摘要:

F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Part 111 Groups IV and V By P. G. Harrison 1 Transient Intermediates The synthesis of the highly reactive 1,l-difluorosiliran (l),which undergoes facile insertion reactions (uide infra) has offered an alternative mechanism for the reactions of difluorosilylene with ethene and ethyne. The preponderance of disilanyl products from the reactions involving :SiF2 has previously been interpreted in terms of an intermediate disilanyl *SiF2SiF2. diradical but the formation of such products may also be rationalised by intermediate siliran and siliren formation,' as shown in Scheme 1. Nevertheless siliran intermediates cannot satisfactorily explain the formation of cis-and trans-isomers in the reaction of thermally generated difluorosilylene with fluoro-alkenes and a mechanism involving attack of *(SiF2); diradical oligomers at the C=C double bond followed by rearrangement was proposed in this case.' New silylenes and also increasingly the generation of silicon and germanium analogues of the multiple bonds shown by:arbon continue to arouse much interest.Trimethyls~!yl(methyl)silylene Me3Si-SiMe and trimethylsilylmethylsilylene Me3SiCH2SiMe are formed during the low-pressure gas-phase pyrolysis of Me3SiSiMe3 and Me3SiCH2SiC1MeSiMe3 respectively at 600-700 0C.3 Photolysis is the alternative to thermal generation and Me2% may be obtained by photolysis of (MezSi)6 which undergoes ring-contraction to (Me2Si)5. Less reactive MePhSi is similarly generated from Me3SiSiMePhSiMe3 or Me3SiSiMePhSiMePhSiMe3.Both silylenes are efficiently trapped by 1,1,3,3-tetramethy1-2-0~0-1,3-disilacyclo-pent ane. 475 Frederick Stanley Kipping who expended so much effort endeavouring to obtain silicon analogues of ketones would have been extremely gratified to observe the variety of multiple bonds involving silicon and germanium which have now been reported albeit as transient species. The alkene analogue 1,1,2,2-tetramethyl- 'I1 G. Eul-enberger,Acta Cryst. 1978 B34 2614. '"T. Platzner J. K. Thomas and M. Gratzel 2.Naturforsch. 1978,33b 614. D. Seyferth and D. P. Duncan J. Amer. Chem. SOC.,1978,100,7724. * C.-S. Liu and T.-L. Hwang J. Am&. Chem. Soc. 1978 100 2577. W. D. Wulff W. F. Goure and T. J. Barton J. Amer.Chem. SOC., 1978 100 6236. H. Okinoshima and W. P. Weber J. Organometallic Chem. 1978 150 C25. M. Ishikawa K.-I. Nakagawa M. Ishiguro F. Ohi and M. Kumada J. Organometallic Chem. 1978,152 155. The Typical Elements HC=CH .SiF HC=CH HCrCH +:SiF + \ 1 3 I I Si F2Si -SiF F2 J/ CH=CH / F,Si* + HC=CHSiF,SiF,CH=CH 1H-transiei HC ZCSi F SiF,CH=CH Scheme 1 disilene MezSiSiMez is generated by pyrolysis of (2) at 600 "C but Kipping's original goal the silanones R2Si=0 are formed by the photolysis of aryl-substituted polysilanes in the presence of DMS0.6.7The reaction of the siliren (3) with DMSO also proceeds via transient Me2Si=0.8 Transient germanones R2Ge=0 are SiMe Me,SiC=CSiMe \/ Si Me2 (2) (3) produced by thermolysis of suitable germanium heterocycles such as germa-oxetans -dioxolans and -oxazalidines and also from adducts of germa-diazolidines with PhNC0.9 Similar adducts of germa-oxazolidenes and -diazolidines with sulphur- containing unsaturated reagents such as CS or PhNCS undergo /3 -elimination reactions to afford thiogermanones RZGe=S.l0 H.Okinashirna and W. P. Weber J. Organometallic Chem. 1978,155 165. 'H. Okinoshima and W. P.Weber J. Organometallic Chem. 1978 149 279. D. Seyferth T. F. 0.Lim and D. P. Duncan J. Amer. Chem. SOC. 1978,100 1626. H. Lavayssiere J. Barrau G. Dousse J. Satge and M. Bouchaut J. Organometallic Chem. 1978 154 c9. H. Lavayssiere G. Dousse J. Barrau J. Satge and M. Bouchaut J. Organometallic Chem. 1978 161 c59.F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Silicon-carbon doubly-bonded intermediates have often been postulated as reac- tion intermediate^.^"'-13 but unequivocal proof of silabenzene formation has been elusive. However the production of 1-silabicyclo[2,2,2]octatriene derivatives (4; R = H or CF,) from the co-pyrolysis of 1-methyl-1-vinyl-1-silacyclohexa-2,4-diene and an alkyne must necessarily pass through such a transient species or its very close equivalent.I3 The sila-imine Me,Si=NSiMe3 is produced in the thermolysis of (5),14 but a more general method is available for the germa-imine intermediates R2Ge=NPh via the reaction of bivalent germanium derivatives with phenylazide. l5 The phosphorus analogue MezGe=PPh results from the exchange of Me,GeCl with 2,5-di- silaphospholans and can be trapped by ethylene oxide and sulphide.'6 The genera- tion of a sila-phosphimine has not been reported but dimethylsilylenephosphorane Ph,$-SiMez has been postulated as an intermediate in the reaction of hexamethyl- siliran with ketones in the presence of PPh3 to give 1,4-dioxa-2,5-disilacyclohexane derivative^.^^ Me Me ,\Si '/SiMe Me,!%-N 'C 'N=N ' 'SiMe The two classical methods of stabilising transient intermediates are by matrix- isolation and by co-ordination to a transition metal.Matrix-isolation has been employed to show that :SiF2 and either SiF2- or a diradical SiF species are the products of the reaction of SiF4 with lithium." Transition-metal complexes of unstable species may be produced in one of two ways substitution at an already co-ordinated ligand or by reaction of a suitable precursor with the transition-metal compound.The former method has yielded (OC)5M,P(NH2)3 (M = Cr Mo or W) [by ammonolysis of (OC)5M,PC13]'9 and (OC)5M,Ge(SR)2 (M = Cr or W) [by reaction of (OC)5M,GeCl,(THF) with silyl thioethersIz0 complexes. Comparison M. Ishikawa T. Fuchikami and M. Kumada J. Organometallic Chem. 1978,149 37. M. Ishikawa T. Fuchikami and M. Kumada J. Organometallic Chem. 1978 162,223. l3 T. J. Barton and G. T. Burns J. Amer. Chem. SOC. 1978 100 5246. l4 N. Wiberg and G. Preiner Angew. Chem. Internat. Edn. 1978 17 362. P. Riviere A. Caze A. Castel M. Riviere-Baudet and J. Satge J. Organometallic Chem. 1978,155 C58.C. Couret J. Satge J. D. Andriamizaka and J. Escudie J. Organometallic Chem. 1978 157 C35. l7 D. Seyferth and T. F. 0.Lim J. Amer. Chem. SOC. 1978,100,7074. D. L. Perry P. F. Meier R. H. Hauge and J. L. Margrave Inorg. Chem. 1978,17 1365. l9 H. Noth H. Reith and V. Thorn J. Organometallic Chem. 1978,159 165. 2o P. Jutzi W. Steiner E. Konig G. Huttner A. Frank and U. Schubert Chem. Ber. 1978 111,606. The Typical Elements 211 of silylenes with carbenes is inevitable and therefore it is rather surprising that silylene-transition-metal complexes are not more common. The rather sophisti- cated extremely air-sensitive silylene-iron complex (6)is formed by the reaction of Me3SiSiMe2H with Fe,(CO) in benzene.'* Phospha- and arsa-ethynes RC=E (E= P or As) co-ordinated to dicobalt hexacarbonyl residues (7) are obtained by the reaction of RCC12EC12 with CO,(CO)~ at -78 "C.The phosphorus and arsenic derivatives differ markedly. The arsenic compound is chemically robust and air- stable in sharp contrast to the quite sensitive phosphorus complex.22723 Significantly C-fluorophosphaethyne FC=P is stable and may be isolated in high yield by slowly passing CF,PH2 vapour over solid KOH at room femperat~re.~~ R I H I Me2Si=Fe(C0)3 I SiMe3 (6) (7) 2 Bivalent Derivatives of Germanium Tin and Lead Although almost half of the publications in this area report the results of structural determinations the most notable observation is that of the oxidative biomethylation of bivalent tin by methyl~obalamin.'~ Biomethylation takes place only in the presence of an oxidising agent such as aquo-cobalamin at pH 1.0 in 1.0M-NaCl.Significantly no biomethylation of Sn'" occurs under similar conditions. Whether the four-co-ordinate pseudo-trigonal-bipyrmidal geometry (8) or the alternative pyramidal stereochemistry (9)is adopted by bivalent tin depends largely upon the ligands involved. Four-co-ordination is preferred when chelating groups [e.g. as in Sn(ONPhCOPh)2 and Sn(S2COMe), reported previously] and also when very electronegative potentially bridging donor atoms are present. However although the geometry at the metal may be similar for different ligands a wide variety of gross structural types may result. Thus the formate bridging in tin(I1) formate in which each tin atom is connected to its four nearest neighbours by four formate groups leads to a two-dimensional sheet structure.26 In contrast the bridging of adjacent tin atoms in tin(I1) bis(dihydrogen phosphate) is via a single oxygen atom from each of four different [H2P04] groups giving infinite [Sn04] chains.27 Oxygen-bridging also occurs in Sn,04(0Me)4 obtained from the careful hydrolysis of tin(I1) dimethoxide but in this case crystals are composed of discrete molecules with the adamantyl-[Sn604] skeleton and triply bridging methoxy-groups (Figure l)." Surprisingly although the structure of SnO itself is also of this type the 21 H.Sakurai Y. Kamiyama and Y.Nakadaira Angew. Chem. Internat. Edn. 1978 17 674. *' D. Seyferth and R.S.Henderson J. Organometallic Chem. 1978. 162 C35. 23 D. Seyferth and J. S. Merola J. Amer. Chem. SOC.,1978 100,6783. 24 H. W. Kroto J. F. Nixon N. P. C. Simmons and N. P. C. Westwood J. Amer. Chem. SOC.,1978,100 446. 2s L. J. Dizikes W. P. Ridley and J. M. Wood J. Amer. Chem. Soc. 1978 100 1010. 26 P. G. Harrison and E. W. Thornton J.C.S. Dalton 1978 1274. 27 R. Herak B. Prelesnik M. Curic and P. Vasic J.C.S. Dalton 1978 566. 28 P. G. Harrison B. J. Haylett and T. J. King J.C.S. Chem. Comm. 1978 112. F. A. Hart A. G.Massey P. G.Harrison and J. H. Holloway Figure 1 The structure of adamantyI-S~~~O~(OMe)~ (Reproduced from J.C.S. Chem. Comm. 1978 112) geometry at tin in the ternary oxide K2Sn203 (prepared by heating 1.lKOo., +SnO at 550°C) is of the pyramidal type (9) in a perovskite-type layer structure.29 A similar variability of structure is exhibited by tin@) fluoride derivatives which can adopt both three- and four-co-ordinate geometries.Pyramidal three-co-ordinated tin occurs in NH4+SnF3-,30 and also in Sn3BrFs,31 the structure of which is built up from [Sn12F20]:"+ macro-cations which interconnect to form infinite layers. However in Sn21F3,32 which also has a layer structure and in Sn(NCS)F,33 which has a 'ladder' structure similar to that in SnClF the tin atoms possess the four-co- ordinated geometry. Anionic tin derivatives of this stereochemistry appear to need a X 29 R. M. Brown and R. Hoppe Angew. Chem. Internat. Edn. 1978,17,449. 30 G. Bergerhoff and H. Namging Actu Cryst.1978 B34,699. 31 S. Vilminot W. Granier and L. Cot Acta Cryst. 1978 B34 35. 32 S. Vilminot W. Granier Z. A1 Oraibi and L. Cot Acta Cryst. 1978 B34 3308. 33 S. Vilminot W. Granier Z. A1 Oraibi and L. Cot Actu Cryst. 1978 B34 3306. The Typical Elements 213 large cation for their stabilisation and in this respect the [C13Sn(OC103)]2- anion with the [(NH3),Co(S02Ph)12' cation as gegenion is no exception. The complex is however unstable giving Sn'" and C103- among the products probably via a mechanism involving oxygen transfer between C104- and With the less electronegative ligands the pyramidal geometry is adopted. Thus tin(I1) thiocyanate has a structure based on the PbC1 type with three short contacts (two Sn-N and one Sn-S),,' and the remarkable tin(I1) chloride adduct (10)also has primary three-co- ~rdination.,~ Very high co-ordination numbers for lead occur in molten PbC12 and PbCl2-LiC1 mixtures.In PbC12 itself the lead ions are surrounded by ca. eight chloride anions at distances close to the sum of the ionic radii but the tendency to form [PbCl,] units increases with increasing LiCl content.37 The chemistry of organometallic derivatives of bivalent germanium tin and lead continues to arouse interest. The bis-cyclopentadienyl compounds all have the 'centrally' bonded skew-sandwich ~tructure.~~ This structure rather than the peripherally bound structure characteristic of the quadrivalent cyclopentadienyl derivatives appears to arise from the presence of a degree of n-bonding in these compounds (photoelectron spectral data).In its absence the peripherally bonded structure is adopted.39 Although the reactions of these compounds have been investigated widely; two new reaction types have been characterised homolytic Sn-C5H5 bond fission and substitution at the co-ordinated ligand. Photolysis of (C5Hs)2Sn in toluene yields the C5H5- radical (e.s.r.) but the other product the C5H5Sn*radical could not be detected and its fate is ~ncertain.~' Substitution at the co-ordinated cyclopentadienyl group was accomplished by refluxing (C,H,),Sn and Me,SnNEt in benzene for 6 h. The product (Me3SnC5H4)2Sn an extremely oxygen- and moisture-sensitive yellowish-green oil is the first example of a molecule containing Sn"-C and Sn'"-C The reaction of (C5H5)2Sn with HMo(CO),(C,H,) in a 1 3 molar ratio to give the tin hydride HSn[Mo(CO),(C,H,)] probably proceeds via initial protolysis yielding the molybdenum analogue of Sn[W(CO),(C,H,)] {obtained previously from the reaction of (C5H5)2Sn and HW(CO),(C5Hs) in a 1:2 molar ratio} which then undergoes insertion into the Mo-H bond of a further molecule of HMo(CO),(C5H5) to afford the isolated product.The hydride may be converted into the corresponding chloride CIS~[MO(CO>~(C~H~)]~ by treatment with chlorinated hydrocarbons but reaction with HC1 or HOAc results in Sn-Mo bond cleavage giving X2Sn[Mo(CO),(C,H,)] (X = C1 or OAc) complexes.42 Such insertion reactions of monomeric bivalent germanium and tin compounds appear to favour radical mechanisms.The insertion of GeCI, SnCl, and SnBr into the Fe-C a-bonds of (C,H,)(C0)2FeR (R = alkyl or aryl) compounds in THF has been shown to occur by a radical-chain process,43 an 34 R. C. Elder M. J. Heeg and E. Deutsch Znorg. Chem. 1978 17 427. '' A. G.Filby R. A. Howie and W. Moser J.C.S. Dalton 1978 1797. 36 M. Veith Chem. Ber. 1978 111 2536. '' H. Ohno M. Yoroki K. Furukawa Y. Takagi and T. Nakamura J.C.S. Faraday Z 1978,74,1861. 38 A.Bonny A. D. McMaster and S. R. Stobart Znorg. Chem. 1978 17 935. 39 S.Cradock and W. Duncan J.C.S. Faraday ZZ 1978 74 194. 40 A. G.Davies and M.-W. Tse J.C.S. Chem. Comm. 1978,353. 41 E.J. Bulten and H. A. Budding J. Organometallic Chem. 1978 157 C3. 42 C.D. Hoff and J. W. Connolly J. Organornetallic Chem. 1978 148 127.J. D. Cotton and G. A. Morris J. Organometallic Chem. 1978,145 245. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway initial allylic rearrangement accompanying the insertion when R is all~l.~~ The insertion of SnC12 into the Ru-Cl bond of (C6H6)RuCl(Me)[Ph2PNHCHMePh] is highly stereospecific but the mechanism of insertion is ~nknown.