloro bisdip hen y le t h y lp ho s phine -platinum(n) has been determined,Y6 and it is inferred that the hydrogenoccupies a co-ordinate position in the phosphorus-chlorine plane trans tothe chloride ion.The platinum-chlorine distance is longer than calculatedfrom the sum of the ionic radii rules and this is associated with the hightrans-directing effect of the hydride ion. Interaction of palladium and theortho-hydrogens of the phenyl groups of dimethylphenylphosphine is indicatedin the X-ray structure 77 of the yellow isomer of di-iodobis(dimethylpheny1-phosphine)palladium( II) . A similar interaction appears also in the complexdichlorotris( triphenylphosphine)ruthenjum( 11) . 78 A related situation occursin the system obtained by reduction of truns-[RuCI,(PP) J, wherePP = Me2P*CH,*CH,PMe2, with arene negative ions ; for the naphthaleneion a complex cis-[Ru(Cl,H8)(PP),~ is obtained.This complex involves atautomeric equilibrium between the structures [Ru(C,,H,)(PP),] andcis-[RuH(2-CI,H,)(PP),]. Pyrolysis of the compound gives naphthaleneand the complex [Ru(PP),]; the latter provides an example of a new classof compound in which hydride transfer takes place from the alkyl sidechain of the phosphine to the metal ion to provide a hydride and a tauto-meric system similar to that postulated for the naphthalene-phosphineG 7 R. F. Heck, Inorg. Chem., 1965, 4, 855.68 A. Rusina and A. A. VlEek, Nature, 1965, 206, 295; J. Tsuji and K. Ohno,6g D. N. Lawson and G. Wilkinson, J . Chem. Soc., 1965, 1900.70 L. M. Vallarino, Inorg. Chem., 1965, 4, 161.71 E. 0. Fischer and A. Vogler, J . Organometallic Chem., 1965, 3, 161.A. J.Chalk and J. F. Harrod, J . Amer. Chem. SOC., 1965, 87, 16.7s J. F. Harrod and A. J. Chalk, J . Amer. Chem. SOC., 1965, 87, 1133.v 4 B. J. Aylett and J. M. Campbell, Chem. Comm., 1965, 217.7aU. Wannagat and H. Seyffert, dngew. Chem., 1965, 77, 457.R. Eisenberg and J. A. Ibers, Inorg. Chem., 1965, 4, 773.7 7 N. A. Bailey, J. M. Jenkins, R. Mason, and B. L. Sham, Chem. Comm., 1965,7* S. J. La Placa and J. A. Ibers, Inorg. Chem., 1965, 4, 778.Tetrahedron Letters, 1965, 3969.237194 INORGANIC CHEMISTRYcomple~.~O A most important development has been the first synthesisof a series of hydrido-trifluorophoraphine metal complexes, HM(PF,)(M = Co, Rh, Ir) and a hydrido-carbonyl complex, HCo(PF3),C0.79@The X-ray structure of the compound HMn3(CO)lo(BH,)2 is the first ofa polyborane-transition-metal carbonyl.The BH, groups are joined by aB-B bond and all three hydrogens of the BH, groups are bonded to man-ganese atoms; the unique hydrogen in the structure is considered to bebonded symmetrically between two manganese atoms.80 A similar typeof hydrogen-bonding system is considered to occur in the molecule[(C5H5),Mo2H(PMe,)(CO),] ; from the X-ray structure it is considered thatthe hydrogen is bonded between the two molybdenum atoms to give it a“ symmetrical, bent, three-centre metal-hydrogen-metal bond.”81 In theRaman spectra of the hydrido- and deuterio-rhenium tetracarbonyl trimer[Re(CO),H], a weak band in the Raman spectrum of the hydride, at1600 cm.-l, moves to 787 cm.-l in the deuteride.82 This is assigned to aRe-H-Re bridging vibration.The infrared and n.m.r. spectra of the com-plexes [HM,(CO),,]- (M = Cr, Mo, W) indicate the proton is equivalentlybonded to both metal ions in a bridged s t r ~ c t u r e . ~ ~The reduction of [CoBr,(diphos),] with sodium borohydride gives thehydride [CoH(diphos),J ; alternative reduction of the compound with potas-sium hydroxide-aqueous ethyl alcohol solutions in an atmosphere of nitrogengives the cobalt(0) compound [Co(diphos),]. This will absorb hydrogen a troom temperature to give the hydride.84 Reduction of the bis(dimethy1-glyoximato)cobalt(m) compounds, CoX(dmg),B (X = halogen; B = pyri-dine, tri-n-butylphosphine ; dmg = the anion of dimethylglyoxirne), withsodium borohydride gives the hydride HCo( dmg) 2B.Interaction of thehydride with the triphenyl-Group IV halides give metal-metal bondedspecies, with liberation of hydrogen halide. 85 Reaction of the correspondinghalogenoiridous acid with cyclo-octa- 1,5-diene gives the halogen- bridgeddimeric hydride [IrHX,(dien)], (X = C1, Br, I). Reaction of these com-plexes with sodium carbonate-methyl alcohol gives the methoxy- bridgedcompounds [Ir( OMe)(diene)]2;86 this may be reconverted into the hydrido-halogeno-complex with halogen acids. The proton n.m.r. of a series ofphosphineplatinum hydrides has been reported.87 The platinum-hydrogencoupling constants are -1200 c./sec. whilst the phosphorus-hydrogencoupling constants axe -15 c./sec.Nitrosgls.-The e.8.r.spectrum of the ions [Cr(NO)(H,0),]2+,7 9 J. Chatt and J. M. Davidson, J. Chem. SOC., 1965, 843.700 T. Kruck, W. Lang, and A. Engelmann, Angew. Chem., 1965, 77,132: T. Kruckand W. Lang, Chern. Ber., 1965, 98, 3060: T. Kruck, W. Lang, and N. Dorner, 2.Natwforsch., 1965, 20b, 705: T. Kruck and W. Lang, Angew. Chm., 1965, 77,860.8 0 H. D. Kaesz, W. Fellmam, G. R. Wilkes, and L. F. Dahl, J . A w r . Chern. SOC.,1965, 87, 2753.8lR. J. Doedens and L. F. Dahl, J . Arner. Chern. SOC., 1965, 87, 2576.8% J. M. Smith, W. Fellmann, and L. H. Jones, Inorg. Chem., 1965, 4, 1361.83 U. Anders and W. A. G. Graham. Chem. Comm., 1965, 499.8 4 A. Sacco and M. Rossi, Chem. Comm., 1965, 602.86 G. N. Schrauzer and G. Kratel, Angew. Chem., 1965, 77, 130.8 6 s .D. Robinson and B. L. Shaw, J . Chem. SOC., 1965, 4997.8 7 J. Powell and B. L. Shaw, J . Chem. SOC., 1965, 3879KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 195[Cr(NO)(NH,) J2+, [Mn(CN)5N0 J2-, [Pe( CN)5NO]3-, and [Cr(CN)5N0]3-,88as well as the ultraviolet and visible spectra of [Fe(CN)5N0]2-,89 have beendetermined and interpreted in terms of mo1ecula.r orbital theory. The anglebetween equivalent NO and CO groups in complexes has been correlatedwith the intensity of the symmetrical and asymmetrical vibrations of thegroups.90 The infrared criterion for determining the mode of bonding ofthe NO group in nitrosyls has been questioned, in particular the rangeappropriate to the NO- bonding scheme has been discu~sed.~~ The electronicspectra of the complexes [CoX*NOL,]+ (L = diars; X = Br, C1, I, CNS;L = en; X = Cl, Br, I, NO,) are readily assigned on the basis of CoIU,with NO- bonding, yet the infrared frequency of the NO groups are-1600 cm.4.92 Nitrosylpentacarbonylvanadium reacts with tetraphenyl-diphosphine to give binuclear complexes maintaining the diphosphine unit(NO)(CO>,*V*PPh,*PPh2~V*(CO),(NO). The corresponding cobalt complexon heating rearranges to the phosphino-bridged complexes(NO)( CO) ,Co*Ph,P-PPh,*Co( CO) ,NO -+ [Co( CO)(NO)PPh,] 2.93Vanadium tetrachloride reacts with nitric oxide t c ~ give a polymeric chlorinebridge nitrosyl [(NO) 3VC12]n.94 The polymeric chloronitrosylmolybdenum[Mo(NO) zC12]n reacts with the maleonitriledithiolate ion (MNT) to give theanionic species ~O(NO),(MNT),]~-.