~' The catalysis of the oxidative additions of PhBr to Sn[CH(SiMe3),J2 and of PhBr and Bu'Cl to Sn[N(SiMe,),] may also be interpreted in terms of a radical chain process involving tin-centred radicals.46 A similar insertion of PbI into alkyl iodides to give mono- alkyl-lead tri-iodides is catalysed by Me3Sb.47 Crown ether complexes of bivalent tin have been prepared for the first time. Complexation of SnC12 and SII(NCS)~ by 18-crown-6 yields complexes of the type [(crown)SnL]'[SnL3]- (L = C1 or NCS) but a complex of composition Sn(crown)- (C104) is formed from Sn(C104)2,3H20.48 Similar lead complexes have been known for some time and two kinetic studies of their complexation decomplexation and ligand-replacement reactions have been rep~rted.~~*'~ Not surprisingly the reac- tions are complex; for example the replacement of a cyclic polyether (Y) by a twelve-membered tetramine (L) in an acetate buffer is simultaneously first-order in [L] [Pb(OAc)'] and [PbY2'].s0 3 Nitrogen Chemistry Nitric oxide reacts with Lewis acids at 77 K to form the red unsymmetrical dimer species O=N-O=N in which the N=O groups retain strong multiple bond character and are joined by a weak N-0 single bond.'l Niobium and nickel readily decompose NO at high temperatures with first-order kinetics to deposit the gases on the surface of the metal.Platinum was inactive." Much effort has been directed towards the evaluation of rate-constant data for reactions involving nitrogen oxide species many of which are important in atmospheric chemistry. Their sheer number preclude an in-depth discussion in this report and so they are only summarised here viz. NO'+e- + N+O (ref.53) NO'+X- -B NO+X (X=C1 Br or I) (ref. 54) NO+C10 + NO;!+Cl (ref.55) Cl+NO+N + ClNO+N (ref.56) 44 J. D. Cotton J. Organometallic Chem. 1978 159,465. " H. Brunner and R. G. Gastinger J.Organometallic Chem. 1978,145 365. 46 M. J. S.Gynane M. F. Lappert S. J. Miles and P. P. Power J.C.S. Chem. Comm. 1978 192. 47 G. Chobert and M. Devaud J. Organometallic Chem. 1978,153 C23. 48 R. H. Herber and A. E. Smelkinson Znorg. Chem. 1978,17 1023. 49 L. J. Rodriguez G. W. Liesegang M. M. Farrow N. Purdie and E. M. Eyring J. Phys. Chem. 1978,82 647. so M. Kodama and E. Kirnura Inorg. Chem. 1978,17,2446. J. R. Ohlsen and J. Laane J. Amer. Chem. SOC. 1978,100,6948. '' J. A. Morgan and A J. B. Robertson J.C.S. Faraday I 1978,74,211. s3 N. A. Burdett and A. N. Hayhurst J.C.S. Faraday Z 1978 74 53. 54 N. A. Burdett and A. N. Hayhurst J.C.S. Faraday Z 1978,74,63. s5 M. T. Leu and W. B. DeMore J. Phys. Chem. 1978,82,2049. 56 J. H. Lee J. V. Michael W. A. Payne and L. J. Stief J. Chem. Phys. 1978,68 5410.The Typical Elements 215 N205 $ N02+N03 (ref.57) 2N03 -+ 2N02+02 (ref.57) O+N20 + products (ref.57) O+N03 -+ 02+N02 (ref.57) N02+N03 -+ NO+02+N02 (ref.57) NO+NO -* 2N02 (ref. 57) NOz-+HCl -* Cl-+HNOz (ref. 58) ClO-+NO -+ NO,-+Cl (ref.58) -+ NOZ-+C10 ClO-+ NO2 +Cl-+ NO3i3 N03-+Cl (ref 58) HN03+C1 HCl+N03 (ref.59) M H02N02 + NOz+HO:! (refs.60 61) In addition the kinetics and mechanisms of the decomposition of the HN203- and of the NO-NH20H reaction have been elucidated. Both reactions involve nitroxyl (HNO) as an intermediate and it is the primary product in the decomposition of the HN203- anion subsequently either dimerising to give N20 or being reduced to N2. The relative amounts of N2 and N20 produced are sensitive to pH and NH20H concentration and at pH8 and with a ten-fold excess of NH20H the reaction product is >97% N2.The reaction of NO with NH20H is also pH-sensitive producing equimolecular amounts of N20 and N2 at pH > 13 but N,O almost exclusively at pH 8. In this reaction the first step is abstraction of a nitrogen-bound H atom by NO to give nitroxyl and the NHOH radical. The NHOH radical then combines with a further NO to form nitrosohydroxylamine which then decomposes to give N20. That the nitroxyl produced in this reaction also gives N20 at pH 8 whereas that from the decomposition of the NH203- anion produces largely N2 demonstrates that different reaction intermediates are involved.62 Steady-state concentrations of ground-state nitroxyl have been generated by the reaction of hydrogen atoms with NO,63 but nitroxyl is more usefully generated by the thermal dissociation of 9,10-dihydro-9,10-epoximino-9,lO-dimethylanthracene at 70 “C,as shown in Scheme 2.The nitroxyl produced decayed rapidly (-1 min) with order 3 64 -3. ” R. A. Graham and H. S. Johnston J. Phys. Chem. 1978,82,254. ’* I. Dotan D. L. Albritton F. C. Fehsenfeld G.E. Streit and E. E. Ferguson J. Chem. Phys. 1978,68 5414. ” G. Poulet G. Le Bras and J. Combourieu J. Chem. Phys. 1978,69,767. 6o R. A.Graham A. M. Winer and J. N. Pitts J. Chem. Phys. 1978,68,4505. 61 A.C. Baldwin and D. M. Golden J. Phys. Chem. 1978,82,644. ” F. T. Bonner L. S. Dzelzkalns and J. A. Bonucci Inorg. Chem. 1978,17,2487. 63 N.Washida H. Akimoto and M.Okuda J. Phys. Chem. 1978,82,2293. 64 J. E.J. Corrie G. W. Kirby A. E. Laird L. W. Mackinnon and J. K.Tyler J.C.S. Chem. Comm. 1978 275. F. A. Hart A. G.Massey P. G.Harrison and J. H. Holloway a-HNO + & 70-100°C Me Me ,,O H Scheme 2 Photolysis of NOCl in an oxygen matrix at 10 K gives chlorine nitrate in high yield. Isotopic substitution shows that the N=O bond remains intact the oxygen atom eventually residing in a terminal position in C10N02. The proposed mechanism involves initial C1-N bond cleavage followed by incipient ClOO formation by the reaction of atomic chlorine with matrix 02.Subsequent oxygen abstraction by the co-isolated NO molecule gives C10 and NO2 radicals which recombine in the same matrix cage to give C10N02.65 As with other nitrosyl derivatives NOCN is bent at nitrogen (113*2") but is also bent at carbon (169.5 f The amino radical NHz is produced by the abstraction of a hydrogen atom from NH by the hydroxy-radical in irradiated aqueous solutions at pH 11.4.In acidic solutions abstraction from the [NH,]' is too slow to be observed. The SO,; and PO4?-radicals react similarly but more slowly. The rates of reaction of the amino radical with substituted phenoxide ions are strongly affected by substituent effects and proceed by electron-transfer o~idation.~~ The electronic changes occurring during the reaction of an amino radical and a hydrogen atom have been the subject of a theoretical study. In the initial stage of the reaction the electron cloud preceding the atomic region of the hydrogen atom is polarised towards nitrogen.In the intermediate stage electron density flows into the N-H overlap region from the region behind the approaching hydrogen nucleus; and in the last stage the reaction is terminated by the rapid increase of repulsive extended gross charge formed between the under-shielded nuclei.68 Ab initio LCAO MO methods have been employed to study the stability and structure of various species. NSF is predicted to be more stable than its isomer SNF in agreement with Similarly HNS and (linear) NNS are predicted to be more stable than HSN and NSN respectively and the order of stability of the isomers of H3NS is predicted to be H2SNH <H3SN< HSNH <SNH,. NzS2 is predicted to be square planar in agreement with recent experimental evidence." The course of the reaction of NF3 with alkyl radicals depends on their size.With smaller radicals the corresponding alkyldifluoroamine is obtained but with isopropyl and t-butyl radicals both alkyldifluoroamine and alkyl fluoride are formed.71 The reaction of N2F4 and SbF in anhydrous HF yields the SbF6- salt of the planar NzF3+ cation. The corresponding SnF,- salt may be obtained by metathesis with Cs2SnF6 also in HF but no stable adduct is formed between N2F4 and BF, even at -78 0C.72 " D. E. Tevault and R. R. Smardzewski J. Phys. Chem. 1978 82 375. 66 R. Dickinson G. W. Kirby J. G. Sweeny and J. K. Tyler J.C.S. Faraduy ZI 1978 74 1393. 67 P. Neta P. Maruthamutha P. M. Carton and R. W. Fessenden J.Phys. Chem. 1978,82 1875. ''H. Nakatsuji T. Koga K. Kondo and T. Yonezawa J. Amer. Chem. Soc. 1978,100 1029. 69 S. P. Su and W. G. Richards J.C.S. Faraduy ZZ 1978 74 1743. 70 M. P. S. Collins and B. J. Duke J.C.S. Dalton 1978 277. 71 P. Cadman Y. Inel and A. F. Trotman-Dickenson J.C.S. Furuduy Z 1978,74,2301. 72 K. 0.Christie and C. J. Schack Znorg. Chem. 1978 17 2749. The Typical Elements 217 4 Rings and Clusters The principal interest in heterocyclic chemistry of elements of Group IV centres around small carbocycles. l,l-Difluoro-2,2,3,3-tetramethyl-l -siliran (1l) synthesised by ring-closure of bis-(a-bromo-isopropy1)difluorosilane using magnesium in THF-ether is much less stable and more reactive that its dimethyl analogue.Its decomposition (tiin THF -1.75 h at room temperature) proceeds by the initial formation of the *F2SiCMe2CMe2- diradical which then undergoes coupling to give the *CMe2CMe2SiF2SiF2CMe2CMe2* diradical leading to the final products (12) (by cyclisation) and (13) (by hydrogen-atom transfer). Compound (11) Me2 Me Me2C-CMe Me2CA\. StFZ I CH =c' -CMe2Si F2SiFzCMe \/ I I Si Me2C ,SiF2 I F2 C CHMe (11) Me2 (13) (12) reacts principally by 'two-atom' insertion with multiply bonded reagents to afford silacyclopentane derivatives.' Four-membered ring systems containing one or two silicon atoms have been studied widely. Silacyclobut-2-enes (14)are easily prepared in moderate yield by the pyrolysis of diallyl~ilanes,~~ whilst 1,2-disilacyclobut-3-enes (15)result from the reaction of tetramethyldisilene with alkynes.These products are extremely air-sensitive and are readily oxidised to the corresponding disiloxanes (16)by molecular oxygen. Ring-expansion also occurs with silylenes Fe2(C0)9 and alkynes affording (17) (18) and (19) respe~tively.~~ The eventual products from the thermal generation of the disilene [Me,SiSiMe,] are the 1,3-disilacyclobutanes (20) and (21). The formation of these compounds involves several no!el types of reaction. Initially the disilene rearranges to the silyl-silylene Me3SiSiMe [whose independent generation also results in the forma- tion of (20) and (21)] which undergoes intramolecular C-H insertion to form disilacyclopropene (22). Subsequently this undergoes Si-Si bond fission accom- panied by either hydrogen- or methyl-migration to form (silylmethy1)-silylenes which ring-close to yield the observed product^.^ 73 E.Block and L. K. Revelle J. Amer. Chem. Soc. 1978,100 1630. H. Sakurai T. Kobayashi and Y. Nakadaira J. Organometallic Chem. 1978,162,C43. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway n Me,Si Me,% .>i-H -+ ZSi-H t I Me H H Me,SiSiMe +Me,Si-SiMe -+ \A/ (20) Si-Si /\ Me Me Me I H I Me (21) Chloro-silacyclobutane undergoes substitution to afford silicon germanium tin iron and manganese derivative~,~’*~~ as shown in Scheme 3. Reagents i NaMn(CO),; ii Ph3MLi (M =Si or Ge); iii Me,SnLi; iv NaFe(CO),(C,H,) Scheme 3 The reaction of 1-methylsilacyclobutane with (Ph3P),(C2H,)Pt results in the -formation of the similar platinum complex (Ph3Pj2(HjPt(Si(Me)CH2CH2CH2}, but its reaction with Fe2(C0)9 yields two products the iron-substituted silacyclobutane (23)and the five-membered 1-sila-2-ferracyclopentane Such complexes may be generally prepared by the reaction of silacyclobutanes with Fe2(CO), and can be obtained by ring-closure of SiMe2[(CH2)3C1]C1 with Na2[Fe(C0)4].78 Four- membered silicon-containing heterocycles such as (25) and (26) result from the reaction of HMe2SiESiMe2H(E =0 or CH,) with suitable transition-metal deriva- tive~.~~ under U.V.photolysis the five-membered With Fe(CO)5 or RU~(CO)~* 7s C. S. Cundy M. F. Lappert and C.-K. Yuen Znorg. Chem. 1978,17 1092. 76 C.S. Cundy M. F. Lappert and C.-K. Yuen J.C.S. Dalton 1978 427. 77 C. S. Cundy and M. F. Lappert J. Organometallic Chem. 1978,144,317. ’13 C. S. Cundy and M. F. Lappert J.C.S. Dalton 1978,665. 79 M. D. Curtis and J. Greene J. Amer. Chem. SOC. 1978,100 6363. The Typical Elements heterocycles (27) are produced. Fe(CO)5 and Me4GezHz0 afford an analogous product.80 Cyclo-(Ph,Si,) contains an essentially square quasi-planar four-membered ring,81 but the five-membered ring in cyclo-(PhloSi5) is puckered.82 Cyclo-(MelzSi6) may be obtained quantitatively in a one-step synthesis in high purity (>99%) by treating MezSiC1 with lithium metal in THF at O"C.83 The reaction of cuw-dichloro-polysilanes C1(SiMez) C1 with LizPPh yields the five- six- and seven-membered heterocyclic phosphasilanes PhP(SiMe,), when n =4-6 but a polymer is obtained when n = 3.Reaction with CIMezSiSiMezC1 yields the six-membered heterocycle (28) and the four-membered ring system (PhPSiMe2)z is produced by reaction with MezSiClZ at -40 "C but at +40 "C trimeric (PhPSiMez)3 is ~btained.,~ This latter derivative and the acyclic sila-phosphine MeSi(PBu2) can function as terdentate ligands affording such cluster complexes as (29)84and (30).,' Me Ee2 y2 / I PhP PPh si-s Me2 Me (28) PhP PPh PPh \1J oc Mo 0 0 (29) (30) J. Greene and M.D. Curtis Znorg. Chem. 1978 17 2324. L. Parkanyi K. Sasvari and I. Barta Actu Cryst. 1978 B34 883. 82 L. Parkanyi K. Sasvari J. P. Declefiq and G. Germain Acta Crysf.,1978 B34 3678.83 M.Laguerre J. Dunogues and R. Calas J.C.S. Chem. Comm. 1978 272. 84 R. T. Oakley D. A. Stanislawski and R. West J. Organometallic Chem. 1978 157 389. 85 J. J. De Boer J. A. van Doorn and C. Masters J.C.S. Chem. Comm. 1978,1005. 220 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Anionic metal clusters were discussed at length last year. A significant addition to the study of such species is the application ofF.T. n.m.r. which has been employed to identify mixed tin-lead and tin-antimony anion clusters in solution. Dissolution of Na-Sn alloys of composition near NaSn2.2 in ethylenediamine results in typical deep orange-red solutions of the Sn94- anion. The "9Sn n.m.f. spectra of such solutions exhibit a single line indicating that the individual environments of the static C4" structure (monocapped square antiprism) are averaged in some manner which observation of 117Sn-119 Sn coupling shows must be intramolecular.Dual '19Snand 207 Pb n.m.r. studies of extraction from Na-Sn-Pb alloys again using ethyl- enediamine show that all the possible mixed cluster anions [Sn9-,Pb,4-] (x = 0-9) are formed. Similar extraction from Na-Sn-Sb alloys yields a new mixed anionic cluster suggested to be either or SbSn9-.86 The reaction of Me2SnH2 with white phosphorus in the presence of DMF yields the tin-rich phosphastannane cluster (31). In the absence of organic bases such as DMF or pyridine the already known cluster (Me2Sn)6P4 is obtained. Organo-tin hydrides containing tin-tin bonds also react with white phosphorus to give heterocycles still more rich in tin; thus tetramethyldistannane affords (Me2Sn)6P2.87 Elemental white phosphorus may be converted directly into trialkyl phosphites in high yield by direct reaction with alkoxide anion in the presence of CC14:s8 P4+ 6RO-+ 6CC14+ 6ROH -+ 4P(OR)3+ 6CHCI3+ 6CI-The mechanism proceeds via initial nucleophilic attack on the [P4] unit followed by rate-determining P-P bond fission.The role of the CC1 appears to be the formation of easily alcoholised P-C1 bonds as shown in Scheme 4. RO:\ RO\ P 1 etc. Scheme 4 n6 R. W. Rudolph W. L. Wilson F. Parker R. C. Taylor and D. C. Young J. Amer. Chem. Soc. 1978,100 4629. B. Mathiasch and M. Drager Angew. Chem. Internat.Edn. 1978 17 767. '* C. Brown R. F. Hudson G. A. Warten and H. Coates J.C.S. Chem. Comm. 1978 7. The Typical Elements 221 The structures of several phosphorus ring and cluster compounds have been resolved by X-ray diffraction studies. The 1 1 adducts formed between amino- phosphinimines R2NP=NBu' and 3u'NNN do not have the imino-bridged triaza- A 5-phosphetine structure (32) as previousIy thought but rather structure (33) containing the almost planar five-membered ",PI ring.g9 The structures of two isomers of N4P4C1,(NMe2) were reported last year. Since then the structure of a third the cis-trans-cis-trans- isomer (34) has been determined. Both crystallo- graphically independent molecules have a ring conformation intermediate between Bu' N/N\ II PNR, N N / 'N' Bu' Bu' the 'saddle' and 'tub' forms expected on the basis of substituent a~rangement.