~~ A study of the e.s.r.spectrum ofaqueous solutions of a variety of iron@) salts with nitric oxide has beenreported; the data indicate an equilibrium in the solutions between dia-magnetic and paramagnetic nitrosyl species.96 The nitrosyl-thiocyanatesof iron, cobalt, and nickel are formed by the reaction of the metal nitrosylhalide with potassium or silver thiocyanate; the reaction of the compoundswith tertiary organic phosphines, arsines, stibines, as well as phenanthrolineis rep~rted.~' Nitrosyl allyl iron compounds are formed by reaction ofallyl iron carbonyl halides, (allyl)Fe(CO),X (X = halogen)? with nitricoxide, or the nitrosyl carbonyl anion [Fe(CO),NO]- with allyl halides.Reaction of the complex (allyl)Fe( CO) ,(NO)a derivative formulated g8 as (4),NOwith triphenylphosphine(4)gives8B I.Bernal, S . 33. Robinson, L. S. Meriwether, and G. Willrinaon, Chem. Comm.,1965, 571; H. B Gray, P. T. Manoharan, J. Pearlman, and R. F. Riley, ibid., p. 62;P. T. Manoharan and H. B. Gray, ibid., p. 324; J. J. Fortman and R. G. Hayes, J . Chem.Phys, 1965, 43, 15; EI. A. Kuska and M. T. Rogers, &d., 1965, 42, 3034; D. A. C.McNeil, J. B. Raynor, and M. C. R. Symons, J . Chem. SOC., 1965, 410.89 P. T. Manoharan and H. B. Gray, J . Amer. Ghem. SOC., 1965, 87, 3340.91 P. Gans, Chem. Comm., 1965, 144.92 R. D. Feltham and R. S. Nyholm, Inorg. Chem., 1965, 4, 1334.98 W. Hieber and R. Kummer, 2. Naturforsch., 1965, 20b, 271.94 W. Beck, K. Lottes, and K.Schmidtner, Angew. Chem., 1965, 77, 134.96 J. Locke and J. A. McCleverty, Chem. Comm., 1965, 102.96 C. C. McDonald, W. D. Phillips, and H.F. Mower,J. Amer. Chem. Soc., 1965,8'9,3319.I~'W. Hieber, I. Bauer, and H. Neurnair, 2. anorg. Chem., 1965, 335, 260. ** R. Bruce, F. M. Chaudhary, G. R. Knox, and P. L. Pauson, 2. Naturforsch.,W. Beck, A. Melnikoff, and R. Stahl, Angew. Chem., 1965, 77, 719.1965, 20b, 73; M. D. Murdoch, ibid., p. 279196 INORGANIC CHEMISTRYThe nitrosyltricarbonyliron anion reacts with fluorinated carboxylic acidsin the presence of triphenylphosphine to give RfCOFe( CO)(NO)( PPh,),(Rf = CF,, C2F6).99 The magnetic properties of nitrosyliron SchiE-baseshave been investigated ; the salic ylaldehyde-ethylenediamineiron ni tros ylcomplex shows a change in the magnetic properties from three unpairedelectrons a t room temperature to one unpaired electron at 180" K .~ O O AnX-ray structure of the black nitrosylpentamminecobalt dichloride,[Co(NH,),NO]CI,, indicates a linear Co-N-0 system, with a long Co-N bondfor the ammonia co-ordinated tram to the nitrosyl group.lO1 cis- and truns-Isomers have been detected for the binuclear complexes (5)X/ \(M = Co, Ni; X = halogen; L = SR, PR,, AsR,),lo2 in the complexesCo(NO),L(CNS)Ni(NO),L,CNS the infrared spectra indicate the bonding isthrough the nitrogen of the CNS group. Bridging thiocyanate groups arepresent in the polymeric nitrosyl complexes [M(NO),CNS], (M = Fe, Co,[Ni(NO)(CNS) 1% ; [Ni( NO)L,( CNS)],) .97Transition-Metal Carbons1 Complexes Containing Metal-Metal Bonds.-Continued interest has been maintained in this series of compounds; thefield has been reviewed.lM Mixed carbonyl-carbonylcyclopentadienylcomplexes C,H,M(CO),-M'(CO), (M = Mo, W; M' = Re, Mn) have beenreported.104 Using the triarsine ligands, v.trias and TTAs, the followingcomplexes have been prepared.[(trias)M-Mn(CO),], [(trias)M],Fe(CO),,[(trias)M-Co(CO),] (M = Cu, Ag).lo5 The X-ray structures of the com-plexes [(TTAs)Cu-Mn(CO),], Ph,Ge*Mn(CO),, and Ph,PAuCo(CO), arereported.lW The manganese complexes are octahedral, whilst the cobaltcomplex is trigonal bipyramidal. In the copper complex the four carbonylscis to the copper are displaced from the equatorial plane towards thecopper atom, similarly in triphenylphosphinegold-cobalt tetracarbonylthe thee CO groups are displaced out of the equatorial plane towardsthe gold atom.The preparation and infrared spectra of a series ofphosphine, arsine, and stibine complexes (L or L') of the gold-manganesecarbonyl system, LAuMn( CO), and LAuMn(CO),L' have been discussed.lo7Complexes with rnercury-metal bonds have been isolated with tungsten99 W. Hieber, W. Klingsliirn, and W. Beck, Chem. Ber., 1965, 98, 307.100 A. Earnshrzw, E. A. King, and L. F. Larkworthy, Chem. Comm., 1965, 180.101 D. Hall and A. A. Taggart, J . Chem. SOC., 1965, 1359; D. Dale and D. Crowfoot102 W. Beck and K. Lottes, 2. anorg. Chem., 1965, 335, 258.lo3 J. Lewis, Pure Appl. Chem., 1965, 10, 11.lo* A. N. Nesmeyanov, K.N. Ainsimov, N. E. Kolobova, and A. S. Beschastnov,Doklady Akad. Nuuk S.S.S.R., 1964, 159, lf84.*lo5 A. S. Kasenally, R. S. Nyholm, and M. H. B. Stiddard, J . Chem. SOC., 1965,5343.106 B. T. Kilbourn, T. L. Blundell, and H. M. Powell, Chem. Comm., 1965, 444.lo7 A. S. Kasenally, J. Lewis, A. R. Manning, J. R. Miller, R. S . Nyholm, andHodgkin, ibid., p. 1364.M. H. B. Stiddard, J. Chenz. SOC., 1965, 3407.* Ref. to the English edition of Russian journalKOHL AND LEWIS : TRANSITION-METAL CARBONYLS 197[W(CO),(bipy)(HgCl),] lo8 and iridium [Ph,P],(CO)ClYIr-HgY (Y = C1, Br,I, OAc, CN, SCN).lOg The infrared spectra of the compounds (XHg),Fe(CO),(X = C1, Br, I) have been determined in the low-frequency region and theHg-Fe stretching frequency assigned.l1° Indium-cobalt complexes havebeen prepared by an insertion of indium bromide between the cobalt atomsof cobalt carbonyl.111C , W \ , co(co)4/ I nTHP ~ 1nBr + CO,(CO)~Br ’ ‘co(co)4The compound loses tetrahydrofuran (THF) under vacuum t o give thebromide-bridged complex [Co( CO),],In.Br,In[Co( CO),].Rhenium-metalbonds are formed by the interaction of the rhenium pentacarbonyl anionwith chlorophenyl derivatives of tin, lead, antimony, and bismuth. Partialbromination of the complex Ph,SnRe(CO), with two molecules of brominegives the dibromophenyltin-rhenium pentacarbonyl, Br,PhSnRe( CO) , ;reaction of this with a further two molecules of the pentacarbonylrheniumanion yields the complex PhSn[Re(CO) ,],.112 Variations on this type ofreaction have produced systems with more than one type of metal-metalbond; the following complexes : [(C,H,)F~(CO),],S~[MO(C~H~)(CO)~]~ 113 and[(CO),Mn]SriMe,[W(CO),(C,H,)J 114 have been prepared by this technique.Complexes of organo-tin and -lead with iron and cobalt carbonyl have beendescribed.l15 Reaction of n-butyltin tricliloride with cobalt octacarbonylgives the complex BU~S~[CO(CO),],.~~~Organometallic Compounds of the Transition Metalsa-Bonded Organometallic Compounds.