~' In contrast the structure of two of the three modifications of decafluorocyclo-pentaphosphazene (F2PN)5 (m.p.-50 "C) obtained by low-temperature crystal- lisation exhibit rather different ring conformations. In one the ten-membered ring is somewhat 'boat' shaped with the molecule possessing a pseudo-two-fold axis (Figure 2a). The conformation of the ring of the ring in the other modification is irregular and resembles to some extent the structure of (Br2PN) (Figure 2b).91 Figure 2 Views of the two different modifications of decafluorocyclopentaphospharene (Reproduced from J.C.S. Dalton 1978 1425) Molecules of a-P4S4 possess D2d symmetry within experimental error (35),92 whereas derivatives of closo-tetraphosphorus hexakis(methy1imide) are based on a central adamantyl-[P4N6] unit.Thus the tetra-P-oxo and tetra-P-thio derivatives 89 S. Pohl E. Niacke and H.-G. Schafer Angew. Chem. Internat. Edn. 1978 17 136. 90 M. J. Begley and D. B. Sowerby J.C.S. Dalton 1978 1094. 91 J. G. Hartsuiker and A. J. Wagner J.C.S. Dalton 1978 1425. 92 P. C. Minshall and G. M. Sheldrick Acta Cryst. 1978 B34 1326.. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway E I P* P Me (35) (36) E = 0or S have virtual (not crystallographic) Td symmetry (36),93and both the orthorhombic (from sublimation) and monoclinic (from crystallisation) modifications of the mono- thio derivative P4S(NMe), have virtual C3 The reaction of P4 and As4 with Co2' or Ni2+ aquo ions in the presence of the triphosphine ligand MeC(CH,PPh,) leads to the replacement of one atom of the tetrahedral unit and the formation of complexes of the triangulo-P3 and -As ligands such as (37) and (38).95*96The same triangulo-As unit is also found in the organocyclotriarsine [MeC(CH2),As3] (39).97 PPP r+ Me (37) (38) E = P or As (39) 5 Molecular Compounds of Group IV Elements The molecular chemistry of the Group IV elements in the quadrivalent state falls into three principal categories the synthesis of new compounds mechanistic studies and structural determinations.The perfluoro-t-butyl fluorosulphonyl peroxide (40) is a 93 F. Casablanca F. A.Cotton J. G. Riess C. E. Rice and B. R. Stults Inorg. Chem. 1978 17 3232. 94 F. A. Cotton J. G. Riess C. E. Rice and B. R. Stults Inorg. Chem. 1978 17 3521. 95 M. Di Vaira C. A. Ghilardi S. Midollini and L. Sacconi J. Amer. Chem. SOC.,1978,100,2550. 96 M. Di Vaira S. Midollini L. Sacconi and F. Zanobini Angew. Chem. Internat. Edn. 1978 17,676. 97 G.Thiele G. Zoubek H. A. Lindner and J. Ellerman Angew. Chem. Infernat. Edn. 1978 17 135. The Typical Elements useful starting material for the preparation of several other perfluoro-peroxides via the peroxy anion (CF3),C02- which is generated in situ by nucleophilic attack of fluoride on (40).98.99Routes to the new peroxides are shown in Scheme 5 (CF3)3COOC(O)OCF31 KF COF (CF3)300S02F A(CF3)3COOK + -S02F2 / -KF I (40) (CF3)3COOC(O)F CIF CsF (CF3)3COOF Hzo'o/ ICSFZ-78T at -78OC (CF3)3COOH (CF3)3COOCF20F -65 "C (CF3)3COOCl a(CF3)3COOCF20Cl -COF2 Scheme 5 The reaction of (CF,),COOK with KOC(CF3) at low temperatures results in the formation of the unstable trioxide (CF3),CO0OC(CF3),.(CF3)3COOF also adds to CF2CFC1 yielding both isomeric products (CF3),COOCF2CF2C1 and (CF3),COOCFC1CF3 indicative of a free-radical process.99 Studies of the peroxy derivatives of the heavier Group IV elements are largely confined to kinetic ones. The decomposition of the silyl- germyl- and stannyl-peroxides RiEOOR2(E =Si Ge or Sn; R1= Me or Et; R2 =But or CMe2Ph) proceeds via the rate-determining formation of a 1:1complex between the peroxide and alkene which subsequently decomposes homolytically'OO as shown in Scheme 6.The addition of catalytic R:EOOR2 +X2C=CY2 $[R:EOOR2X2C=CY2] /\ R:EOCX2CY2 +R20 R20CY2CX2+RAE0 Scheme 6 amounts of KCN to Ph3SiOOGePh2 promotes the rearrangement to the germasiloxane Ph2(PhO)GeOSiPh3. Assistance of base in the rearrangement is reflected in the activation energy which is reduced from 27.7 kcalmol-' for the thermal rearrangement in anisole to 13.5f0.8 kcal mol-' in benzene-isopropyl alcohol mixture with added KCN. The reaction is first-order in peroxide and probably proceeds via the transition state (41) involving co-ordination of base at germanium thus weakening the mutually trans Ge-Ph bond.'" 2-Germa-acetic acid decomposes in dilute acetic acid to yield carbon monoxide an orange-yellow solid of approximate composition GeHo.6 and small amounts of 98 S.-L.Yu and D. D. DesMarteau Znorg. Chem. 1978,17 304. 99 S.-L. Yu and D. D. DesMarteau Znorg. Chem. 1978 17,2484. 100 Yu. A. Alexandrov V. V. Gorbarov N. V. Yablokova and V. G. Tsvetkov J. Organometallic Chem. 1978,157,267. lo' V. A. Yablokov G. S. Kalinina N. V. Yablokova T. A. Basalgina N. S. Vyazankin and G. A. Razuvaev J. Organometallic Chem. 1978 153. 25. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway germane. In strongly acidic solution however carbon monoxide is evolved quan- titatively and no solid hydride or germane forms; rather the solution contains the GeH,' [or GeH,(OH,)'] cation. It would appear therefore that the germyl cation is not stable in less acidic solution forming germylene which disproportionateslo2 as shown in Scheme 7.H3GeC02H+ H' $ H3GeC{lA' GeH3' + CO + H20 [ 11 2-x 2 -GeH4+ -GeH c GeH2+ H' 4-x 4-x (X= -0.6) Scheme 7 Convenient high-yield syntheses of perfluoromethyl derivatives of the heavier Group IV metals are still elusive. Although several new routes have been investi- gated none are satisfactory. Controlled low-temperature direct fluorination of Me4Sn does yield partially fluorinated derivatives but Sn-C bond cleavage occurs as well. lo3 Bis(trifluoromethy1)mercury is a useful CF group source and undergoes group exchange with a number of germanium tin and lead compounds. Exchange with GeBr and GeI yields all the perfluoromethyl derivatives (CF,) GeX4- (n = 1-4; X = Br or I),but only mono- and bis-tin derivatives can be prepared using SnBr4.'04 Exchange of one CF group for one methyl group occurs for Me4Sn Me,SnCF, and Me,Pb but product yields are low.Metal-metal bond cleavage with formation of Me3SnCF3 occurs with Me,Sn2 but no analogous reaction takes place with Me& or the hexaphenyl derivatives Ph6M2 (M = Ge Sn or Pb).lo5 Organotin(1v) chlorides of co-ordination number greater than four through intermolecular co-ordination of a donor function remote in the organic ligand have provoked much interest. 0-Carbonylethyltin chlorides are obtained in high yield by the reaction of a carbonyl-activated alkene HC1 and either tin(I1) chloride or tin metal. When tin(I1) chloride is used five-co-ordinate monoalkyl-tin trichloride derivatives (42) are formed but the major products starting from tin metal are the corresponding dialkyl-tin dichlorides (43).'06 Although the syntheses are exceed- ingly simple the mechanisms by which the products are formed are not totally clear.The initial suggestion that the reactions proceed via the formation of chlorostannane intermediates such as HSnCI, which has been reported to be formed as an etherate lo' D. J. Yong and W. L. Jolly Znorg. Chem. 1978 17 621. lo3 E. K. S. Liu and R. J. Lagow Znorg. Chem. 1978,17,618. R. J. Lagow R. Eujen L. L. Gerchman and J. A. Morrison J. Amer. Chem. Soc. 1978 100,1722. lo5 R. Eujen and R. J. Lagow J.C.S. Dalton 1978 541. '06 R. E. Hutton J. W. Burley and V.Oakes J. Organometallic Chem. 1978 156 369. The Typical Elements R1C4i ,a c1 I RzR C-Sn' I 'CI CI (42) (43) when HCl is passed through a suspension of SnC12 in ether and their subsequent addition to the alkene appears to have no foundation. Rather the composition of the pale yellow oily phase which separates out in the SnCl,-HCl-ether system has since been shown to be principally the tetrachlorostannate(I1) species HzSnCl4,2EtzO with only small amounts of HSnC13,Et20. The protons in such species are highly acidic and the preferred mechanism has been rationalised in terms of a 1,4-addition involving initial protonation of the carbonyl oxygen atom of the carbonyl-stabilised alkene as shown in Scheme 8. It is also unlikely that the reactions involving tin metal I I Cl3Sn-C-CH-C=O S Cl3Sn-C-C=C-0H II Ill Scheme 8 proceed via such species as H2SnC12 or HSnC1.Since tin metal and HCl in ether yields the identical H2SnC14,2Et20 phase as does SnC12 under the same conditions and in addition tin metal promotes the disproportionation of mono-organotin trichlorides to the corresponding diorganotin dichlorides it would appear that the reaction with tin metal follows a similar course to that for SnClz alone with a subsequent disproportionation of the organotin trichloride initially produced. lo7 Triorganotin halides with an intramolecularly co-ordinated amino-substituted aryl group are obtained by the reaction of diorganotin dihalides with aryl-lithium aryl-copper or aryl-goldlithium intermediates.This method has been employed to synthesise the chiral triorganotin bromide (44) whose absolute configuration was determined by X-ray crystallography,"* and also ionic bromides (45).lo9 Br (44) (45) lo' E. J. Bulten and J. W. G. van den Hurk J. Organometallic Chem. 1978 162 161. G. van Koten J. T. B. H. Jastrzebski J. G. Noltes W. M. G. F. Pontenagel J. Kroon and A. L. Spek J. Amer. Chem. SOC. 1978 100 5021. lo9 G. van Koten J. T. B. H. Jastrzebski J. G. Noltes A. L. Spek and J. C. Schoone J. Organometallic Chem. 1978,148,233. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Unlike (Ph3Si),0 whose linear SiOSi skeleton was preliminarily reported last year,11o (Ph3Sn),0 is bent at oxygen."' It wo:ild appear therefore that the linearity of the silicon compound is truly a consequence of electronic rather than steric effects.The tendency to achieve co-ordination numbers greater than four is quite pronounced in the heavier Group IV metals and both Ph3SnOH and Ph3PbOH adopt chain structures with five-co-ordinated metal atoms and bridging hydroxy- groups. Both chains are bent at oxygen.'12 When tin is bonded to four organic groups the metal is too weakly Lewis acidic to increase its co-ordination number above four even in Ph3SnCH21 where the proximity of the large iodine atom causes no perceptible deviation from tetrahedral geometry at tin. Some perturbation of the electronic distribution is however apparent from the l19Sn n.m.r. data.113 Four-co- ordination also persists when weakly donating atoms such as sulphur or selenium are bonded to tin and dimethyltin selenide has been shown to possess the same trimeric structure with a 'twist-boat' conformation and four-co-ordinated tin as the cor- responding ~u1phide.l'~ The trimeric form of di-isopropyltin sulphide is the one initially obtained from the substitution of Pr',SnCl by Na2S.However on allowing the product to stand under DMF this form is transformed into a polymeric one-dimensional chain structure modification (46) again with four-co-ordinated tin.' l5 Replacement of organic groups by highly electronegative ligands permits the achievement of very high co-ordination numbers. Thus Ph2Sn(N03) and Ph3P0 form a 1:1 complex with seven-co-ordinated tin with a pentagonal-bipyramidal arrangement (47).'16 6 Phosphorus Arsenic and Antimosy Compounds The effect of very high pressures on reaction rates is rarely studied but the reactions of PF3 with SOzand H,S are strongly influenced by the application of pressure.Thus whereas reaction with SO2at 150 "C produces elemental sulphur and OPF3 in only 4% yield at 670 atmospheres an 84% yield is obtained when the pressure is increased to 4000 atmospheres. Similarly yields from the PF3-H2S reaction at 200 "C increase from only 3% at 1350 atmospheres to 35% at 4000 atmospheres. Both reactions eventually become quantitative when longer reaction times are 'lo C. Glidewell and D. C. Liles Acta Cryst. 1978 B34,125. "' C.Glidewell and D. C. Liles Acta Cryst. 1978 B34,1693. 'I2 C.Glidewell and D.C. Liles Acta Cryst. 1978 B34,129. P. G. Harrison and K. C. Molloy J. Organometallic Chem. 1978 152 53. M. Drager A. Blecher H.-J. Jacobsen and B. Krebs J. Organometallic Chem. 1978,161 319. 'I5 H. Puff,A. Bengartz R. Severs and R. Zimmer Angew. Chem. Znternat. Edn. 1978,17 939. 'I6 M. Nardelli C. Pelizzi and G. Pelizzi J.C.S.Dalton 1978 131. The Typical Elements employed. The mechanistic implication of these observations is of course that both reactions proceed via an associative rather than a dissociative mechanism.' l7 Contrary to previous reports 1,2-diphenyl-diphosphine,HPhP-PPhH is formed by the reaction of KPPhH with 1,2-dibromoethane. However the pure compound is better prepared by the alcoholysis or hydrolysis of Me3SiPPh-PhPSiMe in the dark.Although stable at -30 "C HPPh-PhPH decomposes at room temperature to give a complex mixture of products including PhPH, higher homologues in the series H2(PPh). and cyclic phenylphosphines particularly (PPh),. One of the major decomposition products the triphosphine H(PPh),H is itself not stable at room temperature and undergoes similar disproportionation reactions leading to the same variety of products.' l9 "J Unlike Ph3As the perfluorinated analogue (C6F5),As has only a very low co-ordinating ability although the neutral and cationic silver complexes 03C10Ag,As(C6F5)3 and A~[As(C,F,),],C~~~ have been isolated.' lY The cor- responding antimony compound (C,F,),Sb has an even lower donor capacity and no complexes of this ligand have yet been isolated.Surprisingly though (C6F5),Sb undergoes hydrolysis of one Sb-C bond to give [(C6F5)3Sb]20.'20 Both (C6F5),As and (C6F5),Sb are easily oxidised by C1 or TlCl to the metal(v) dichlorides (C$5)3MC12 (M =As or Sb) which in turn may undergo a variety of substitution reactions.120*121 Direct halogenation of triorganometal(II1) derivatives is a common route to Group V organometal(v) dihalides and this method has been successfully applied to the synthesis of the corresponding fluorides of arsenic antimony and bismuth using CFC1 as the solvent. In addition alkylene diarsines and distibines of the types (48) and (49) may be obtained by the same procedure but the fluorination of diphenylarsine yields Ph2AsF3. 122 Me F FI 1 1 IR2M-CH2-MR2 FI IR,As-(CH2) FI I-AsR~ C Ill C MeI /' I\Me-Sb F F F F CIllC Me (48) M =As or Sb (49) Me (50) Oxidative halogenation or quaternisation followed by treatment with alkyl- lithium is the general route to peralkyl-antimony(v) derivatives and all five members of the series Me,Sb(CH2SiMe3),- (n=0-4) have been prepared this way starting from Me,Sb or Sb(CH2SiMe3)3.123 Similarly Et,SbMe and Et,Sb(C_CMe) are produced by the reaction of Et,SbCl with the appropriate A.P. Hagen and B. W. Callaway Inorg. Chem. 1978,17,554. M. Baudler B. Carlson D. Koch and P. K. Medda Chem. Ber. 1978,111 1210. M. Baudler D.Koch and B. Carlson Chem. Ber. 1978 111 1217. A. Otero and P. Royo J. Organometallic Chem. 1978,149,315. A. Otero and P. Royo J.Organometallic Chem. 1978 154 13. 121 122 I. Ruppert and'V. Bastian Angew. Chem. Internat. Edn. 1978,17,214. 123 H. Schmidbauer and G. Hasslberger Chem. Ber. 1978,111 2702. 228 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway alkyl-lithium. As expected Et,Sb(C_CMe) exhibits the trigonal-bipyramidal geometry (50),with the alkynyl groups occupying the axial Penta-alkyl-stiboranes are extremely sensitive to protolysis. Phosphonic and phosphinic acids cleave one Sb-Me bond of Me,Sb to yield tetramethylstibonium phosphonates and ph~sphinates.'~' Protolysis also occurs at the Sb-Me bond in Et3SbMe2 with a wide variety of reagents affording the monosubstituted products Et,MeSbX (X = OR ONR2 02CMe 02PMe2 C1 or 02PF2).124 Treatment of (Me3SiCH2),Sb with HCl yields covalent (Me3SiCH2),SbC1 which on dehydrohalogenation is transformed into the unstable ylide (Me,SiCH,),Sb=CHSiMe, thermal isomerisation of which gives the more stable ylide Me(Me3SiCH2)2Sb=C(SiMe3)2.123 A further type of product chloromethine-bridged phosphonium salts [R3P=C(C1)-PR3]+ C1- has been isolated from the reactions of tertiary phosphines with CC14.126 Dechlorination of the analogous salt [Ph3P=C(C1)=PPh2Cl]+ C1- using P(NMe2)3 yields the chloro-substituted double ylide Ph,P=C=PPh2C1 (5l) which dimerises to the cyclic diphosphonium salt (52) and reacts with water and HCl to afford the phosphonium salts (53) and (54).Dechlorination of (54) in turn gives the phosphino-substituted ylide Ph3P=CHPPh2.'27 Ph,P=C=PPh,CI Ph,P-c-PPh ]'+ Ii 1 c1-+ [Ph PCH P(0)Ph ,] ph -Ph (53) (54) (52) Phosphoryl chloride and bromide undergo protonation at the phosphoryl oxygen in highly acidic solvents such as 100°/~H2S04,HSC103 HSFO, and 25 and 65 oleum the extent of protonation depending upon the acid sirength.The resulting solutions are stable except for those of PBr,O in 100°/~H2S04 and 25 oleum when solvolysis occurs and in 65 oleum when condensation uia HBr elimination takes place. PCl dissolves in the same solvents to give [PCl,'] or [PCl,(OH)]' cations or both as the initial product depending on the solvent. PBr similarly forms the [PBr,'] cation in all solvents except 65 oleum in which it is stable. The solutions are generally unstable however and undergo further solvolysis.'28 The [PPhC13]+ cation and the corresponding neutral species PPhC14 are good acceptors towards Lewis bases giving six-co-ordinate complexes in every case.Thus C1- adds to PPhCl in the presence of large cations to give the [PPhC15]- anion whilst unhindered pyridines afford the molecular complexes PPhC14,L. The complex cations [PPhCI,(L,)]' are obtained from either PPhC14 or the [PPhCl,]' cation with bidentate ligands such as bipyridyl or phenanthroline (L2). 129 The catechol (cat) 124 N. Tempel W. Schwarz and J. Weidlein J. Organometallic Chem. 1978,154,21. 125 G. E.Graves and J. B. van Wazer J. Organometallic Chem. 1978,150,233. R. Appel and H.-F. Scholer Chem. Ber. 1978 111 2056. 12' R. Appel and H.-D. Wihler Chem. Ber. 1978,111,2054.12* K.B.Dillon M. P. Nisbet and T. C. Waddington J.C.S. Dalton 1978 1455. 129 K.B.Dillon R. N. Reeve and T. C. Waddington J.C.S. Dalton 1978 1318. The Typical Elements 229 derivatives PCl,(cat) PCl(cat), [PCl,(cat)]' and [P(cat),]' behave similarly afford- ing such complexes as [PCl,(cat)]' [PCl(L,)(cat)]' and [P(phen)(~at)]'.'~' 7 Metal Oxides An ab initio SCF calculation has predicted a 'Xi electronic ground state and Dmh symmetry for molecular Si02,131 which may be matrix-isolated by condensing evaporated SiO and atomic oxygen generated by microwave excitation. Force-constant data for matrix-isolated SiO and SiO are very similar indicating no further increase in bond order in the two-atom species (cf. CO and C02).13 The principal current interest in the reaction chemistry of silicon(1v) and tin(1v) oxides involves their chemisorption properties.Chemisorption on to silica from the gas phase has been studied for some time and investigations in this area are largely concerned with silica-supported metal catalyst systems but their volume precludes coverage here. Novel however are studies of chemisorption from solution. Two main types of surface-adsorbate interaction can be identified from heptane solutions of anis01es'~~ and involving the formation of hydrogen-bonds between silanol groups and the aromatic .rr-electron systems and the oxygen atom in the adsorbate [(55)-(57)]. Electron-withdrawing substituents weaken both types of interaction. In addition hydrogen-bonds may also be formed with suitable functional substituents on the aromatic ring e.g.nitro-groups (58). Similarly hydrogen-bond formation takes place between surface silanol groups and mono- and di-ketones from CC1 The relative proportions of adsorption from two- and three-component liquid systems have also been evaluated from i.r. absorbance data.136 Me I Me I Me X X' / I H' I H / /H H / 0 0 0' I I 1 0 I /si\ Ai\ (55) (57) 13') K. B. Dillon R. N. Reeve and T. C. Waddington J.C.S. Dalton 1978 1465. 13' J. Pacansky and K. Hermann J. Chem. Phys. 1978,69 963. 13' H. Schnockel Angew. Chem. Internat. Edn. 1978 17 616 133 C. H. Rochester and D. A. Trebilco J.C.S. Furuduy I 1978 74 1125. 134 C. H. Rochester and D. A. Trebilco J.C.S.Furuduy I 1978,74 11 37. S. N. W. Cross and C. H. Rochester J.C.S. Furuduy I 1978,74 2130. 13' A. D. Buckland C. H. Rochester D. A. Trebilco and K. Wigfield J.C.S. Furaduy I 1978 74 2393. 230 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Chemisorption and catalysis studies involving tin(1v) oxide and metal-'doped' tin(1v) oxide systems are of increasing importance. Tin(1v) oxide differs from silica by having a high Lewis acidity and a high oxidising capacity but low Bronsted acidity. This is however increased in mixed oxide systems such as Sn02,Sb203 and Sn02,Mo03. Both tin(1v) oxide and transition-metal-'doped' tin(1v) oxide catalyse the CO-O2 and CO-NO reactions important in vehicle exhaust emission control and much effort has been invested in the elucidation of the surface species present and the mechanisms involved.Water adsorption isotherms on neat Sn0 exhibit a discontinuity due to physisorption of water molecules with surface hydroxy-groups probably on the [1001 crystal plane.'37~'38 The discontinuity can be removed by pretreatment in vacuo or by hydrogen but was restored by treatment with oxygen. Surface unidentate carbonate and bicarbonate are formed slowly when Sn02 is exposed to CO-0 mixtures essentially independent of the composition of the gas mixture in the range 10-70% CO but pretreatment at 723 K affords a unidentate carbonate. Hydration of the surface severely inhibits adsorption as does pretreat- ment with ammonia which with CO leads to the formation of a surface arba am ate.'^' Adsorption of NO on reduced Sn02 causes replacement of oxide deficiencies in the surface layer with the formation of N2 and N20 even at room temperature.On oxidised Sn02 the NO radical is first co-ordinated to a Sn4' site and then reacts with further NO to give surface (NO) dimer species.14o Catalysis of the CO-NO reaction by Sn02 starts below 200 "C but complete conversion is only achieved at temperatures in excess of 300 "C. Very large increases in the rate and amount of adsorbed NO are obtained by adding 1%Cr203 to Sn02 and complete conversion in the CO-NO reaction occurs at temperatures of 150-220°C. CO however soon poisons oxide surfaces towards the CO-NO reaction but rather surprisingly such poisoned surfaces are still highly active for the CO-0 reaction catalysed by tin(1v) Catalysis of the CO-NO reaction by SnO ion- exchanged with Cr"' Mn" Fe"' Co" and Cu" has been studied by monitoring the adsorption of CO and NO individually and of CO-NO mixtures.Adsorption of CO takes place via carbon at a surface transition-metal cation for all except for the Cu"-exchanged oxide to which CO bonds via oxygen. Surface carbonate species also bound to transition-metal sites were observed which could either be unidentate or bidentate depending on the transition metal. The nature of the surface species resulting from NO adsorption varies significantly with the transition metal. The presence of carbonate species and in most cases physisorbed C02 is consistent with a redox mechanism for the CO-NO reaction catalysed by these oxides.Interestingly however the mechanism for the Cur'-exchanged oxide appears to be different from the others. The Cu"-exchanged oxide preferentially adsorbs CO from CO-NO mixtures and selectively reduces NO to N2. Others notably the Co'I- Ni"- and Fe"'-exchanged oxides adsorb NO from CO-NO mixtures and selectively reduce NO to N,0.'42 The mechanism of the CO-NO reaction on Sn0,-Cr203 has been proposed to involve dissociative chemisorption of NO to give surface nitrogen sites. 13' S. Kittaka S. Kanemoto and T. Morimoto J.C.S. Faraday I 1978 74 676. 13* T. Morimoto Y. Yokata and S. Kittaka J. Phys. Chem. 1978,82 1996. 139 P. G. Harrison and E. W. Thornton J.C.S. Faraday I 1978 74,2597. 140 M. Niwa T. Minami H. Kodama T.Hattori and Y. Murakami J. Catalysis 1978,53 198. 141 F. Solymosi and J. Kiss J. Catalysis 1978 54,42. P. G. Harrison and E. W. Thornton J.C.S.Faraday I 1978 74 2703. 14' The Typical Elements 231 These could then react with further NO to give surface ]-N-N-0 (which desorbs as N20) or CO to give surface isocyanate groups ]-N-C-0 (which react with further NO giving N2 and C02).141 The mechanism of formation of surface isocyanate on Sn02,0.55Cu0 has been intensively studied using 13C 15N and "0 isotopic substitution. The results of this study however show unequivocally that the oxygen atom of the surface isocyanate originates from NO rather than the oxide surface or CO which indicates a mechanism involving initial dissociative chem- isorption of CO and formation of an intermediate fulminate which rearranges to give the isocyanate as shown in Scheme 2]+CO + )-o+)-c PO FNCO + &C-N-0 Scheme 9 Bronsted acidic oxides such as Sn02,Mo03 and Sn02,Sb203 are catalysts for alkene isomerisation and oxidation and for alcohol dehydrogenation.Oxidation of propene to acetone over Sn02,Mo03 proceeds via oxidation of strongly surface- bound propene by lattice oxygen to give surface isopropoxide groups which then undergo oxidative Isomerisation of alkenes over room- ternperature-outgassed Sn02,Sb203 probably proceeds via a carbonium ion type of mechanism with Bronsted acid sites as the source of protons. The rates of reaction increase with increasing antimony content to a maximum at -50 atom% Sb and decline thereafter.Oxides outgassed at higher temperatures were only active at compositions with less than 50 atom% Sb and could be poisoned by treatment with bases or sodium a~etate.'~~'~~' The structures of antimony and bismuth oxide derivatives follow closely those of similar tin and lead compounds. Thus the structure of Sb205 is related to the rutile structure adopted by Sn02 with octahedral co-ordination for the Sb atoms and is quite different from that of AS^^^.^^^ The analogy of Sb"' with the Sn" is markedly exemplified in the structure of Sb406C12 in which the two crystallographically independent Sb atoms exhibit the two main co-ordination types shown by Sn" pyramidal and pseudo-trigonal-bipyramidal.The gross structure is made up of layers of edge- and corner-sharing [SbO,] and [SbO,] units with chlorine atoms located between the layers.'49 The antimony atoms in Sb2(0H),(SO4),,2H20 also have pseudo-trigonal-bipyramidalco-ordination.In this compound the two anti- mony atoms are bridged by two hydroxy-groups in equatorial positions whilst axial positions are occupied by oxygen atoms of water and sulphate groups. Intra- and inter-molecular hydrogen bonding is very extensive.15' The tendency to form large oxo-cations exhibited by Pb" is also shown by Bi"' in the basic nitrate [Bi605(OH)3](N03)5,3H20, which contains cage-like [Bi605(OH)3] clusters with oxygen atoms and hydroxy-groups above the centres of the octahedral faces of a Bi octahedron.151 143 P. G. Harrison and E.W. Thornton J.C.S. Faraday I 1978 74 2604. 144 Y. Takita Y. Moro-Oka and A. Ozaki J. Catalysis 1978 52 95. T. Ono and Y. Kubokawa,J. Catalysis 1978 52 412. 146 E.A.Irvine and D. Taylor J.C.S. Faruday I 1978,74,206. E. A. Irvine and D. Taylor. J.C.S. Faraday I 1978,74 1590. M. Jansen Angew. Chem. Internat. Edn. 1978 17 137. 149 C. Sarnstrand Acta Cryst. 1978 B34 2402. J. Douglade R.Mercier and H. Vivier Acta Cryst. 1978 B34 3163. F.Lazarini Acta Cryst. 1978 B34 3169. 14'

ISSN:0308-6003    

DOI:10.1039/PR9787500208