-The first stable allrylzirconiumcompounds have been prepared by the reaction 117(C,H,),ZrCI-O-ZrCl(CjH,), + 2Mc,A1+ 2(C,H,),ZrClMe + Me,AlOAlMe,The cyclopentadienylzirconium chloro-oxy-compound also reacts withlithium aryls with replacement of the chlorine to give aryl-zirconium deriva-tives.118 Methyl derivatives of chromium-(In) and -(II) have been isolatedas the dioxan adducts Li,Cr(CH3),,3C,H,O, and Li,Cr(CH,)4,2C4~80, fromthe reaction of methyl-lithium with anhydrous chromium-(rc) and - (111)chloride.The chromium(n1) compound is paramagnetic (per -- 3.75 B.M.),lo* M. C. Ganorkar and M. H. 13. Stiddard, Chem. Comm., 1965, 22.Io9 R. S. Nyholm and K. Vrieze, J. Chem. SOC., 1965, 5337.I1O D. M. Adams, D. J. Cook, and R. D. W. Kemmitt, Nature, 1965, 205, 589.l l a A. N. Nesmeyanov, K. N. Anisimov, N. E. Kolobova, and V. N. Khandozhko,113 S. V. Dighe and M. Orchin, J. Amer. Chem. SOC., 1965, 87, 1146.11* H. R. H. Patil and W. A. G. Graham, J . Arner. Chem. SOC., 1965, 8’9, 673.l15F. Hein and W.Jehn, Anrzalen, 1965, 684, 4 .116 S. D. Ibekwe and AX. J. Newlands, Chem. Comm., 1965, 114.11’ J. R. Surtees, Chenz. Comm., 1965, 567.118 E M Braimina, G. G. Droryantseva, and R. Kh. Freidlina, Doklady Akad. NaukD. J. Patmore and W. A. G. Graham, Chern. Conzm.. 1965, 591.Doklady Akad. Nauk S.S.S.R., 1964, 156, 502.”S.S.S.R., 1964, 156, 1375.’* Ref. to the English edition of Russian journal198 INORGANIC OEEMISTRYbut the chromium(rr) compound is diamagnetic and dimerio in benzene.119A corresponding 1 : 4 butane compound has been prepared with chro-dUm(III), Lj,Cr(C,H8),,2.5C,H802 ( p , ~ = 3-9 B.M.) and a diamagnetic1 : 5 pentane adduct for chromium(n), Li2Cr(C5Hl,),,LiBr,3Et20.120 Inter-action of 2-, 3-, or 4-bromomethylpyridine salts with chromium(rr) salts givesstable a-bonded compounds of chromium of the type [2-Py-CH,*Cr(H20),]3+ ;using 2-( bromomethy1)pyridine bromide yields the first compound containinga, secondary carbon-chromium bond.121 The benzylchromium complexPhCH2-Cr(C6H6N) has been isolated by treating benzyl chloride withdichlorobispyridinechomium(n) in pyridine at Ooc.l22 The interaction ofa-bonded organochromium compounds with carbon monoxide and ketoneshas been investigated.12, Vinylcyclopentadienyliron dicarbonyl has beenprepared by reacting cyclopentadienyliron dicarbonyl chloride with vinyl-magnesium bromide.124 a-Bonded organocyanocobalt(n) complexes may beprepared by interaction of the cobalt cyanohydride ion, [Co(CN),HI3-, withan activated olefin or cobalt pentacyanide ion [co(cN),]3- with organichalides.125 Previous attempts to prepare alkyl deriva-tives of CoIII porphyrins lead to reduction to CoII.The methyl and ethyl Coin derivatives of aetio-porphyrin may be prepared by reacting the bro-mide complex with alkylmagnesium halide.126The trisacetylacetonatoplatinum(n) anion, whichcontains two carbon-bonded acetylacetone groupsand one bidentate oxygen-bonded acetylacetonegroup, reacts with acid to give a rnetal-diene complex (6) of the compound.12'Carbon-metal bonding occurs in platinum and palladium in the metal-azobenzene adducts (7) ,l2*CH3(6)H3C $310,CH3q N"N/ MI, C!'CIN119 E.Kurras and J. Otto, J . OrganometaZGc Chem., 1965, 4, 114.lao E. Kurras and J.Otto, J. Organometallic Chem., 1965, 3, 479.lal R. G. Coombes, M. 0. Johnson, M. L. Tobe, N. Winterton, and Lai-Yong Wong,la2 R. P. A. Sneeden and H. P. Throndsen, Chem. Corn., 1965, 509.lea R. P. A. Sneeden, T. F. Burger, and H. M. Zeiss, J . Organometallic Chem., 1965,124 M. L. H. Green, M. Ishaq, and T. Mole, 2. Naturforach., 1965, 20b, 698.126 J. Kwiatek and J. K. Seyler, J . Organom,etaEZic Chem., 1965, 3, 421.lea D. Dolphin and A. W. Johnson, Chem. Comm., 1965, 494.12' D. Gibson, C. Oldham, J. Lewis, D. Lawton, R. Mason, and G. B. Robertson,128 A. C. Cope and R. W. Siekman, J . Amer. C h . Soc., 1965, 87, 3272.Chem. Comm., 1965, 251.4, 397.Nature, 1965, 208, 680KOHL AND LEWIS: TRANSITION-METAL CARBONYLS 199(M = Pt, Pd). A similar type of interaction has been postulated in someiron derivatives.129 Arylazoplatinum compounds formed by reaction of adiazonium salt with platinum hydride complex decompose to give aryl-platinum complexes.130[PhNd?]BF, + HPt(PEt,),Cl+ [PhN =NH-Pt(PEt3),C1]+BFI- -+ PhPf(PEt,),Cl.The preparation and the i.r.and n.m.r. spectra of triethylplatinum chloridehave been reported.131 The X-ray structure of p-ethylenediaminebis-[trimethyl( acetylacetonafo)platinum(Iv) J has been reported ; the acetylace-tone is oxygen-bonded to the metal and the two platburn groups areconnected through a bridging ethylenediamine The nature ofethylzinc iodide solutions has been in~estigated,~~~ and new preparativemethods for RHgC1 and R,Hg (R = Me; CH, = CH-, Ph) from NH,(RSiF,)and mercuric chloride discussed.134 The preparation of the complexesPhHgL (L = CCl,, CBr,, CClBr,, CC1,Br) has been reported.13jFluorke-Contahing a-carbon Complexes.-The infrared spectra in thecarbonyl region for some fluoro-organo-maganese and -rhenium penta-carbonyl adducts have been interpreted in terms of reduction of thesymmetry around the metal ion from C,, by the ligand gr0up.13~ TheX-ray structure of iodocarbonylcyclopenta~enylpentafluoroethylrho~ium,C5H,Rh(CO)C2F51, has been determined and the Rh-C bond length fromthe pentafluoromethyl group has been interpreted as indicating metal-carbon double bonding between the metal and pentafluoroethyl group.137Metal-to- carbon double bonding in perfluoroalkyl compounds has also beeninferred from the infrared spectra of perfluoromethylmanganese penta-carb0ny1.l~~ The synthesis of the pentafluorophenylcyclopentadienyl com-pounds of zirconium and titanium, (C,F,),M(C,H,), from pentafluorophenyl-lithium has been reported.13@ This reagent and pentafluorophenylmagnesiumbromide have been used to prepare phosphine-halide complexes of platinum-(II) containing the pentafluorophenyl group.140 The interaction of carbonylperfluoroalkylcyclopentadienylcobalt iodide with a variety of ligands suchas triphenylphosphine, in the presence of silver perchlorate, has been shamto give complexes of the type [C,H,CO(CO)(PP~,)C~I?,]C~O,.