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Part IV Groups VI VII and VIII By J. H. Holloway 1 GroupVI Oxygen.-One of the last issues of Berichte der Bunsen gesellschaft fur physikalische Chemie for 1978*"is devoted to atmospheric chemistry. Rate constants for the reactions OH + H02+H20+ O2,l6 OH with halocarbons (CHClF2 CH2ClF CH2ClCF3 CH3CClF2 and CH3CHF2)lC are included and a summary of the kinetics experimental data and theoretical predictions for the reactions OH + NO2 OH + NO OH + SO2 C10 + NO2,and H02 + NO2 is also given.ld Critical properties are emphasized in recent tabulations of thermodynamic data for a wide range of substances including both inorganic and organic oxygen-containing compounds.2 Current interest in the possibility of obtaining chemical fuel from light has promoted several approaches to ways of producing O2(and H2)from water.Photo- redox reactions of the type hu A+D === A-+D' A encounter two main obstacles. One is related to the reversibility of the reaction; the second is the conversion of the chemical potential of the stabilized A-and D' into useful products. To do this A and D may be selected such that in aqueous solution evolution of oxygen and hydrogen is thermodynamically feasible 2A-+ H20 -+ 2A+ 20H-+ H2 (2) It has now been demonstrated for the first time that the production of O2via reaction (3) can be facilitated by Ce4' or R~(bipy),~' reduction using PtO or Ir02 redox cataly~ts.~ A second approach involving chlorophyll a dihydrate polycrystals (Chl ~,2H~0)~>~ as a unique assembly that is capable of photolysis of water,4a has thrown light on the observed '2 quanta per electron transferred' requirement for plant photo~ynthesis.~' The solubility of oxygen in aqueous fluorocarbon emulsions correlates directly with that in neat perfluoro- compound^.^ This is of importance because of their utilization in artificial blood.' (a) Ber. Bunsengesellschafrphys. Chem. 1978,82 issue No. 11; (b)W. Hack A. W. Preuss and H. Gg. Wagner ibid. p. 1167; (c)V. Handwerk and R. Zellner ibid. p. 1161; (d)R. Zellner ibid. p. 1172. D. Rathman J. Bauer and P. A. Thompson Ber. Max-Planck-Znst. Stroemungsforsch. 1978,6 77pp. J. Kiwi and M. Gratzel Angew. Chem. Znternat. Edn. 1978,17,860. * (a)F. K. Fong and L.Galloway J. Amer. Chem. SOC.,1978 100 3594; (b)L. Galloway J. Roettger D. R. Fruge and,F. K. Fong ibid. p. 4635. C. M. Sharts and H. R. Reese J. Fluorine Chem. 1978,11,637. The Typical Elements The superoxide ion 02-, has been obtained during the photo-oxidation of tryp-tophan,6a and 0,-and the hydroxy-radical (OH-)have been obtained from the base-induced decomposition of H202.6' The rate constant of the reaction 02-+ H202+0H + OH-+ O2is less than 0.3 dm3 mol-' s-' in dilute aqueous solution and cannot therefore occur significantly in biological systems unless catalysed by some cellular agent.6' The nucleophilicity and reducing power of 02-are already well documented and it has now been demonstrated that 02-cannot act directly as an oxidant in aprotic media in which it is stable and moreover arguments and preliminary data have been presented to show that solutions are strongly basic.6d Almost 30 years ago Criegee7 proposed a mechanism for ozone-olefin reactions'" which has since been supported with only minor modifications.Recently ab initiu calculations on the peroxymethylene intermediate CH200 have been combined with existing thermodynamic data to analyse possible modes of ozonolysis.'' The first unambiguous structure determination on an ozonide epoxybenzodioxepinone (l),has revealed the presence of a five-membered ring in an epoxide-oxygen envelope configuration. '' Visual representations of electron density have contributed to our understanding of chemical bonding.Theoretical electron distributions have been calculated for the (2) (a)J. P. McCormick andT. Thomason J. Amer. Chem. SOC.,1978,100,312; (b)J. L. Roberts Jr. M. M. Morrison and D. T. Sawyer ibid.,329; (c)W. H. Melhuish and H. C. Sutton J.C.S. Chem. Comm. 1978 970; (d)D. T. Sawyer M. J. Gibian M. M. Morrison and E. T. Seo J.Amer. Chem. SOC.,1978,100,627. ' (a)R. Criegee and G. Wenner Annalen 1949,546,9; (b)R. Criegee Records Chem. Progr. 1957,18 111. (a)P. S. Bailey and T. M. Ferrel J. Amer. Chem. SOC.,1978,100 899; (b) L. B. Harding and W. A. Goddard 111 ibid.,p. 7180; (c)J. Karban,J. L. McAtee Jr. J. S. Belew D. F. Mullica W. 0.Milligan and J. Korp J.C.S. Chem. Comm. 1978,729. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway ground states of the H20 and H2S molecules in the gaseous state (2).' The results of valence-shell electron-pair interactions in H20 and H2S have been compared with localized Hartree-Fock and relaxed orthogonal Hartree product calculations of Coulomb exchange and overlap repulsions.Some agreement has been found. The bond pair-bond pair repulsions however affect the equilibrium geometry more strongly than do the lone pair-lone pair or bond pair-lone pair repulsions and it is concluded that a simply physical explanation of the equilibrium bond angles in the molecules remains to be given." Ionization energies of H20have been calculated from Valence Bond and Molecu- lar Orbital wavefunctions,lla and the first fully ab initio calculation of the free energy of liquid water has been used together with the previously determined internal energy to derive an entropy value."' Hydrogen-bonded and long-chain molecules have been shown to have abnormally high liquid heat capacities.These can only be accounted for by postulating an isomerization reaction and if the heat capacity contribution ACp(imm), of the isomerization reaction AeB is analysed it can be shown that Cp(isom) can amount to as much as 34-42 J mol-' K-'. For water it has now been shown that AH = 9.0*0.8 kJ mol-' AS = 8.0* 1e.u. will account for the excess AC over the 0-100"C range.12 The highly simplified concept that water contains an equilibrium concentration of 'free' OH and lone-pair groups has been used to give a quantitative explanation of the large changes that have been observed for certain hydrolyses on the addition of co-solvents.l3 Molecular organization 14a*' absorption of polar molecules14c and monolayer polymerization at air-water interface~,'~~ reactions occurring in organized monolayer assemblies films and assembly- or film-solution interfaces14e have been reviewed or discussed.The formation theory of formation kinetic^,'^' dynamics,15c and properties of mi~elles,~'~ and fast reactions in them,'5d have been reviewed. New clathrate hydrates of hydrogen- and fluorine-containing molecules (S02F2 SeF, CF31 C2F6 Me2S EtSH etc.) have been identified from characteristic n.m.r. lineshapes when the hydrates were prepared using D20.16= Heats of formation of CC12F2 and CHClF hydrates and deuteriates have been determined from their dissociation pressure measurements,16b and i.r.spectra of CF31 hydrates have &en studied.16" J. Bicerano D. S. Marynick and W. N. Lipscomb J. Amer. Chem. Sac. 1978,100,732. lo W. E.Palke and B. Kirtman J. Amer. Chem. SOC.,1978,100,5717. l1 (a)D. M.Chipman J. Amer. Chem. SOC.,1978,100 2650; (b)M. Mezei S. Swaminathan and D. L. Beveridge ibid. p. 3256. l2 S.W. Benson J. Amer. Chem. SOC.,1978,100,5640. l3 M. C. R. Symons J.C.S. Chem. Comm. 1978,418. l4 (a)D. Mobius Ber. Bunsengeseflschuftphys. Chem. 1978,82,848; (b)E. Sackman ibid. p. 891; (c)D. Baumer H. Mang and G. H. Findenegg ibid.,p 878; (d)D. Day H. H. Hub H. Ringsdorf and W. Siol ibid. p. 878; (e)D. G. Whitten D. W. Eaker B. E. Horsey R.H. Schmehl and P. R. Worsham ibid. p. 858. Is (a)P. Mukerjee Ber. Bunsengesellschaft phys. Chem. 1978 82 931; (b)E. A. G. Aniansson ibid. p. 981; (c)H. Hoffmann ibid. p. 988; (d)J. K. Thomas F. Grieser and M. Wong ibid. p. 937. l6 (a)J. A. Ripmeester and D. W. Davidson Mol Crystals Liquid Crystals 1977 43 189; (6) D. Yu. Stupin V. N. Tezikov and A. P. Seleznev Zhur. priklud. Khim. 1978 51 589; (c) V. V. Dyrkheev D. Yu. Stupin and V. N. Tezikov Zhur. fiz. Khim. 1978.52.2096. The Typical Elements The oxonium salts H30+BiFg-,17" H30+NbF6- H30+ TaFg- H30+WOFs-,17b H30+ IrF6- H30+ PtF6- and H30' RuF6- 17' have been prepared for the first time and the last three have been shown to have rhombohedra1 cells with almost identical With excess of water PtF6 gives (H30)2+PtF62-.17' X-Rayl8"- and neutron-diffraction studies18d on HC1,6H20,18" CF3S03H,4H20,"' and CF3S03H.5H2018' indicate that the compounds should be formulated H904+C1-,2H20 H904+CF3S03- and H30+CF3S03-,4H20 respectively.A neutron-diffraction study designed to give information on the geometry of the H30+ ion in H30+ CF3S03- shows that the hydrogen-bonded acceptors are arranged asymmetrically about the oxonium ion (3).18d (3) Electron-diffraction studies on F~XOXFS (X = S Sk or Te) have shown that the X-0-X bond angles are close to 145 '. It is suggested that the chalcogen-oxygen bonds are double (pd)-~ bonds.'' Considerable new work on peroxy-compounds has been reported. The powerful oxidizing properties of peroxdisulphuryl fluoride S206F2 have been exploited in the synthesis of new fluoro-sulphates of high oxidation state from metal carbonyls.20 A large range of pentafluorosulphur peroxides have been made in recent years.The vibrational spectra of some of them (SFSOOH SFSOOF and SFsOOC1) have now been obtained and evidence for a trioxide SFsOOOSFs has been produced.2'" The kinetics of the thermal decomposition of SF500SFs in the presence of CO have been reported.21b Several members of a new class of fluorinated peroxides containing the perfluoro-t-butyl group have been prepared from (CF,),COOC(O)F which was obtained by the nucleophilic displacement reaction (4).21c l7 (a)K. 0.Christe W. W. Wilson and C. J. Schack J. Fluorine Chem. 1978,11,71;(b)H. Selig W. A. Sunder F.C. Schilling and W. E. Falconer ibid. p. 629;(c) H. Selig W. A. Sunder F. A. Disalvo and W. E. Falconer ibid. p. 39. (a)I. Taesler and J.-0. Lundgren Acra Cryst. 1978,B34,2424;(b)J.-0. Lundgren ibid. p. 2428; (c) J.-0. Lundgren ibid. p. 2432;(d)J.-0. Lundgren R. Tellgren and I. Olovsson ibid. p. 2945. (a)H. Oberhammer and K. Seppelt Angew. Chem. 1978,90,66;(b)H. Oberhammer and K. Seppelt Inorg. Chem. 1978 17 1435. S.D. Brown and G. L. Gard Znorg. Chem. 1978,17 1363. (a)D.D. DesMarteau and R. M. Hammaker,Israel J. Chem. 1978,17,103;(6)J. Czarnowski and H. J. Schumacher Internat. J. Chem. Kinetics 1978 10 111; (c) S.-Y. Yu and D. D. DesMarteau Inorg. Chem. 1978,17. 304; (d)S.-Y. Yu and D. D. DesMarteau ibid. p. 2484. F. A. Hart A. G. Massey P.G. Harrison and J. H. Holloway KF (CF3)3COOS02F+COF2 (CF3)3COOC(CO)F+S02F2 (4) It is suggested that the reaction involves the unstable anion (CF3),C0O- and this has now been obtained from reaction (4)by substitutiing CsF for KF. Its controlled oxidation by fluorine has given (CF3)3COOF which with KOC(CF,), forms the unstable trioxide (CF3)3COOOC(CF3)3.21d The matrix i.r. spectrum of the hitherto unknown 02Br radical has been reported22" and Russian workers have confirmed the existence of the analogous fluoride.226 Attempts to reproduce the structure of 02F2by Restricted Hartree- Fock and Configuration Interaction calculations with a number of basis sets have yielded the experimentally determined bond angles but unsatisfactory bond lengths.23 The reaction of 02F2with polymeric VF5 at low temperatures led first to 6+ 6-the reaction intermediate F-0--O-F--V2Flo or 02F++F-+ V2F10.AS the temperature was increased the new compound 02+ V2F11+ was A ten-step mechanism has been proposed for the reaction of hydrogen with OF2.25 Sulphur.-The preparation and chemistry of sulphido- seleno- and telluro-halides of the transition elements,26n and of sulphur selenium and tellurium cations,266 have been reviewed. Information on Group VI binary fluorides is contained in a review of the vibrational spectra of Main Group elements.26c New vibrational spectroscopic data has extended the characterization of S3-and S2-radical anions and S4-has been tentatively identified. Evidence of a neutral S4 species has also been An X-ray crystal structure has revealed the S22-ligand in the novel complex [(S2)2Mo(S2)2Mo(S2)2]2-.27b Four cationic sulphur species S4+ S2+,S2*+,and S42+,have been obtained by anodic oxidation of sulphur in a NaC1-AlCl3 melt at 1500C.28 Cyclo-heptasulphur S, has been isolated in pure form from quenched cyclo- octasulphur melts by fractional extraction and crystallization exploiting the tendency of S7 to form supersaturated solutions in CS2.29a Reduction of S8 with lithium triethylborohydride has provided a convenient means of preparing organic sulphide and disulphide derivatives.296 An X-ray single-crystal structural analysis of cyclo-decasulphur Sl0 has been carried out (4).29c Monoclinic Se3S has been shown to be isostructural with monoclinic S8(y).29d 22 (a)D.E. Tevault and R. R. Smardzewski J. Amer. Chem. SOC.,1978,100 3955; (b)V.A.Legasov G. N. Makeev and E. P. Talzi 5-1 Vses. Siwpoz. Po Khimii Neorgan. Ftoridov. Dnepropetrovsk 1978 160 (Chem. Abs. 1978,89,207 217). 23 R. R. Lucchese H. F. Schaefer 111 W. R. Rodwell and L. Random J. Chem. Phys. 1978,68,2507. 24 J. E. Griffiths A. J. Edwards W. A. Sunder and W. E. Falconer J. Huorine Chem. 1978,11 119. *' T. J. Homer Znternat. J. Chem. Kinetics 1978,10,773. 26 (a)D.A. Rice Co-ordination Chem. Rev. 1978,25,199; (b)J. Passmore in 'Homoatomic Rings Chains and Macromolecules of Main-Group Elements,' ed. A. L. Rheingold Elsevier Amsterdam 1977 p. 539;(c) N. R. Smyrl and G. Mamantov Adv. Znorg. Chem. Radiochem. 1978,21,231. 27 (a)R. J. H. Clark and D.G. Cobbold Inorg. Chem. 1978 17 3169; (6)A.Muller W.-0. Nolte and B. Krebs Angew. Chem. Znternat. Edn. 1978,17 279. 28 R. Fehrmann N. J. Bjerrum and F. W. Poulsen Znorg. Chem. 1978,17 1195. 29 (a)R.Steudel and H.-J. Made Angew. Chem. Internat. Edn. 1978 17 56; (b)J. A. Gladysz V. K. Wong and B. S. Jick J.C.S. Chem. Comm. 1978 838; (c) R.Reinhardt R. Steudel and F. Schuster Angew. Chem. Znternat. Edn. 1978,17,57; (d)C. Calvo R. J. Gillespie J. E. Vekris and H. N. Ng Acta Cryst.,1978 B34.911. 237 The Typical Elements Trifluoroperoxyacetic acid reacts with (S,N),SO and S7NH to give the previously unknown heptasulphurimide 3-oxide S7NH0 the properties and vibrational spec- tra of which have been Reactions of S,NH S7NBC12 and 1,4-S6N2H2 with SbC1 in liquid SO2give S2N+ SbC16-.30b Other novel cyclic sulphur compounds include S60(the smallest known cyclo-polysulphur and S702.31b Both are formed on oxidation of sulphur rings with trifluoroperacetic acid as shown in equations (5)and (6).S6 +CF3C03H -B S6O +CFjCOZH (5) Ss +4CF3C03H -P s702+SO2 +4CF3C02H (6) Through the co-condensation of sulphur vapour and reactive plasma-generated trifluoromethyl radicals a new route to perfluoroalkyl polysulphides (CF3Sn CF3 C2F5SnCF3,and C2F5SnC2F5; n = 2-4) has been Interest in macrocyclic sulphur analogues of the crown ethers has led to a number of new sulphides. The preparation and crystal structure of 1,1,5,5,9,9,13,13-octamethyl-3,4,7,8,11,12,15,16-octathiacyclohexadecane[containing the sixteen-membered (c&)4ring]33 has provided detailed structural information on one of the first macroheterocyclic polydisulphides.Theoretical molecular orbital studies have been made on S4N4,34Q'b S2N2 34b,c and several small S-N molecules (NSF HSN N2S and H3NS).34C The crystal structure of S2N2C0 has shown that the molecule is a five-membered planar ring. Various related adducts S2N2C0,L and (S2N2CO),,L (where L is a Lewis acid) have been prepared and their structures Although the structure of S4N4is known a new low-temperature crystallographic study has been carried out to provide more accurate bond lengths and to measure the temperature dependence of the S--S distance~.~" The reaction of S4N4with Br2 or IC1 vapours is reported to give 30 (a)R.Steudel and F. Rose Z. Naturforsch. 1978,33b 122; (b)R. Faggiani R. J. Gillespie C. J. Lock and J. D. Tyrer Znorg. Chem. 1978 17 2975. 31 (a)R. Steudel and J. Steidel Angew. Chem.Znternat. Edn. 1978,17,134;(b)R. Steudel andT. Sandow ibid.,p. 611. 32 T. Yasumura and R. J. Lagow Znorg. Chem. 1978,17 3108. 33 M. Braid G. T. Kokotailo P. S. Landis S. L. Lawton and A. 0.M. Okorodudu J. Amer. Chem. Soc. 1978,100,6160. 34 (a) K. Tanaka T. Yamabe A. Tachibana H. Kato and K. Fukui J. Phys. Chem. 1978 82 2121; (b)R. R. Adkins and A. G. Turner J. Amer. Chem. Soc. 1978,100,1383;(c)M. P. S. Collins and B. J. Duke J.C.S. Dalton 1978 277. 35 (a) H. W. Roesky E. Wehner E.-J. Zehnder H.-J. Deiseroth and A. Simon Chem. Ber. 1978,111 1670; (6) M.L. DeLucia and P. Coppens Znorg. Chem. 1978 17,2336. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway conducting metallic solids [SN(Br),.,] and [SN(ICl)o.4]x respectively. 36a Gas-phase products from vapour-brominated S,N and (SN) were identical consisting of Br2 NSBr (SN) isomers and smaller amounts of HBr S2Br2 and other S-N compounds while the reaction of S4N4 with ICl vapour yielded the volatiles 12,IC1 S4N4 NSCl HCl HI and small amounts of S2Clz and other S-N species.366 Reactions of S4N4 with bromine or iodine monochloride liquids however appear to produce S4N3Br3 and S,N31C12 re~pectively.~~' The reaction of S4N4 with alkali- metal or tetra-alkylammonium azides in ethanol produces either S,N,-(Li' Na' or K+),S3N3- (Cs+ Me," Et,N' Pr;Nf or BuiN') or a mixture of S,N,- and S3N3- (Rb+).37a Vibrational spectra suggested a cyclic structure for S3N3- and this has been confirmed by X-ray crystallographic analysis on Bu4N' S3N3-.37b An X-ray structure analysis of S4N4,S03380 has shown that the 'cage' of the S4N4 is analogous to that in S4N4,SbClS and i.r.spectra of the adducts S4N4,L (L = PhBC12 TeF, TeCl, TiBr, TiI, ZrCl, HfC14 NbF, NbCl, or TaCl,) S4N4,2L' (L'= GaC13 InC13 or FeC13) S4N,,4TiF4 and 2S,&,L" (L = SnC1 or SnBr,) suggest that these two have similar conformations in the S4N4 part of the molecules. The spectra of S4N4,WC14 and S4N4,WBr4 are suggestive of another structural type and S4N4,2AlBr3 S4N,,SeC1, S,N,,TaF, and S4N4,4SbFS are diff e~ent.~'~ The struc- ture of thiotrithiazyl nitrate S4N3+ NO3- has been redetermined.39 An X-ray crystallographic study of S,N,Cl prepared from S3N3C13 and Me3SiNSNSiMe3 has revealed a new predominantly ionic structure involving the S4N5+ cation (5).40 Another new sulphur nitride S5N6 prepared from the reaction of Bu4N' S,N,- and Br2 in methylene chloride has a structure in which an -N=S=N- unit bridges two sulphur atoms in an S4N4 cradle (6).41 In the meantime theoretical arguments suggest that SSN5+ should have the [lolannulene structure and that there should be a re-examination of the two experimental X-ray structure determination^.^' A sulphur-nitrogen ring the newly synthesized twelve-membered cyclo-tetra(azadithiane) (7),43is even larger than S5N5+.Polymeric (SN) has attracted considerable interest due to its characterization as a strongly anisotropic metal.Normally S2N2 is prepared as crystals from the vapour at 0 "C and then allowed to polymerize over several months at room temperature. It has now been shown that S2N2 single crystals grown in THF solution can be 36 (a)M. Akhtar C. K. Chiang A. J. Heeger J. Milliken and A. G. MacDiarmid Znorg. Chem. 1978,17 1539; (b)R. D. Smith and G. B. Street ibid. p. 938; (c) G. Wolmershauser and G. B. Street ibid. p. 2685. 37 (a)J. Bojes and T. Chivers Znorg. Chem. 1978 17 318; (b)J. Bojes and T. Chivers J.C.S. Chem. Comm. 1978,391. (a) V. Gieren B. Dederer H. W. Roesky N. Amin and 0.Petersen 2.anorg. Chem. 1978,440,119; (6) G. G. Alange and A. J. Banister J. Znorg.Nuclear Chem. 1978,40,203. T. N. Guru Row and P. Coppens Znorg. Chem. 1978,17 1670. 39 40 T. Chivers and L. Fielding J.C.S. Chem. Comm. 1978 212. 41 T. Chivers and J. Proctor J.C.S. Chem. Comm. 1978 642. 42 R. Bartetzko and R. Gleiter Znorg. Chem. 1978 17 995. 43 B. Krebs M. Hein M. Diehl and H. W. Roesky Angew. Chem. Internat. Edn. 1978.17,778. The Typical Elements 5 S n n 240 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway photoinduced at temperatures as low as -65 "C to give high quality (SN),.44" The origins of hydride impurity in the thermal polymerizations have been investigated and it has been demonstrated that water is involved in the formation of this Crystal surfaces of (SN) have been chemically modified so that they will electrocatalyse the oxidation of iodide to iodine.44' The structure of (4-tolyl-SNSNSNS-toly1-4)Cl in which the SN chain assumes a cis-trans-trans-cis geometry apparently to maximize the electrostatic interactions between itseIf and the chloride counter-ions has been investigated because of its resemblance to (SN),.The values of the various S-N bond lengths suggest appreciable delocalization of charge over the chain.44d A number of thiadiazetidinones have been synthesized and the structure of one (8) has been obtained by X-ray crystallography at low temperature. The mutually C /-\ perpendicular SN=S=NS and C-N N-C fragments are almost planar.45n. \/ 3-An interesting mixture of electron-rich and electron-deficient elements occurs in the first BNS ring which has been prepared by the reaction of bis(dimethy1-amin0)phenylborane with sulphonyl di-isocyanate as shown in equation (7).45b NMe, I c=o I c=o I NMe 14 N chemical shifts have been measured for a wide range of sulphur-nitrogen compounds with S-N bond orders from 1 to 2.5.The singly bonded compounds resonate at high field. 46a*b Doubly bonded nitrogens have resonances down-field of this in which the shielding increases XN=O <XN=NX< XN=CX2 == XN=SX (X = an organic or inorganic ligand). Within the XN=SX2 series the shielding increases as the ligands on S become more electronegati~e.~~~ Lithium bis(trifluoromethyl)sulphimide LiN=S(CF,), has provided a route to several new bis(trifluoromethy1)sulphimines and bis[bis(trifluoromethyl)]sulphimides.46' Although the reaction of S,Cl with nitrogen-containing organometallic compounds can give rise to compounds of the types =N-S-N= and (a) P.Love H. I. Kao G. H. Myer andM. M. Labes,J.C.S. Ch. Comm. 1978,301;(b)R. D. Smith J. R. Wyatt D. C. Weber J. J. DeCorpo and F. E. Saalfeld Inorg. Chem. 1978 17 1639; (c) A. N. Voulgaropoulos R. J. Novak W. Kutner and H. B. Mark Jr. J.C.S. Chem. Comm. 1978,244;(d)J. J. Mayerle J. Kuyper and G. B. Street Inorg. Chem. 1978 17 2610. (a)F. M. Tesky R. Mews B. Krebs and M. R. Udupa Angew. Chem. Internat. Edn. 1978 17,677; (6)H. W. Roesky and S. K. Mehrotra ibid. p. 599. (a)D. A Armitage J. Mason and J. G. Vinter Inorg. Chem. 1978 17 776; (b)J.Mason W. van Bronswijk and 0.Glemser J. Phys. Chem. 1978 82 463; (c)S. D. Morse and J. M. Shreeve Znorg. Chem. 1978,17,2169. The Typical Elements 24 1 I c3 I -N=S-N- no examples of -N=S-N- species have yet been made.47a A crystal structure of the product of the reaction of CF3S02N(SnMe3) with SC1 shows that the formulation as (9) is not valid.47b The S-N bond lengths lie between 1.553(6) and 1.688(5)A and it is clear that hybridization oxidation state and valence angles about the sulphur and the co-ordination numbers of S and N all play a part. How they work together for each bond is not The compounds NSF2NSF2 and NSF,NSOF contain S-N bonds which can be formally ascribed as having triple- double- and single-bond character. An X-ray structure of a compound containing the NSF,NSO,F-anion which is isoelectronic with NSF2NSOF2 has shown that the S-N bond lengths can be ascribed to bond orders of 2.5 1.35 and 1.9.48"The crystal structure of AsF,N(Me)SOF has shown that N rather than 0 is co-ordinated to The synthesis and chemistry of N-alk- ylidene-arenesulphinamides (10)have recently been examined and special attention has been paid to the use of the compounds for the synthesis of arenesulphenic acids.49 The synthesis of thiatriazaphosphorine (11)"" by the reaction of CF3CC12N=PC13 0 II Ar-S /CHR N/ with SO,(NH,) has led to a detailed study of a large number of sixamembered S,N,P,C ring systems.50b*c The first spirodiazasulphurane (a sulphurane with two apical nitrogen-centred ligands) has been prepared (Scheme 1)and its X-ray crystal 47 (a)H.W. Roesky M. Diehl H. Fuess and J. W. Bats Angew. Chem. Internat. Edn. 1978 17 58; (b)J. W. Bats H. Fuess M. Diehl and H. W. Roesky Znorg. Chem. 1978 17 3031. 48 (a)B. Buss D. Altena R. Hoefer and 0.Glemser J.C.S. Chem. Comm. 1978,226; (b)S. Bellard and V. A. Rivera Acta Cryst. 1978 B34 1034. 49 F. A. Davis A. J. Friedman and U. K. Nadir J. Amer. Chem. Soc. 1978 100 2844. 50 (a)W. Heidner and 0.Glemser Chem. Ber. 1978,111,731; (6) W. Heidner B. Hoge and 0.Glemser ibid. p. 737; (c) W. Heidner and 0.Glemser ibid. p. 745. 242 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway structure shows a slightly distorted trigonal-bipyramidal geometry about the Proton affinities of SO2 S02F HS03F H2S04 CF3S03H and H2S have been measured.A comparison of solution and gas-phase data indicates that compounds whose gaseous proton affinities are less than that of HS0,F are not predominantly protonated in solution in HS03F while those whose proton affinities are larger are.52a Xa scattered-wave calculations on SOz and S02F2 have established the presence of substantial 7r-bonding and significant participation of 3d orbitals in both 0-and .n-bonds in the High-pressure high-temperature reactions of H2S and SO2 with PF3 have been shown to give OPF3 (84% yield) and SPF (35% yield) re~pectively.’~ ACO,H 0 ay acJ< 0 II Reagents i SOC12 reflux for 10 h; ii PriNH2 (excess); iii Bu‘OCl; iv KH THF Scheme 1 Although the metals Li Na Be Ca Ga T1 Sb and Bi will not dissolve in SO or DMSO separately they dissolve in the mixed solvent.The metals Mg Al In and Sn react with DMSO-S02 to form metal disulphates and Sr Ba and Pb give sulphates. Phase studies and Raman spectra suggest that an SO,-DMSO adduct is responsible for the reactions.54 Stability constants of the weak charge-transfer complexes S02,X-,SOC12,X- and SO2CI2,X- (X = C1 Br or I) have been determined spectroscopically in different mixtures of MeCN and DMSO and found not to be constant; hence they must be 51 L. J. Adzima C. C. Chiang I. C. Paul and J. C. Martin J. Amer. Chem. SOC.,1978 100 953. ’* (a)D. E. Smith and B. Munson J. Amer. Chem. SOC.,1978,100,497; (b)L. Noodleman and K. A. R. Mitchell Znorg. Chem.1978 17 2709. ’’A. P. Hagen and B. W. Callaway Znorg. Chem. 1978 17 554. 54 W. D. Harrison J. B. Gill and D. C. Goodall J.C.S. Dalton 1978 1431. The Typical Elements dependent on solvent3olvent interaction^.^^" When iodine reacts with Cl- Br- or SCN- ions the extent of displacement depends on complex stability the nature of the replacing ligand and the solvent Electron-diff raction studies of SO,F (and Se02F2) have shown that the geometries are consistent with VSEPRT prediction^,^^" while that of S02C1(NCO) can be interpreted in terms of two sets of geometric parameters which differ in the relationship between the C=O and N=C bond lengths and in which the con- formational properties may be characterized in two ways.566 The mean amplitudes of vibration of the S02F- ion have been calculated from known spectroscopic data and features of the bonding have been Fluorination of sulphuryl chloride by lead fluoride in acetonitrile under anhydrous conditions has been shown to yield high-purity S0,ClF in about 40% yield.This preparative method has the advantage that high temperatures and pressures are not required.57a Reduction of S02C1F by anhydrous HI gives HzS,HCl HF HzO and I but S02F2 does not rea~t.~” The reaction of sulphenic fluorides R,SF with PF has produced mercapto- tetrafluorophoranes R,SPF (R = CF3 or CF2Cl) which with excess of R,SF give RtSSRf.58a Good evidence for sulphuranyl radicals [CF,SSR,]. (R = H or alkyl) has been obtained for the first time by e.s.r. from photochemically generated trifluoromethylthiyl radicals and dialkyl s~lphides,~~’ thus giving support to the predictions of Symons.58cpd Trithiapentalene (6a-thiathiophthene) and its derivatives have caused consider- able interest and activity because of their unusual chemical bonding. Three-co- ordinated anionic sulphurane salts e.g. (12)and (13) have now been synthesized for the first time and their reactions with electrophiles de~cribed.’~ +q0;-K+ M+ Me Me (12) (13) M=KorBu4N The importance of sulphonium cations as synthetic intermediates is well known. New examples include RS(OR2)+ and RS(OR)(NR,)’ (R = alkyl or aryl) which can be synthesized quantitatively by alkylation of sulphinic acid derivatives as shown in 55 (a)S. B. Salama S. Wasif and M.M. Omer J.C.S. Dalton 1978,918;(6)M. A. Khan S. Wasif and S. B. Salama. ibid. p. 915. S6 (a)K. Hagen V. R. Cross and K. Hedberg J. Mol. Strucrure 1978,44,187;(b)J. Brunvoll I. Hargittai and R. Seip J.C.S. Dalton 1978,299; (c) E. J. Baran and I. L. Botto. Monatsh. 1978,109,745. 57 (a)D. K. Padma and V. S. Bhat J. Fluorine Chem. 1978,11,187;(b)D. K. Padma and V. S. Bhat Nut. Acad. Sci. Letters (India) 1978,1 211. ’* (a)W. Gombler 2. anorg. Chem. 1978,439 207; (b)J. R. M. Giles and B. P. Roberts J.C.S. Chem. Comm. 1978,623;(c)R. L. Petersen D. J. Nelson andM. C. R. Symons J.C.S.PerkinII 1978,225;(d) M. C. R. Symons ibid. 1974 p. 1618. 59 P. H. W. Lau and J. C. Martin J. Amer. Chem. Soc. 1978,100 7077. F. A. Hart A. G. Massey P. G.Harrison and J.H. Holloway equation (8).60aTheir importance in biochemistry as key intermediates in a variety 0 [ R'-SR +Et30+BF4-+ R'-S <::-/BF4-+ Et2O (8) 'R2 of transmethylation reactions has also been recognized for some fifteen years. However the newly reported co-ordinated sulphonium ions open up a new area of alkylation of metal-co-ordinated dialkyl sulphides. Several manganese and chromium derivatives have been obtained and the crystal structure of one of them [(75-MeC5H,)Mn(SMe),Et)]+ PF6- has been obtained.606 The reactivity of R3S+ ion incorporated into a layer silicate has been examined and compared with that of the free salt.60c This also has a novelty which may be of synthetic value. Although there is evidence for alkyl-sulphuranes as intermediates in nucleophilic displacement reactions of sulphonium salts none has been isolated until the recent preparations of the new perfluoroalkyl-sulphuranes e.g.