~~~A ready method for the formation of a-bonded fluorinated organometalliccompounds is from the fluorinated olefins and a metal hydride complex.129 M.M. Bagga, P. L. Pauson, F. J. Preston, and R. I. Reed, Chem. Comm., 1965,130 G. W. Parshall, J . Amer. Chew,. SOC., 1965, 8’9, 2133.l31 S. F. A. Kettle, J . Chem. SOC., 1965, 5737, 6664.132A. Robson and M. R. Truter, J . Chem. Xoc., 1965, 630.133M. H. Abraham and P. H. Rolfe, Chem. Comm., 1965, 325.13* R. Miiller and C. Dathe, Chem. Ber., 1966, 98, 235.135 D. Seyferth and J. M. Burlitch, J . Organometallic Chm., 1965, 4, 127.136 J. B. Wjlford and F, G. A. Stone, Inorg. Chem., 1965, 4, 389.137 M. R. Churchill, Inorg. Chena., 1965, 4, 1734.138 F. A. Cotton and J. A. McCleverty, J . OrganometaUic Chem., 1965, 4, 490.13s C. Tamborski, E. 5. Soloski, and S . M. Dee., J . OrganornetalZic Chern., 1966,I4OD.T. Rosevear and F. G. A. Stone, J . Chem. SOC., 1965, 5275.141 P. hl. Treichel and G. Werber, Inorg. Chem., 1965, 4, 1098.543.4, 446200 INORGANIC CHEMISTRYReaction of an olefin with the hydrocarbonyls of manganese, rhenium,cobalt, and dicarbonylcyclopentadienyliron hydride, and hydrides of theplatinum-phosphine-halide systems, have been shown to yield 0- bonded~omp1exes.l~~ An insertion of tetrafluoroethylene in manganese-tin bondsto give M~,SIYCF,*CF,*M~(CO)~ has been shown to occur.143 With tri-fluoroethylene the corresponding reaction did not occur and a o-bondedfluoro-olefin was produced, CHF = CF*Mn(C0),.144 This class of compoundis also prepared by reaction of fluorinated olefins with the metal carbonylanions of rhenium and manganese, the dicarbonylcyclopentadienylironanion a.nd tetra carbon y ltrip hen ylp hos phinemang anese anion.145 With per -fluorocyclobutene the following reaction occurs :corresponding reactions have been established with perfluoro-propene-ethylene, -&clohe~ene.l~~ The anion Re(CO),- will replace fluorine inperfluorobenzene to give C,F,Re(CO),; the same compound may be obtainedby decarbonylation of C,F,CORe(CO> ,. The reaction of tetrafluoroethylenewith the cyanide and cyanohydride of cobalt yields the complexesK [ ( CN ) ,CoC zF & o ( CN ) 5], K [ C o ( CN ) , *CF ,* CF ,H 1, l4 The X-ray structureof the last compound has been reported and the metal-carbon distance ofthe fluorinated alkyl-metal system has been interpreted in terms of multiplebonding between the metal and the alkyl residue.147Caxboxylation Reactions.-The interaction of methyl- and phenyl-rnanganese pentacarbonyls with phosphines, arsines, or stibenes occurs withthe formation of acyl intermediates which may lose carbon monoxide togive the cis- and trans-isomers of the corresponding alkyl or aryl substitutedtetracarbonyl ~omp1ex.l~~ With methylmanganese pentacarbonyl this reac-tion has been extended to charged nucleophiles to give ions of the type[CH,COM~I(CO),I]-.~~~ Propionylcobalt tetracarbonyl and cobalt carbonylare formed from interaction of triethylaluminium with cobalt stearate inhexane under a carbon monoxide pressure.l50 Interaction of phenylmercuricnitrate with carbon monoxide (247 atm.) in benzene solution yields phenyl-mercuric benzoate.151The field of organo- Olefin-metal Complexes.-Nono-oZe$n complexes.142 J.B. Wilford, A. Forster, and F. G. A. Stone, J . Chem. SOC., 1965, 6519; J. B.Wilford and F. G. A. Stone, Inorg. Chem., 1965, 4, 93; M. L. H. Green and A. N. Stear,2. Naturforsch., 1965, gob, 812.143 H. C. Clark, J. H. Tsai, and W. S. Tsang, Chem. Comm., 1965, 171.14*H. C. Clark and J. H. Tsai, Chem. Comm., 1965, 111.145 P. TV. Jolly, M. I. Bruce, and F. G. A. Stone, J. Chem. Soc., 1965, 5830; P. W.Jolly and F. G. A. Stone, Chem. Cmm., 1965, 85.1 4 6 M . J. Mays and G. Wilkinson, J. Chem. Soc., 1965, 6629.14' R. Mason and D. R. Russell, Chem. Comm., 1965, 152.l4* W. D. Bannister, M. Green, and R. N. Haszeldine, Chern. Cornm., 1965, 54;C.S. Kmihanzel and P. K. Maples, J . Amer. Chem. Soc., 1965, 87, 5267.140 F. Calderazzo and K. Noack, J. Organometallic Chem., 1965, 4, 250.L50 P. Szabb and L. Markb, J . Organometallic Chem., 1965, 3, 364.151 L. R. Barlow and J. M. Davidson, Chem. and Ind., 1965, 165GKOHL AND LEWIS: TRANSXTION-METAL CARBONYLS 201metallic compounds of nickel has been reviewed.152 A series of olefin-arenechromium compounds have been reported, (arene)Cr(CO) tL, whereL = cycloheptene, cyclopentene, eth~1ene.l~~ The preparation of' bis-acraldehydemolybdenum dicarbonyl is described. The structure is con-sidered to be polymeric and as in the structure suggested for bisacraldehyde-nickel, bonding through both the olefinic and oxygen groups are envisaged.lj4The first tetrafluoroethylene complexes in which bonding occurs throughthe n-system have been established for rhodium;146, 155 the compIexes maybe prepared by displacement of ethylene from bis( ethylene)acetylacetonato-rhodium(1) or the bridged chlorobisethylenerhodium dimer.The reactionof chlorobis(triphenylphosphine)carbonyliridium(I) with tetrafluoroethylenegives (Ph,P) 21rC2F,(CO)C1.155 The tetrafluoroethylene is considered to bondin a similar manner to oxygen in the complex (Ph,P),Ir(CO)Cl*O,. Thecompound chlorobis( triphenylphosphine) (tetrafluoroethylene)rhodium( I) wasprepared from the tris( tripheny1phosphine)rhodium chloride by direct reac-tion with tetrafl~oroethylene.~~~ An n.m.r. study has established thatethylene exchanges rapidly with Zeise's salt, [K(C2H4PtCl3)H,O], and bis-ethyleneacetylacetonatorhodium(~) .156 New olefm complexes of platinum(I1)have been established with 4-vinylcyclohexene, and cyc10-ocfene.~~~ Theinfrared and n.m.r.spectra of a large number of olefin-silver complexeshave been studied.l58 Diphenylvinylphosphine is considered ta interactwith silver ion to bond by both the olefin group and phosphorusOlefin complexes of gold are reported from interaction of tetrachloroaurateion with cyclopentene, cyclohexene, cis-cyclo-octene, and trans-cyclo-decene.160 The various mechanisms for the isomerisation of olefins havebeen discussed.l61 The isomerisation of octenes by the iridium-phosphine-hyclride complexes, IrHC12( PEt,Ph), and IrH,( PPh,) 3, are considered toinvolve primary co-ordination to the Platinum-tin chloridecomplexes [PtC1,(SnCl,),-,.2- have been shown to catalyse double-bondmigration in higher olefins and a hydride intermediate is postulated in therea~ti0n.l~~ Ethylene-rhodium complexes are suggested as intermediatesin the rhodium chloride-catalysed dimerisation of ethylene to linearbuteiies .164Tris(tripheny1phosphine)rhodium chloride has been shown to be ahomogeneous hydrogenating system for olefins and a~ety1enes.l~~ A detailed152 C.N. Schrauzer, Adv. Organometallic Chem., 1965, 2, 2 .153 W. Strohmeier and H. Hellmann, Chem. Ber., 1965, 98, 1598.and F. J. Knoll, Inorg. Chem., 1965, 4, 1323.155 0. W. Parshall and R. Cramer, J . Amer. Chem. Soc., 1965, 87, 1392.lS6 R.Cramer, Inorg. Chem., 1965, 4, 445.15' E. Kuljian and H. Frye, 2. Naturforsch., 1965, 20b, 204.158 H. W. Quinn, J. S. McIntyre, and D. J. Peterson, Cunad. J . Chem., 1965, 43,159 C. Wu and F. J. Welch, J . Org. Chem., 1965, 30, 1229.160 R. Huttel and H. Dietl, Angew. Chem., 1965, 77, 456.161 J. F. Harrod and A. J. Chalk, Nature, 1965, 205, 208.162 It. S. Coffey, Tetrahedron Letters, 1965, 3809.163 G. C. Bond and M. Hellier, Chem. and Ind.. 1965, 35.ls4R. Cramer, J . Amer. Chern. SOC., 1965, 87, 4717.165 F. H. Jardine, J. A. Osborn, G. Wilkinson, and J. F. Young, Chem. and Ind.,D. P. Tate, A. A. BUSS, J. M. Augl, B. L. Ross, J. G. Grasselli, W. M. Ritchey,2596.1965, 560202 INORGANIC CHEMISTRYstudy of the behaviour of this complex in solution has established anequilibrium 1166, 167(Ph,P),RliCl s (Ph,P),Rh(solvent)Cl + Ph,P.1 [(Ph$)&hCl], + PhSPThe n.m.r.spectrum of a solution of this complex, through which hydrogengas is bubbled, indicates that the solvated bisphosphine compound formsit hydride intermediate, which interacts with the olefin or acetyIene.167Related ruthenium systems RuCl,(PPh,), or RuC12( PPh,), also act ashomogeneous hydrogenating systems.168 The solutions are considered toinvolve solvated intermediates of the type RuC1,(Ph3P),(solvent), x = 2 or 3,but in contrast to the rhodium systems the presence of ethanol as a cosolventis necessary. Catalytic hydrogenation of olefins also occurs with thehalogenocarbonylbistriphenylphosphine complex of rhodium and iridium,[(Ph,P),MCOX]; this process is also considered to occur via a hydride-olefin co-ordinating system.leg The rhodium carbonyl chloride complex,RhCOCl(Ph,P), is also an effective hydroformylation catalyst as is theruthenium complex Ru(CO),(PP~,),.