(CF,),S(OCF,) and (14) and perfluoroalkyl-sulphurane oxides e.g. (CF,),S(O)(OCF,) and (CF,),S(O)- [N=C(CF3)2]2.610 The first stable members of a new family of sulphuranes contain- ing four-co-ordinated sulphur(1v) (15) have also been synthesized.61b I R' (15) R' = Ph or Ph&2 R2= Me or OMe The simplest sulphenic acid CH,SOH has been generated for the first time by flash vacuum pyrolysis and characterized by microwave spectroscopy. It contains two-co-ordinated rather than three-co-ordinated sulphur i.e. R-S-OH not RS(0)H. This is of importance because structural information on simple sulphenic acids has not been available hitherto and because of the recent demonstration that specific sulphydryl groups in some enzymes can be oxidized by stable sulphenic acids with a resultant alteration of the catalytic activity.62" The first sulphene reaction in complex chemistry a sulphene insertion into a metal-hydrogen bond has now been confirmed by 2H-labelling The super-acids HS03Rf(SbF5) (n =0-5; Rf=F CF, or C2F5) have been prepared; low-temperature high-resolution 19Fn.m.r.spectra have shown that the 6o (a)H.-U. Wagner and A. Judelbaurn Angew. Chem. Internat. Edn.,1978,17,460; (b)R. D. Adam and D. F. Chodosh,J.Amer. Chem. Soc. 1978,100,812;(c)J. Gosselck and I. Stahl Angew. Chem. Internat. Edn. 1978 17 274. 61 (a)T Kitazurne and J. M.Shreeve Znorg. Chem. 1978,17 2173; (b)T. Kitazurne and J. M. Shreeve J. Amer. Chem. Soc. 1978,100,985. 62 (a)R. E. Penn E. Block and L. K. Revelle J. Amer. Chem. Soc. 1978 100 3622; (6) I.-P. Lorenz Angew. Chem. Internat. Edn. 1978.17.285. *! The Typical Elements SbF group retains the cis-polymeric onf figuration.^^" It has been suggested that the oxidizing agent in the oxidation of alkanes by HS03F is S"' rather than the proton since no molecular hydrogen could be detected in reactions in acid alkaline or neutral ~ol~tion~.~~~ Using monoprotonated g-methoxybenzaldehyde (pKBH2+ = 19.5) the relative acidity of the super-acids HF-SbF and HS03F-SbF has been compared. It has been concluded that HF-SbF is weaker than HS03F-SbF5 only when the SbF content is below 0.6 mol '/o .63c Graphite trifluoromethanesulphonate (C26+CF3S03-,1.63CF3S03H) has been prepared by anodic oxidation or oxidation with K2Cr207 of graphite in CF3S03H The i.r.spectrum of matrix-isolated SF has been observed for the first time,64a but no details except that the bond angle is as observed earlier,646 have been reported. Reactions of SCl and S,Cl with the trimethylsilyl derivatives of nitrogen hetero- cycles have given six new azole sulphur-transfer reagents which have produced interesting reactions with thiols amines and alcohols. Of particular interest is the formation of sultines (16) and (17)? The reactions of monosilylated sulphamides with SClz and of disilylated sulphamides with SZCl2 in the presence of sulphur have produced a variety of sulphur amides and imide~.~" Reactions of S2C12 with alkali-metal iodides produce iodine-sulphur mixtures.In contrast the reaction of HI with S2C12 at low temperatures produces a solid which from its i.r. spectrum appears to contain S21z and an adduct of S212 with iodine.66" Spectroscopic investi- gations in the u.v.-visible region have suggested the existence of SOI and that earlier reports on S12 and S0212may be erroneous.666 (16) E.p.r. and crystallographic data from y-irradiated single crystals of SF3+ BFs- have been ascribed to the planar SF radical which appears to contain two equivalent fluorine atom^.^' An X-ray structure determination on crystals of SCI3+ IC14- shows that the cation is pyramidal. Three other contacts to chlorine from the planar IC14- give rise to a distorted octahedral arrangement of chlorines about the sulphur.68n Raman spectroscopic data on the solid compounds SCl4,MC1 (M = Nb or Ta)68b and the new SBr3+MF6- (M=As or Sb)68c are consistent with them containing pyra- midal cations.63 (a) D. Brunel A. Germain and A. Cornrneyras Nouveau J. Chim. 1978,2,275;(b)A. Jobert-Perol and M. Herlern Compt. rend. 1978,287 C,109; (c)J. Sornmer S. Schwartz P. Rirnmelin and P. Canivet J. Amer. Chem. SOC.,1978,100 2576; (d)D. Horn and H. P. Boehm Mater. Sci. Eng. 1977 87. 64 (a)A. Haas and H. Willner Ber. Bunsengesellschaft phys. Chem. 1978 82 24; (b)W. H. Kirchhoff D. R. Johnson and F. X. Powell J. Mol. Spectroscopy 1973 48 157. 65 (a) D.N. Harpp K. Steliou and T. H. Chan J. Amer. Chem. Soc. 1978,100 1222; (b)R. Appel and M. Montenarh Chem. Ber. 1978,111,759. 66 (a) G. Vahl and R. Minkwitz 2.anorg. Chem. 1978,443,217; (6)K. Manzel and R. Minkwitz ibid. p. 165. J. R. Morton K. F. Preston and S. J. Strach J. Chem. Phys. 197g 69 1392. 67 68 (a)A. J. Edwards J.C.S.Dalton 1978,1723;(b)F. W. PoulsenandR. W. Berg J. Znorg. NuclearChem. 1978,40,471;(c)J. Passmore E. K. Richardson and P. Taylor Inorg. Chem. 1978 17 1681. 246 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway A qualitative MO model of valence electronic structures of AB4 complexes including the sulphur tetrahalides has been described and comparison is made with AB6 complexe~.~~ Sulphur tetrafluoride has been shown to form SF4L2- [L= (CF,SO,)- (FS03)-,70" or (CF3COO)- 706].A new method for the preparation of CF3SF3 involves the direct fluorination of CF,SSCF at -120 "C under carefully controlled conditions. Extension of reaction times leads to conversion into CF3SF5.70C Methylenesulphur tetrafluoride H2C=SF4 in which the methylene group is coplanar with a pair of fluorines has been prepared uia H3C-SF5 (the carbon analogue of HO,SF,). The new compound undergoes a number of reactions analogous to those of carbene~.~'~ Hexahalides are emphasized in a description using qualitative MO methods without d-orbital participation to study six-co-ordinate and a similar approach has been applied to AB5 systems such as SF5-.71b Ionization potentials of SF6have been calculated by the Xamethod71c and electron affinities of SF (and SF and SF,) have been obtained from a study of the negative-ion products resulting from collisions between fast alkali-metal atoms and SF6.72 An electron-diff raction study of SF6 has confirmed the octahedral arrangement with an S-F bond length of 1.561(2) A.73 Studies of the i.r.74a and Raman746*' spectra and of laser-induced photochemistry of matrix-isolated SF6,74d*C continue to be of interest.The preparations of various hexafluoride radicals including SF6- have been reported and their e.p.r. spectra c~mpared.~ The Urey-Bradley force constants of SFSO- SF5Br and SF5Cl have been deter- mined by a least-squares-fit method using published fundamental frequencies.The results suggest that some reported assignments are q~estionable.~~" Simple S-Cl bond cleavage seems to be the primary photolytic reaction in reactions of SF5C1 that are induced by a carbon dioxide Stepwise defluorination of SF5X (X = C1 or Br) and CF3SF4Cl with the reactive nucleophile LiN=C(CF3) has produced a variety of stable five- and four-co- ordinated sulphur (VI) and now the stereochemical aspects of octa- hedral sulphur have been investigated through reactions of compounds such as SF5Cl SF5Br CF3SF4Cl cis-CF3SF4CF3 cis-SF4(OS0,F), and cis-SF4(OCF3) with C,F,SiLi CF,SLi C6H5Li and LiN=C(CF3)2.776 A general method of synthesis of mono- and di-hydryl-pentafluorosulphur-F-alkanesSFSCHZRf and SF,CH(R,), where R,= F or CF3 has been de~eloped.~" The first examples of a 69 B.M. Gimarc and S. A. Khan J. Amer. Chem. SOC.,1978,100,2340. 70 (a)S. Brownstein J. Bornais and G. Latremouille Canad.J. Chem. 1978,56,1419; (6)S. Brownstein ibid. p. 343; (c)R. W. Braun A. H. Cowley M. C. Cushner and R. J. Lagow Znorg. Chem. 1978,17 1679; (d)G. Kleeman and K. Seppelt Angew. Chem. Internat. Edn. 1978,17,516. 71 (a)B. M. Gimarc J. F. Liebman and M. Kohn J. Amer. Chem. SOC.,1978,100,2334;(b)B. M. Gimarc ibid. p. 2346; (c)G. L. Gutsev and A. A. Levin Chem. Phys. Letters 1978 57 235. 72 R. N. Compton P. W. Reinhardt and C. D. Cooper J. Chem. Phys. 1978,68,2023. 73 L. S. Bartell and S. K. Doun J. Mol. Structure 1978,43 245. 74 (a)K. Fox J. Chem. Phys. 1978,68 2512; (6)B. Rubin T. K.McCubbin and S. R. Polo Jr. J. Mol. Spectroscopy 1978,69,254; (c)R. J. H. Clark and N. R. D'Urso J.C.S.Dalton 1978,170; (d)B. Davies A. McNeish M. Poliakoff M. Tranquille and J. J. Turner J.C.S. Chem. Comm. 1978 36; (e)R. A. Crocombe N. R. Smyrl and G. Mamantov J. Amer. Chem. Soc. 1978,100,6526. '' A. R. Boate J. R. Morton and K. F. Preston J. Magn. Resonance 1978 29 243. 76 (a)S. P. So K. K. Li and L. K. Hung Bull. SOC.Chim. belges 1978,87,411; (6) K. M. Leary J. L. Lyman and L. B. Asprey J. Chem. Phys. 1978 68 1671; (c)R. R. Karl and J. L. Lyman Jr. ibid. p. 1196. 77 (a)T. Kitazume and J. M. Shreeve J. Amer. Chem. SOC.,1977,99,3690; (b)T. Kitazume and J. M. Shreeve ibid. 1978 100 492; (c)R. A. De Marco and W. B. Fox J. Fluorine Chem. 1978 12 137. The Typical Elements fluorine-containing dichlorosulphur and fluorinated five-co-ordinate dichlorosul- phimides have been obtained (see Scheme 2).78 Reagents i excess ClF at 0 "C,for 12 h; ii 2MeN(SiMe3)2 at 25 "C for 10 h; iii excess ClF at 25 "C for 12 h; iv 2LiN=C(CF3)2 THF for 24 h Scheme 2 E.p.r.spectra of y-irradiated NSF in SF6 have resulted in the identification of the planar radical NSF3 and possibly FNSF.79a The reaction of NSF with polar reagents such as RF has been suggested to proceed via the mechanism shown in equation (9). N2F,+R6'-F6-+{RN=SF3+ F-} + {RN=SF4} + {RNSFS- R+} + R2N-SFS (9) Using the cation CH,OSO' as a methylating agent stepwise addition of methyl fluoride has now permitted the isolation of two of these intermediates i.e.CH3NSF3+ and CH3N=SF4.79b New mono- and di-S-substituted thiazynes have been prepared by the reaction of NSF3 with various organolithium compounds at -789C.79c Selenium and Tellurium.-Reviews on aspects of selenium and tellurium chem- istry26 have already been mentioned. Monoclinic Se3S5 has been shown to be isostructural with S8(y)29a and Se4S4 contains alternate S and Se atoms.80a X-Ray methods have shown that the dark-red material resulting from the fractional distillation of the product of reaction of H2S and TeCl in dichloromethane contains mixed crystals of TeS7 Te2S6 and S8,80band orthorhombic tetraselenocan (CH2Se), has a twisted chair conformation (18).'OC Theoretical studies on As4Se4 and As4Se4- have shown that the anion is of lower energy.34a The dominant telluride ion when tellurium is dissolved in LiC1-KCl and LiF-BeF molten salts is Te-.The suggestion that Te,- is also present81a seems unlikely in view of the recent synthesis of the first alkali-metal polytelluride which has the form K2Te3.'lb Indium polytelluride In2TeS (phase II) consists of sheets of chains of four-membered In-Te rings cross-linked by Te3*- polyanions,"' the structure being related to that of an earlier reported phase In2TeS (phase I).81d 78 T. Kitazume and J. M. Shreeve J.C.S. Chem. Comm. 1978 154. 79 (a)A. R. Boate and K. F. Preston Znorg. Chem. 1978,17,1669;(b)R.Mews Angew. Chem. Internat. Edn. 1978,17,530;(c)A.F.Clifford,J. L. Howell and D. L. Wopton. J. Fluorine Chem. 1978,11,433. (a)A.Datta and V.Krishnan Indian J. Chem. 1978,MA,335:(b) M. Pupp and J. Weiss 2.anorg. Chem. 1978,440,31;(c)G.Valle G. Zanotti and M. Mammi Acta Cryst. 1978,B34,2634. (a)L.M. Toth and B. F. Hitch Znorg. Chem. 1978,17,2207;(b)B. Eisenmann and H. Schafer Angew. Chem. Internat. Edn. 1978,17,684;(c) P. D. Walton H. H. Sutherland and J. H. C. Hogg Acru Cryst. 1978,B34,41. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Se C (18) High-resolution 125Te and 77Se F.T. n.m.r. spectroscopy has been used for characterization of the previously known Te$+ Te2+ Se42' and Te2Se2+ cations and has established the occurrence of the hitherto unknown mixed species in the +$(Te3Se2' cis- and trans-Te2SeZ2+ and TeSe,") and +f(Te3Se32+) oxidation states.82a Members of the Te,Se,-42' (n=14)series have also been indepen- dently characterized using '25Te and 123Te F.T.n.m.r.82b This establishes an entirely new approach to the study of polyatomic cationic species. Meanwhile well-known polyatomic cations of Sessa and Te83b,c have been observed in solution in HSO3C1. Two tetraoxyselenuranes (19)have been prepared and it has been shown that the intramolecular reorganization of ligands in these species follows that for ~ulphuranes.~~ (19) R=HorMe A detailed understanding of selenate- and tellurate-(rv) chemistry requires accurate knowledge of the dimensions of the unpolarized Te032- anion. A recent structure determination of K,Te03,3H20 has produced bond lengths and angles for the purely i~nicTeO~~- and the radius of the 5s2electron pair has been estimated.85a The free lone pair on Te'" is also of importance in the structure of the mixed oxotellurate K2Te1VTeV13012 which is of further interest because of the simul- taneous presence of Te'" and TeV' in a metallic cation.85b Trigonal-pyramidal TeS3'- ions have been observed X-ray crystallographically in K3(SH)TeS3.85' (a)G.J. Schrobilgen R. C. Burns and P. Granger J.C.S. Chem. Comm. 1978,957;(b)C.R.Lassigne and E. J. Wells ibid. p. 956. 83 (a) S. A. A. Zaidi Z. A. Siddiqi and N. A. Ansari Acta Chim. Acad. Sci. Hung. 1977 93 395; (b) S.A.A. Zaidi Z. A. Siddiqi and N. A. Ansari ibid. 1978 97 207; (c)R.C.Paul D. Konwer D. S. Dhillon and J. K. Puri Indian J. Chem. 1978 16A 253. 84 D.M.Denney D. Z. Denney and Y. F. Hsu I. Amer. Chem. Soc. 1978,100,5982. 85 (a)G. B. Johansson and 0.Lindquist Acra Crysf. 1978 B34,2959; (b)F.Daniel J. Moret M. Maurin and E. Philippot ibid. p. 1782;(c)G.Dittmar and H. Schaefer 2.anorg. Chem. 1978,439 212. The Typical Elements 249 Reactionsof NaHSe03 or Te02 with BllH14- ion produce BllHllSe and BllHllTe in heptane-water solutions thus demonstrating a new method for the insertion of Se and Te into borane and carbaborane anions.86a Tellurate(1v) anions are reduced by BH4- [or the products of its hydrolysis i.e. BH30H- and BH(OH),-] to Te and H2Te.86b The mixed oxides Te02,M20 Te20,,2M20 and Te03,M20 (M = Na or K) have been prepared by solid-state reaction at -400 "C and their structures disc~ssed.~' The pure rotational Raman spectrum of Se03 monomer in the gas phase has been obtained for the first time," and the molecular structure of Se02F2 has been determined by gas-phase electron diff ~action.'~" Monofluoro-selenite and -tellurite anions have been obtained and characterized by i.r.and Raman spectroscopy in the compounds M(Se02F) (M = Cs Me4N or Et,N) and M'(TeO,F)'(M = Na K or Me4N).89 The enthalpies of formation and standard entropies for the species TeOC12(g)90"*b and TeOBr2(g)"" and the polymeric oxide halides Te6OI1X2 (X = C190" or Br9'") have been calculated and a comparison has been made with theoreti- cal The association of selenate with bivalent metals has been compared with that of sulphate on the basis of enthalpy and entropy values obtained by calorimetric measurement~.