~~~, l70The interaction of butadiene with cyclopentadienyl-manganese tricarbonyl in ultraviolet light gave in addition to theproduct C5H51VfnCO(c4H6) reported previously, two new complexes,C,H5&h(C0) ,butadiene and C,H5( CO) ,Mnbutadiene Nn( CO) 2( C5H5) .I71Dibutadienerhodium( I) chloride has been prepared by reaction of rhodiumtrichloride and butadiene at -5".The X-ray structure of the compoundis reported.172 The synthesis of unsaturated esters from conjugated or non-conjugated dienes, carbon monoxide, and phosphinepalladium halides hasbeen reported for a variety of olefins.173 Dimerisation of norbornadieneby nitrosyliron carbonyl has been studied.174The interaction of iron carbonyl with 1,6-diphenylhexatriene yields atricarbonyl complex.176 The interaction of tetraphenylallene with ironcarbonyl gives a red diamagnetic adduct (Ph,C,)Fe(CO), from which thetetraphenylallene can be displaced with triphenylphosphine.Tetraphenyl-butatriene gives the complex Ph,C,Fe,(CO),. Cumulene is unstable, butmay be stabilised by co-ordination to a metal. The reaction of 1,4-dibromo-but-2-yne with iron carbonyl in the presence of zinc dust yields C4H4Fe,(CO),,as a stable red crystalline compound.176 Tetraphenylallene and tetraphenyl-PoZyene systems.hl.A. Bennett and P. A. Longstaff, Chem. and Ind., 1965, 846.16' J. F. Young, J. A. Osborn, F. H. Jardine, and G. Wilkinson, Chem. Comm.,168 D. Evans, J. A. Oaborn, F. H. Jardine, and G. Wilkinson, Nature, 1965, 208,L. Vaska and R. E. Rhodea, J . Amer. Chem. Soc., 1965, 87, 4970.170 J. A. Osborn, G. Wilkinson, and J. F. Young, Chm. Comm., 1965, 17.171 M. L. Ziegler and R. K. Sheline, Inorg. Chem., 1965, 4, 1230.172 L. Porri, A. Lionetti, G. Allegra, and A. Immirzi, Chem. Comm., 1965, 336.173 S. Brewis and P. R. Hughes, Chem. Comm., 1966, 157, 489.174 P. W. JolIy, F. G. A. Stone, and K. Mackenzie, J . Chem. Soc., 1965, 6416.175 H. W. Whitlock, jun., and Yow Nan Chuah, Inorg. Chem., 1965, 4, 424.176 A. Nakamura, P. J. Kim, and N.Hagihara, J . Organometallic Chm., 1965, 3, 7 .1965, 131.1203KOHL AND LEWIS : TRANSZTION-METAL CARBONYLS 203butatriene also react with chromium carbonyl; addition occurs to the phenylgroup in both cases.177The X-ray structure of dipenteneplatinum(n) chloride has been investi-gated. The axis of one of the double bonds is perpendicular to the PtC1,unit whilst the other double bond is a t 62" to this ~lane.1~8 The proton-proton coupling in the n.m.r. spectra of dieneiron tricarbonyl complexeshas been interpreted in favour of 1,4-addition of iron to the d.ie11e.1~~Sodium borohydride reduction of the complex [C5H5lvC&6(CO)]PE", givesreduction of the co-ordinated benzene to the 1,3-diene, C5H5WC6H,(CO)H.Reduction of the corresponding molybdenum complex with lithium alu-minium hydride gives C,H 5MoC6H6.1s0 The preparation of the cyclohexa-1,3-&ene complex of iridium and the octafluorocyclohexa- 1,3-diene complexof rhodium have been reported.lg0y 181The X-ray structure of c y clo p entadienyl ( benz o ylc y clopent adiene ) cob altestablishes that the benzoyl is exo to the metal atom.In contrast to thephenyl complex the carbon-carbon distances within the cyclopentadienering suggest that the four bonding carbon atoms are in a sp2-hybrid state andbonded symmetrically t o the metal.ls2 However, the structure of dimethyl-mcyclopentadienyl(methylcyc1opentadiene)rhenium shows bond lengths of1-31 and 1.45 A for the part of the cyclopentadiene bonded to the rheniumand favours a n-olefin-o-bonding pattern of the butadiene fragment.ls3 Thefirst perfluorocyclopentadiene complexes have been prepared from cobaltoctacarbonyl, iron carbonyl, and cyclopentadienylcobalt djcarbonyl.In thecobalt compounds [C5F,Co(CO),],, [C5F,Co(CO)C5H5], the ligand bonds asa dienyl, in the iron compound, C,F,[Fe(CO),],, it is suggested that eachdouble bond co-ordinates to separate iron atoms.ls*The isomerisation of cyclo-octa-l,5-diene t o the 1,3-isomer by iridiumand rhodium complexes has been studied; reaction of the 1,5-diene withchloroiridic acid gives the hydride [IrHCl,( 1 ,5-CsH1,)].185 With chromiumcarbonyl, in the appropriate solvents, cyclo-octa-I ,5-diene is transformedinto o-xylene. The cyclo-octa- 1,3-diene reacts with molybdenum andtungsten carbonyl to give complexes of the 1,5-isomer.l86 The stereo-chemistry of the molecules obtained by nucleophilic attack of methoxideion on metal complexes of bicyclopentadienyl has been investigated byn.m.r.spectro~copy.~~~ Nucleophilic attack on the cyclo-octa- 1,5-diene-palladium dichloride complex by ethyl malonate or ethylacetoaceOone leadsto substitution in the organic ring.lS8 The X-ray structure of cyclo-octa-177 A. Nakamura, P. J. Kim, and N. Hagihara, J. Organometallic Chem., 1965,3, 355.178 N. C. Baeziger, R. C. Medrud, and J. E. Doyle, Acta Cryst., 1965, 18, 237.179 R. S. Gutowsky and J. Jon&#, Inorg. Chem., 1965, 4, 430.180 E. 0. Fischer and F. J. Kohl, Chem. Ber., 1965, 98, 2134.Is1R. L. Hunt and G. Wilkinson, Inorg. Chem., 1965, 4, 1270; G.Winkhaus andH. Singer, 2. Naturforsch., 1965, 20b, 602.lE2 M. R. Churchill, J . Organometallic Chem., 1965, 4, 258.18s N. W. Alcock, Chern. Comm., 1965, 177.lS6 J. K. Nicholson and B. L. Shaw, Tetrahedron Letters, 1965, 3533.ls8 G. J. Leigh and E. 0. Fischer, J . Organometallic Chem., 1965, 4, 461.lE7 J. K. Stille, R. A. Morgan, D. D. Whitehurst, and J. R. Doyle, J . Amer. Chem.J. Tsuji and H. Takahaski, J . Amer. Chem. SOC., 1965, 87, 3275.R. E. Banks, T. Harrison, R. N. Haszeldhe, A. B. P. Lever, T. F. Smith, andJ. B. Walton, Chem. Comm., 1965, 30.Sm., 1965, 87, 3282204 INORGANIC CHEMISTRYI ,5-dieneduroquinonenickel indicates that both sets of double bonds fromthe ligands are perpendicular to each other and that the co-ordinated nickelatom has an idealised tetrahedral configuration.lSg The relative bond lengthsof the co-ordinated double bonds for the two ligands are discussed in termsof the stability of the nickel-ligand bonds.A refinement of the crystalstructure of norbornadienepalladium(n) chloride indicates that, contrary tothe initial report, the bond length of the co-ordinated C=C system is barelysignificantly longer than normal.lgO The use of tricarbonyltris( acetonitrile)-tungsten as an intermediate for the preparation of (olefin)W(CO) , complexes,(olefin = cycloheptatriene, cyclo-octatriene, cyclo-octatetraene) has beendeveloped .l 91Aceblene Complexes.-The X-ray structure of the red-orange and darkred isomers, Fe,(CO),(C,H,),, produced from acetylene and iron carbonylshow condensation of three acetylene groups to a 3-methylenepenta-l,4-dienylene bridge in the red-orange isomer and methylcyclopentadienylbridge in the dark red homer.The structure of the violet and black formsof diphenylacetylene-iron carbonyl adducts (Ph,C,)Pe,(CO),, show co-ordination of two diphenylacetylene groups to opposite sides of a triangleof iron atoms, whilst in the black isomer a ferrocyclopentadiene ring isformed with n-bonding from the ring to both iron atoms on opposite sidesof the ring.192 The X-ray analysis of the complex (Ph,C,),Fe(CO), showsit to be a tetraphenylcyclobutadiene derivative.lg3 Diphenylacetylene orhex-3-yne reacts with the hiscarbonylchlororliodium(1) dimer to give cyclo-pentadienonerhodium derivatives.lg4 Hexafluorobut-2-yne reacts withtricarbonyltris( acetonitri1e)tungsten to give an analogous derivative to thecomplexes reported last year, [(CF,) 2C2]3W(NCMe),191 whilst carbonylchloro-bis( tripheny1phosphine)iridium gives the compound (Ph,P) ,COClIr( CF,) ,C2,which in the solid state evolves hexafluorobut-2-yne.This is considered asa derivative of RIP1 with the acetylene bonded by two o-bonds to the metal,and not by a n-acetylene b0nd.1~5 The n-bond structure occurs in therhodium complex (PPh,),RhCl[(CF,),C,] with the acetylene trans to thechloride.146 Hexafluorobut-2-yne also reacts with dicyclopentadienylvana-dium to give a derivative of vanadium(Iv), (C,H,),V(CF,),C,, which isformulated with two a-bonds from the acetylene unit.lg5Ally1 Complexes.-The chemistry and structure of metal-ally1 complexeshas been re~iewed.1~~ Reaction of the lialogenopentacarbonyl anions ofmolybdenum and tungsten [M(CO),X]- (X = C1, Br, I) with ally1 halidesC,H 5kT( Y = C1, Br) give halogen-bridged binuclear allylcarbonyl complexesEt,N[M,Y,(C,H5)2(C0)4] (M = Mo, W).197 Reaction of allene with iron189 M.D. Glick and L. F. Dahl, J . Organometallic Chena., 1965, 3, 200.180 N. C. Baenziger, G. F. Richards, and J. R. Doyle, Acta Cryst., 1965, 18, 925.191 R. B. King and A. Fronzrtglia, Chem. Conam., 1965, 547.192 J. Meunier-Piret, G. S. D. King, and M. Van Meerssche, Acta Cryst., 1965, 19,78; E. H. Braye and W. Hiibel, J . Organometallic Chem., 1965, 3, 38; J. Meunier-Piret,P.Piret and M. Van Meerssche, Acta Cryst., 1965, 19, 85.193 R. P. Dodge and V. Schomaker, J . Organometallic Chem., 1965, 3, 274; ActaCryst., 1965, 18, 614.194 P. M. Maitlis and S. McVey, J . Organometallic Chem., 1965, 4, 254.195 R. Tsumura and N. Hagihara. Bull. Chm. SOC. Japan, 1965, 38, 861.196 M. L. H. Green and P. L. I. Nagy, Adv. Organometallic Chem., 1964, 2, 325.1 9 7 H. D. Murdoch, J . Organometallic Chem., 1965, 4, 119KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 205carbonyl gives the complex [C,H,Fe(CO),], which is considered to have a2,Z’-bis-n-allylene structure. The n.m.r. spectrum suggests the presence ofvalency tautomerism between a n-ally1 and a n-olefin-bonded structure.1a*The X-ray structure of tricarbonylbicyclo[3,2,l]octadienyliron tetrafluoro-borate favours interaction by separate n-ally1 and n-olefin bonds, ratherthan a delocaljsed n-system.lg9 Reactions of ruthenium trichloride withisoprene yields a bridged chloro-complex of ruthenium with 2,7-dimethylocta-2,6-diene, the ligand co-ordinates to the metal with double n-ally1 chelakingarrangement [see (S)] .200iI cAcyl- and allyl-cobalt tetracarbonyl react with ap-unsaturated aldehydcsor ketones to form 1-acyloxy-n-allylcobalt tricarbonyl.The complexes aremost readily isolated as the monotriphenylphosphine derivative.201 Thereactions of (C, ,H,,)RhCb, produced from all-trans- cyclododeca- 1,5,9- trieneand rhodium trichloride, with carbon monoxide, ethylene, and a variety ofnitrogen ligands have been reported.The X-ray structure of the ethylene-diamine complex, trans-dichloro( ethy1enediamine)cyclododeca- I ,5-dienyl-rhodium(u1) indicates a bonding through a n-allylic system and the presenceof an unco-ordinated olefin gr0up.20~ The structure of acetylacetonato-(cyclo-octa-2,4-dienyl)palladium(11), also involves a co-ordination of an a,llylgroup with an unco-ordimted double bond remaining in the cyclic ligandgrouping .203A repeat of the X-ray structure with three-dimensional data,204 and a tlQ8 A. Nakamura and N. Hagihara, J . Organmnetallic Chern., 1965, 3, 480.lQ9 T. N. Margulis, L. Schiff, and M. Rosenblum, J . Ainer. Chm. SOC., 1965, 87,L. Porri, M. C. Gallazzi, A. Colombo, and G. Allegra, Tetrahedron Letters, 1965,3369.4187.201 R.F. Heck, J . Amer. Chem. SOC., 1965, 87, 4727.202 G. Paiaro, A. Musco, and G. Diana, J . Organometallic Chent., 1965, 4, 466.203 M. R. Churchill, Chem. Comm., 1965, 635.2 0 4 W. E. Oberhansli and L. F. Dahl, J . Organometallic Chem., 1965, 3, 43206 1NORUANI.O OHEXISTRY-140°c,205 of the z-allylpalladium chloride dimer indicates that the planeof the three allylic carbons is not perpendicular to the plane of the palladiumchloride bridged system; the dihedral angle between the two planes beingreported as 108" and 111.5". Interaction of z-allylpalladium chloridedimers with triphenylphosphine converts the compounds to o-ally1 complexes.A study of the n.m.r. spectra of the complex chlorotriphenylphosphine-(methylallyl)palladium(n), suggests a bonding structure of the ally1 groupintermediate between a n-ally1 and o-ally1 arrangement.206 A series ofn-allylpalladium complexes with bridging carboxylates have been preparedfrom the corresponding chloride with the silver carboxylate 207 and complexescontaining z-allylic palladium cations by interaction of the n-allyl-chloro-dimer with ethylenediamine or bipyridyl.20* Di-z-cyclododecenepalladiumchloride is formed from cyclododecene and palladium chloride.20 Dimerisa-tion of propene with palladium chloride in glacial acetic acid leads to acomplex formulated as a bridged chloro-mallyl complex.210 Nucleophilicattack occurs on the mallyl system of the z-allylpalladium chloride dimerby l-morpholinocyclohex-1 -ene, ethyl acetoacetate, and diethyl malonate.21fCarbonylation of allenepalladium complexes, and other allylic derivativesto give unsaturated esters has been studied.211 The reaction of octafluoro-cyclohexa-lY3-diene with di-z-cyclopentadienylnickel gives a complex (9) inwhich a n-cyclopentadienyl ring is condensed with the fluorocarbon to yielda bicyclic system with a z-ally1 bond to the metal.ls1F F FThe formation ofCyclobut adienediallylzinc has been studied.212Complexes.-cis-3,4-Dichlorocyclobutene reacts with ex-cess of iron ennacarbonyl to give cyclobutadieneiron tricarbonyl ; withtrans-dibromobenzocyclobufene, iron ennacarbonyl gives a cyclobutadienecomplex (The reactions of cyclobutadieneiron tricarbonyl indicate that it is aromatic,206 A.E. Smith, Acta Cryst., 1965, 18, 331.206 J.Powell, S. D. Robinson, and €3. L. Shaw, Chem. Comm., 1965, 78.207 S. D. Robinson and B. L. Shaw, J . Organometallic Chern., 1965, 3, 367.208 G. Paiaro and A. Musco, Tetrahedron Letters, 1965, 1583.209 R. Huttel and H. Dietl, Chern. Ber., 1965, 98, 1753.210 I. I. Moiseer, A. P. Belov, and G. Yu. Pek, Rzcss. J . Inorg. Chern., 1966, 10,180.J. Tsuji, H. Takahashi, and M. Morikawa, Tetrahedrort Letters, 1965, 4387;J. Tsuji and T. Susuki, {bid., p. 3027; J. Tsuji and S . Hosaka, J . Arner. Chew. SOC.,1965, 87, 4975.21sK. H. Thiele, W. Hanke, and P. Zdunneck, 2. anorg. Chem., 1965, 337, 63;J . Organometallic Chem., 1965, 4, 10.218 G. F. Emerson, L. Watts, and R. Pettit, J. Amer. Chem. Soc., 1965, 87, 131KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 207and find a close parallel in the substitution reactions of f e r r ~ c e n e .~ ~ ~ Decom-position of cyclobutadieneiron tricarbonyl in the presence of acetylenederivatives gives compounds with the Dewar benzene structure : phenylace-tylene gives hemi-Dewar biphenyl (1 l).215 Attempts to prepare compoundsof this type from tetraphenylcyclobutadienepalladium dichloride wereunsuccessfuL21eThe reaction of tetraphenylcyclobutadienepalladium or nickel dihalide hasbeen studied with cyclopentadienyliron dicarbonyl dimer and cyclopenta-dienylmolybdenum tricarbonyl dimer. With the iron compound, transferof cyclopentadienyl to the palladium or nickel occurs [ (Ph,C,)MC,H,]FeX,(M = Pd, Ni; X = C1, Br), but with the molybdenum compound thereaction gives (Ph,C4)Mo(C5H,)CO*X (X = Br, Cl).217 The cyclobutadiene-cyclopentadienylpalladium bromide reacts with cobalt octacarbonyl to give[Ph,C,]Co(C,H,). This is the first example of the simultaneous transferof two organic n-ligands from one metal to another.218 Reaction of tetra-phenylcyclobutadienepalladium dibromide with cobalt carbonyl yields then-comp1ex[Ph4C4]Co(C0),Br. This complex is paramagnetic, per N 3.5 B.M.The compound reacts with benzene or methyl-substituted benzenes, in the pre-sence of aluminium chloride to give the complexes, (~-arene)(Ph,C,)CoBr.~~~Diphen yla ce t ylene and di-p - c hlor op hen y la ce t y lene react with bis benz onitrile -palladium &chloride to give a polymeric cyclobutadienepalladium dichloridepolymer in which two cyclobutadienepctlladium dichloride units are con-nected by palladium dichloride units, [ (Ph,C,)PdCl,](PdCl,>,[ PdCl,( Ph,C,)].Alkoxides react with tetraphenylcyclobutadiene-metal derivatives to givecyclobutenyl derivatives by nucleophilic attack on a carbon atom of thecyclobutadiene ring.Both exo- and endo-derivatives may be obtained.220The X-ray structure of the two isomers of the cyclobutenyl complexes(Ph,C,OC,H,PdCl) have been determined.221 The cyclobutenylnjckelcomplex (Me4C4C5H,)NiC ,H5 is obtained by reaction of tetramethyl-butadieneniclcel dichloride with cy clopentadienylsodium ; the X-raystructure indicates a non-planar 1,2,3,4-tetramethyl-exo-cyclopentadienyl-butenyl anion bonded to the nickel by an allylic fragment of the cyclo-butenyl ring.Z22Cyclopentadiene Complexes.-The synthetic methods used in the pre-paration of cyclopentadiene-metal complexes has been reviewed.223 The13C n.m.r.spectra of a series of transition-metal cyclopentadienyl andcyclopentadienyl-carbonyl derivatives 224 and the mass spectra of someSoc., 1965, 87, 3254.G. D. Burt and R. Pettit, Chem. Comnz., 1965, 617.214 J. D. Fitzpatrick, L. Watts, G. F. Emerson, and R. Pettit, J . Amer. Chem.215 L. Watts, J. D. Fitzpatrick, and R. Pettit, J . Amer. Chem. SOC., 1965, $7, 3253;218 R. C. Cookson and D. W. Jones, J . Chem. SOC., 1965, 1881.a17 P. M. 3laitlis and A. Efraty, J . Organometallic Chem., 1965, 4, 172.21* P. M. Maitlis, A. Efraty, and M. L. Games, J. Amer. Chm. Soc., 1965, 87, 719.P. M. Maitlis and A. Efraty, J . Organometallic Chem., 1965, 4, 175.220P. M. Maitlis, D. Pollock, M. L. Games, and W. J. Pryde, Canad. J . Chem.,221 L. F. Dahl and W. E. Oberhansli, Inorg. Chem., 1965, 4, 629.222 W. Oberhansli and L. F. Dahl, Inmg. Chem., 1965, 4, 150.223 J. Birmingham, Adv. Organometallic Chem., 1964, 2, 365.224P. C. Lauterbar and R. B. King, J . Amer. Chem. Soc., 1965, W, 3266.1965, 43, 470208 INORGANIC CHEMISTRY7t- bonded organometallic compounds have been reported.225 The X-raystructure of the carbon-bridged cyclopentadienyliron complexes, a-oxo-1 ,l'-trimethyleneferrocene 226 and 1 ,l'-tetramethylethyleneferrocene, havebeen determined.227 In the cc-keto-complex the cyclopentadienyl rings areparallel to each other and nearly eclipsed, whilst in the ethylene-bridgedcompound the rings are tilted with respect to each other with an angleof 23" between the planes. The details of the structure of the moleculebiscyclopentadienylmolybdenum dihydride discussed last year have beengiven.228 In tricyclopentadienyluranium chloride, the three cyclopenta-dienyl rings and chlorine atom are arranged tetrahedrally around theuranium .229 The synthesis of the first transuranic cyclopentadienyl com-plex has been made, (C,H,),PU.~~* The radiochemical synthesis of aneptunium compound is also reported :231B-239U(C5H5)3C1 + 239Np(C,H,),C1.23 min.The first cyclopentadienyl complexes of bivalent lanthanides have beenprepared in dicyclopentadienyl-europium and -yttrium ;232 the compoundsare ionic, being similar to the calcium compound. The first cyclopentadienylisonitrile complexes of the lanthanides are also reported for iM(C5H,),CNC,H,(M = Y, Ho, Tb).233The reactions of dicyclopentadienyltitanium dichloride with hydrogens~lphide,~,~ ammonia, rneth~lamine,~35 and the anion (MNT)2- 236 havebeen reported. Methylcyclopentadiene( cyclopentadieny1)dimethylrhenium isformed from methyl iodide and 1,l -dilithiumdicyclopentadienylrheniumhydride which in turn is formed from dicyclopentadienylrhenium hydrideand n-b~tyl-lithium.~~' The binuclear ions [ C ,H 5Fe( CO) 2-X-Fe(CO) 2C5H5]+(X = Br, I), have been prepared by reaction of dicarbonylcyclopentadienyl-iron bromide or iodide with aluminium chloride. The ions are sensitive tonucleophilic attack to give [C,H,Fe(CO),X]+ (X = py, NCPh, NH,Ph).238The methoxycarbonyl complexes of iron, MeOCOFe( CO) 2( C5H,), andmanganese, MeOCOIL\/In(NO)(CO)C,H,, have been obtained.239 The firstn-bonded organic complex of platinum(1v) has been obtained as trimethyl-c yclopent ad ienylplatinum( IV) . 24 O2 2 5 N. Maoz, A. Mandelbaum, and M. Cais, Tetrahedron Letters, 1965, 2087.226 N. D. Jones, R. E. Marsh, and J. H. Richards, Actu Cryst., 1965, 19, 330.z2' M. B. Laing and K. N. Trueblood, Actu Cryst., 1965, 19, 373.228 M. Gerloch and R. Mason, J. Chem. Soc., 1965, 296.2zB C. M70ng, T. M. Yen, and T. Y. Lee, Acta Cryst., 1965, 18, 340.23O F. Baumgartner, E. 0. Fischer, B. Kanellakopulos, and P. Laubereau, Angew.2 3 1 F. Baurngartner, E. 0. Fischer, and P. Laubereau, Naturwiss., 1965, 52, 560.232 E. 0. Fischor and H. Fischer, J . Organometallic Chern., 1965, 3, 181.233K. 0. Fischer and H. Fischer, Angew. Chem., 1965, 77, 261.2 3 4 H . Kopf and IX. Schmidt, Angew. Chem., 1965, 77, 965.235A. Anagnostopoulos and D. Nicholls, J . lnorg. Nuclear Chem., 1965, 27, 339.336 H. Kopf and M. Schmidt, J. Organometallic Chem., 1965, 4, 426.237 R. L. Cooper, M. L. H. Greon, and J. T. Moelwyn-Hughes, J . Organometallic238 E. 0. Fischer and E. Moser, J . Organometallic Chem., 1965, 3, 16; 2. Naturforsch.,239 R. B. King, M. Bisnette, and A. Fronzaglia, J. Orguizonaetallk Chern., 1965, 4,2 4 0 % D. Robinson and B. L. Shaw, J . Chem. SOC., 1965, 1529.Chena., 1965, '77, 866.Chern., 1965, 3, 261.1965, 20b, 184.256KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 209An interesting development in the chemistry of n-complexes has beenthe preparation of a series of carborane analogues of cyclopentadienylcompounds ; reduction of the ion BgC2H, 2- with sodium in tetrahydrofuranand interaction of the resultant ion (BgC2Hll)2- with ferrous chloride givesthe ion [Fe(BgC2H,l)2]2-, this oxidises readily to the ion [Fe(BgC,Hl,),]-.241The (B,C2H,,)2- ion is considered to contribute six electrons to the bondingand to be bonded to the metal through open faces of the BgC2Hl12-icosahedraand be analogous to the behaviour of n-cyclopentadienyl groups.The cyclopentadienyl derivative [ (C5H5)(BsC,H,l)Fe] and the ion[(C,H5)(BgC2H11)Fe]- have also been prepared by carrying out the reactionin the presence of cyclopentadienylsodium.242 A determination of the X-raystructure of the compound [C,H,Fe(B,C,H,,)] confirms the bonding srrange-inent suggested for the carborane group.243 The tricarbonyl derivatives ofmanganese and rhenium, Cs[(B,C2H,,)M(CQ)3] (M = Mn, Re) are preparedfrom the sodium salt and the corresponding pentacarbonyl-metal bromide.244The cobalt complexes [(BsC2Kll)2Co]n- (n = 1, 2) and [Co(C5H5)(B9C2Hll)]have also been reported.245 A study of the e.s.r. spectra of a series of theiron(m) salts suggest similar bonding of the carborane to the cyclopenta,dienylsystem .24Metal-Arene Complexes.-The far-infrared spectra of arenetricarbonyl-chromium derivatives have been discussed in terms of molecular orbitalthe0ry.~~7 The molecular structure of benzene and hexamethylbenzenetricarbonyl have been determined and the data favour a complete delocalisa-tion of the n-electron system within the co-ordinated benzene, with D,,symmetry.248 The electron diffraction of gaseous dibenzenechromiuin isinterpreted in a similar inanner.249Vanadium carbonyl reacts with aromatic compounds to give the newcationic species [ V( CQ),L]+[V(CO),]- (L = 1 ,%dimethyl-, 1,2,3-trimethyl-,1,2,4,5-tetramethyl-, and hexamethyl-benzene). Poor yields of the relatedcompounds were also obtained with anisole and naphthalene .2so Dimesit -ylenevanadium rexts with carbon monoxide to give [V(CGH,Me3),][V(CO),].As the [v(co)6]- ion may readily be oxidised to vanadium carbonyl thisprovides a good route to vanadium carbonyL251 Tricarbonylanthrscene-chromium has been prepared and n.m.r. studies indicate that the Cr(CO),group is bonded to the outer ring of the a n t h r a ~ e n e . ~ ~ ~ Dibenzene-chromiumand -molybdenum react with terpyridyl (terpy), in cyclohexane to giveM(terpy) 2, Benzenechromium tricarbonyl with phenanthroline(phen) or2p1 M. F. Hawthorne, D. C. Young, and P. A. Weper, J. Amer. Chem. Soc., 1965,87. 1818. - _'Z82M. F. Hawthorne and R. L. Pilling, J. Amer. Chem. SOC., 1965, 87, 3987.243 A. Zalkin, D. H. Templeton, and T. E. Hopkins, J . Amer. Chenz. SOC., 1965,244M. F. Hawthorne and T. D. Andrews, J. Amer. Chem. Soc., 1965, 87, 2496.246 X. F. Hawt,horne and T. D. Andrews, Chenz. Comm., 1965, 443.246 A. H. Malri and T. E. Berry, J. Amer. Chem. Soc., 1965, 87, 4437.2 4 7 D. A. Brown and D. G. Carroll, J. Chenz. Soc., 1965, 2522.2p* 35. F. Bailey and L. F. Dahl, Inorg. Chenz., 1065. 4, 1395, 1314.249 A. Haaland, Acta Chem. Xcand., 1966, 19, 41.250 F. Calderazzo, Inorg. Chem., 1965, 4, 223.251F. Calderazzo and R. Cini, J. Chenz. SOC., 1965, 518.252 B. R. Willeford and E. 0. Fischer, J. Organo?netallic Chem., 1965, 4, 109.87, 3988210 INORGANIC CHEMISTRYbipyridyl(bipy) give Cr(phen),, Cr(bipy),, and with ferpyridyl Cr(terpy).253The first series of substitution reactions of dibenzenechromium have beenreported, utilising the reaction of pentyhodium with dibenzenechromiumas the intermediate r e a c t i o ~ ~ ~ 4 Reaction of methoxycyclohexadienes withchromium, molybdenum, or tungsten carbonyl gives the arenemetal tricar-bony1.255 A new bisarenemetal complex has been prepared with two metalatoms contained between two arene rings, by reaction of palladium dichloridewith a,lminium, aluminium chloride, and benzene, the structure of thecompound [PdAl&l,(C6H6)], is shorn in ( 12).256I I I II ICI-Al- CI-AI -Cl -P d-CCI - A l - CI -41 - CICI CI CI CI (12)IThe stereochemistry of tricarbonylcycloheptatrienechromium derivativesobtained by anionic addition to the tricarbonylcycloheptatrienechromiumsalts has been established as the exo-isomers. The endo-isomers are preparedby reaction of substituted cycloheptatriene with chromium hexacarbonylor tripyridinechromium tri~arbonyl.~~' The evidence for the stabilisationof aromatic carbonium ions by n-complexing with a metal carbonyl hasbeen discussed.258 The preparation of a cyclo-octatetraenemolybdenumtricarbonyl complex has been reported and the protonated compound,[C,H,Mo(CO), I+, has been formulated as a monohomotropylium derivative.259153 H. Behrens, K. Meyer, and A. Miiller, 2. ~aturforsck., 1965, ZOb, 74.254 E. 0. Fiecher and H. Bmnner, C h . Ber., 1965, 98, 175.s66A. J. Birch, P. E. Cross, and H. Fitton, Chem. Cmm., 1965, 366.266 G. Allegra, A. Immirzi, and L. Porri, J . Amer. Chem. SOC., 1965, 87, 1394.257 P. E. Baikie, 0. S. Mills, P. L. Pauson, Cr. H. Smith, and J. Valentine, Chem.268 J. D. Holmes, D. A. K. Jones, and R. Pettit, J. Organometallic Chem., 1965,S. Winstein, H. D, Kaesz, C. G. Kreiter, and E. C. Friedrich, J . Amer. Chem.Comnt., 1965, 425.4, 324.Soc., 1965, 87, 3267