~' Raman spectra of orientated single crystals of K2Se04 have shown that earlier spectra contained spurious and incorrectly assigned bands.92 Tetra- hedral SeO4 groups in crystalline NaNH4Se04,2H2093a are linked and SC(S~O,)~~~~ together in three-dimensional networks and in CuTeO, idealized (Te0,);"- layers are distorted by copper co-~rdination.~~~ Force constants bond orders and mean amplitudes of vibration have been estimated from the vibrational spectrum of Te2OS2- in the magnesium A crystal-structure determination on (NH4)2Te205,2H20 has shown that the Te205 groups are connected to form In the rarer (Pb)2Te308 two crystallo- graphically independent Te atoms are linked into endless chains parallel to the a axis by bridging oxygen atoms and the other two are linked into isolated Te30$- ions.95b A simple relationship has been established between bond length and the 1291 isomer shift and coupling constant for a selection of tellurium iodide compounds a-TeI a-Me2Te12 p-EtOC6H4Te13 CsTeI, and TeI4 by Mossbauer spectros- 86 (a)G.D. Friesen and L. J. Todd J.C.S. Chem. Comm. 1978,349;(6)E. S. Kotelevets V. S. Khain and E. N. Marinova Zhur. neorg. Khim. 1978 23 676. E. Gutierrez M. L. Veiga and C. Pico J.C.S. Dalton 1978 948. 88 N. J. Brassington H. G.M. Edwards D. A. Long and M. Skinner J. Raman Spectroscopy 1978,7,158. 89 J. Milne Znorg. Chem. 1978 17 3592. 90 (a)G. I. Novikov V. V. Zvezdina and V. P. Bochin Zhur. fiz.Khim. 1978,52,1067; (6)H.Opperman Z. anorg. Chern. 1977,434 239; (c) H. Oppermann V. A. Titov G. Kunze G. A. Kokovin and E. Wolf ibid. 1978 439 13. 91 R. Aruga Znorg. Chem. 1978 17 2503. 92 C. Caville V. Fawcett and D. A. Long J. Raman Spectroscopy 1978 7 43. 93 (a)Yu. Z. Nozik L. E. Fykin V. Ya. Dudarev L. A. Muradyan and A. E. Rustuntseva Kristallografiya 1978 23 617; (6)J. Valkonen Acta Cryst. 1978 B34 1957; (c) L. Falck 0.Lindquist W. Mark E. Philippot and J. Moret ibid. p. 1450. 94 E. J. Baran 2.anorg. Chem. 1978,442 112. 95 (a)G.B. Johansson Acta Cryst. 1978 B34,2830; (b)J. C. Dewan A. J. Edwards G. R. Jones and I. M. Young J.C.S. Dalton 1978 1528. 250 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway copy.96 Heats of formation of Se2Br2(l) SeBr4(s) TeBr(s) and TeBr4(s) have been measured calorimetrically.97 Trigonal-pyramidal SeC13' found in the crystal struc- ture of SeC13'MoOC14- implies that there is a lone pair of electrons on the The structure of tetrakis(ethylenethiourea)tellurium(rI) hexachloro-tellurate(1v) consists of square planar [Te(etu),I2+ cations and TeC16*- anions stacked in chains along the a axis.98b Crystallographic data on a large number of amino-acid salts containing hexabromoselenate(~v),~~' hexabromotellurate(~~),~*~ and hexaiodotellurate(~v)~~" have also been published.N.q.r. resonances of 35Cl in (MeNH3)2Te&(X = C1 Br or I) have been used to monitor phase transitions with respect to temperature in the complexes.99 A qualitative MO treatment of AB (A = Se or Te B =Hal) molecules has been de~cribed.~'Thermochemical properties of solid SeCl and SeBr4 loo" and solid and liquid TeF4100b have been obtained and molecular vibration analyses of the selenium and tellurium tetrachloride tetramers and of the selenium tetrachloride monomers carried out."' Selenium and tellurium five-~o-ordinate'~~ systems have and ~ix-co-ordinate~~" been described using qualitative MO methods.Electron affinities for SeF6 and TeF6 have been reported'' and vapour-phase intensity studies of the Raman bands have provided information on electronegativities and bond p~larizabilities.~~" Infrared investigations of SeF6 using matrix isolation and isotopic substitution techniques have yielded force constants and band contours of Y3(FI,,) and Y4(Flu) for SeF6.lo2" The isotopically selective i.r.photodissociation of SeF6 has been reported. lo*' The molecular structure of gaseous TeF6 has been obtained from electron diffraction at 20,90 and 150 OC.lo3 The e.p.r. spectra of the selenium and tellurium hexafluoride radicals have been Urey-Bradley force constants for SeF5C1 and TeFSCl have been determined.76" Alkoxo-tellurium fluorides TeF6-,(OR) (x = 1-5; R = alkyl) have been prepared for TeF6 with the appropriate alcohol from TeF5(OMe) or cis-TeF4(0Me) with NaOMe or by low-temperature fluorination of Te(OR),. lo4 The preparation and structures of the new tellurium oxide fluorides cis-and tran~-F,Te(OTeF~)~ cis-and truns-F,Te(OTeF,), FTe(OTeF,), and Te(OTeF,) have been prepared and the structures of two forms of Te(OTeF5)6 determined by single-crystal X-ray method^.^" The exceedingly high electronegativities of the (OSeF,) and (OTeF,) groups have been exploited in their reactions with iodine to give compounds of the 96 C.H. W. Jones and M. Mauguin J. Chem. Phys. 1978,68,3067. 97 V. G. Tsvetkov Zhur. neorg. Khim. 1978,23 1976. 98 (a) A.Gleizes and J. Galy Compr. rend. 1978 286 C 29;(6) H.K. Ault and S. Husebye Acta Chem. Scand. 1978 A32,157; (c)A.Hempel Z. Dauter and S. Szwabski 2.Krist. 1978,146,318; (d) A.Hempel Z. Dauter and R. Pastuszak ibid. p. 317;(e)Z.Dauter A. Hempel and H. Jedrzejczak ibid. p. 320. 99 Y. Kume R. Ikeda and D. Nakamura J. Phys. Chem. 1978,82 1926. loo (a)A. D. Westland and R. Makhija Cunad. J. Chem.1978 56 1586; (b)J. Carre P. Claudy and M. Kollmannsberger J. Fluorine Chem. 1978 11,613. S. J. Cyvin B. N. Cyvin W. Brockner and A. F. Demiray 2.Naturforsch. 1978 36a 714. Io2 (a)F. Koeniger A. Mueller and H. SeEg Mol. Phys. 1977,34,1629;(b)J. J. Tiee and C. Wittig Appl. Phys. Letters 1978 32 236. Io3 G. Gundersen K. Hedberg and T. G. Strand J. Chem. Phys. 1978,68,3548. G. W.Fraser and G. D. Meikle J.C.S. Dalton 1977,1985. D. Lentz H. Pritzkow and K. Seppelt Znorg. Chem. 1978,17 1926. The Typical Elements 25 1 type F,I(OXF,),-,,'06 and the bonding"" and in related oxygen compounds F,XOXF (X = Se or Te) have been studied. 2 GroupVII A book on fluorine-containing free radicals includes reviews on crossed-beam fluorine chemistry and the e.s.r.spectra and structures of inorganic fluorine- containing free radicals. Another dealing with the inorganic chemicals industry "" contains excellent coverage of the chlorine and chlor-alkali industries; fluorine HF and inorganic fluorides and the bromine and bromine chemicals industries. Comparison of enthalpies of formation of a wide range of inorganic and organic fluoro-compounds with those of corresponding hydroxy-compounds has revealed a lack of thermodynamic data in some areas. Reviews on the synthesis of inorganic solid-state compounds under high pressure1o86 and the value of the cleavage of cyclic compounds as a means of synthesis for fluorine compounds'08c are of considerable interest as are those on the application of electron-deflection spectroscopy as an aid to structure determination of binary fluorides and oxide fluorides,'08d complex fluoro-cations,108e and ferromagnetism in Interest in the reactions of atomic fluorine has continued with for example studies on dissociative attachment of electrons to fluorine 109a*b and the reactions of atomic fluorine with H2 lo9' HI 109d and other hydrogen-containing rn01ecules~'~~ and oxygen.losf The kinetics of the spontaneous reaction of fluorine with H2Shave also been studied."' Photochemical reactions of chlorine initiated by an argon laser"' and work on the kinetics of oxidation of hydrazine by iodine are also significant the latter being of importance for the iodometric determination of hydrazine. Novel aspects of halogenation methodology are evidenced by an investigation of the use of silica-supported tetrabutyl- tetraethyl- and benzyltrimethyl-ammonium potassium and caesium fluorides as non-hygroscopic sources of fluoride ion '13" the use of bromine on a molecular sieve as a selective brominating agent '13' and concern with the absorption spectra of liquid F2 and the fluorides NF3 N2F4 CF4 BF3 and SF6.113' This latter investigation shows that the absorption spectra do not differ significantly from those of gas-phase species which has implications for some lo6 D.Lentz and K. Seppelt Angew. Chem. Internat. Edn. 1978 17 355. (a)'Fluorine-containing Free Radicals' ed. J. W. Root The American Chemical Society Washington 1978; (b) 'The modern Inorganic Chemicals Industry' ed.R. Thompson The Chemical Society London 1977. lo' (a)A. A. Woolf J. Fluorine Chem. 1978,11,307;(b)R. Hoppe Israel1 Chem. 1978,17,48;(c)A. Shanzer ibid. p. 100; (d)W. E. Falconer ibid. p. 31; (e)V. Ya. Rosolovskii Koord. Khim. 1978.4 867; (f)A. Tressaud J.-M. Dance and P. Hagenmuller Israel I. Chem. 1978 17 126. log (a)B. I. Schneider and C. A. Brau Appl. Phys. Letters 1973,33 569; (b)R. J. Hall J. Chem. Phys. 1978,68,1803;(c)W. Jakubetz ibid.,p. 1783;(d)I. Burak and M. Eyal Chem. Phys. Letters 1977,52 534; (e) S. N. Foner and R. L. Hudson J. Chem. Phys. 1978 68 2987; (f)P. P. Chegodaev V. I. Tupikov and E. G. Strukov Khim. vysok. Energii 1978,12 116. 'lo V. G. Fedotov and A. M. Chaikin Kinetics and Catalysis (U.S.S.R.), 1977 18 1367. '" L.N. Krasnoperov N. L. Lavrik and Yu. N. Molin Khim. vysok. Energii 1978 12,262. 'I2 S. E. King J. N. Cooper and R. D. Crawford Inorg. Chem. 1978 17 3306. 'I3 (a)J. H. Clark J.C.S. Chem. Comm. 1978,789;(6)P. A. Risbood and D. M. Ruthven J. Amer. Chem. SOC., 1978,100,4919;(c)V. A. Legasov G. N. Makeev V. F. Sinyanskii and B. M. Smirnov J. Huorine Chem. 1978,11 109. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway reactions involving inorgnic fluorides which proceed efficiently only at low tempera- ture in the liquid state. The structures of solid and liquid chlorine have been studied extensively in the past but little has been done on the (Clz)z dimer. Theoretical considerations have now indicated that the most likely geometry is the ‘L’ onf figuration.^^^ The direct observation of photo-formed C12- radical anion has helped with the elucidation of the photolytic mechanism of formation of chloro-copper(I1) complexes in non-aqueous media.The accommodation of polyiodide ions in the differing types of cationic sites in the versatile solid-state structure T1616Mi/+n(14)2- (M=Ag Au T1 Pb Bi Ln Zr Hf or Th) has been Resonance Raman and 1291 Mossbauer spectroscopy have unambiguously solved an old mystery by showing that the dominant polyiodide in the blue-black adduct of starch-iodide is 15-.Il5= IN3 has been prepared in organic solvents and the i.r. and Raman spectra of the compound in solid dichloromethane at low temperatures has been assigned on the basis of C syrnmetry.’l6 Reactions of the electropositive chlorine compounds ClF R,OCl SF50Cl CF300C1 SF500C1 CIOSOzF ClOClO, and C10N02 with fluorocarbons have been reviewed for the first time 117a and the new C1’ derivatives CF3C(0)OCl and CF3SO20C1 have been prepared.lt7’ The latter is perhaps the most electrophilic compound ever prepared. Recent solution chemistry of inorganic species in anhydrous HF has been reviewed and it has been postulated that speciation of solutes particularly cationic entities is simpler in HF than in water.ll* Properties such as dipole quadrupole and octupole moment diamagnetic contributions to the magnetizability the nuclear magnetic shielding the electric field gradient at the nuclei and the polarisability of HF have been calculated as functions of internuclear separation using an MCSCF wavefunc- tion.Results are in good agreement with experiment. 119a Thermodynamic studies of the halogen acids in n-methylpropionamide have revealed a dependence of the ion-solvent interactions on anionic size in agreement with classical electrostatic theory. *I9’ The hydrogen fluoride dimer being a key example of hydrogen bonding has been widely studied using ab initio molecular orbital techniques. An intermolecular potential function for (HF):! has now been determined which is suitable for use in J. Prissette and E. Kochanski J. Amer. Chem. Soc. 1978 100,6609. (a)J. Sykora; I. Giannini and F. D. Camassei J.C.S. Chem. Comm. 1978,207;(b)A.Rabenau and W. Stoeger Angew. Chem. Znternat. Edn. 1978,17,599;(c)R. C. Teitelbaum S.L. Ruby andT. J. Marks J. Amer. Chem. SOC.,1978 100 3215. U.Englehardt M. Feuerhahn and R. Minkwitz 2. anorg. Chem. 1978,440 210. (a)C. J. Schack and K. 0.Christe Israel J. Chem. 1978,17,20;(6)D. D. DesMarteau J. Amer. Chem. Soc. 1978 100 340. T. A.O’Donnell J. Fluorine Chem. 1978,11 467. (a)R.D.Amos Mol. Phys. 1978,35,1765;(6)H.P.Bennett0 and I. K. Kamboj J.C.S. Chem. Comm. 1978.523. The Typical Elements 25 3 Monte Carlo simulations of liquid HF and super-acid solutions.120a A pairwise intermolecular force model for (HF) has also been developed from Hartree-Fock calculations1206 in a similar way to that used successfully for H20. Neutron- diffraction scattering has been demonstrated as a useful means of investigating the low-frequency vibrational modes of solid and liquid HF.l2OC An appropriate value for the heat of mixing of HCN and HF in the liquid phase'20d and the enthalpies of formation of hydrogen-bonded complexes between HF and cyclic ethers have added to our knowledge of the energetics of formation of hydrogen bonds. Much information has been obtained on energy transfer in the HF-HF system. An understanding of the details of this fast transfer is important for the development of chemical lasers. Semi-classical calculations of rate constants making allowance for the polar nature large rotational velocity and strong intermolecular attractive forces have now been made121a and a new method of studying relaxation which is an extension of the laser-excited vibrational fluorescence technique,'216 has also been reported.The relative acidities of the super-acids HF-SbF5 and HSO,F-SbF have been HX2- species are of interest because of their strong hydrogen bonds and the resultant high stability. Preliminary results of an i.r. investigation on HF2- in an argon matrix have produced new structural information on this anion. Di-organodichlorophosphonium hydrogen dichlorides made by the reaction of dithio-phosphinic acids with C12 as shown in Scheme 3 have been formulated as R'R2P(S)SH+ 3C12 + [R'R2PCl2]+ [ClHClI-+ S2C12 R' = 4-MeOC6H4; R2 =Me Ph or 4-MeOC6H4 HS(S)P-R2-P(S)SH +6C12 + [(C12P-R2-PC12]2'[Cl-H-C1]2-+2S2C12 I I I I R' R' R' R1 R' = 4-MeOC6H4; R2 = 1,4C6H4 or -(CH2)4-Scheme 3 [R'R2PC12]'[CIHC1]-on the basis of mass spectrometric and X-ray structural information.'226 A search for the neutral FHCl and FHF free radicals from the photolysis of F2in HF or HCl in argon matrices at 14 K has produced no evidence for FHF but weakly bonded HF-C1 which has a different structure to the FHCI- anion has been detected.122 The preparation properties and structures of fluorohalogenates XF2-' XF4-'11 and XF6-" have been reviewed.', The reaction of fluorine with each of the 120 (a)W.L. Jorgensen and M. E. Cournoyer J. Amer. Chem. SOC.,1978,100,4942; (b)M. L. Klein I. R. McDonald and S. F. O'Sheh J. Chem. Phys. 1978,69,63; (c)J. W. Ring ibid. 1978,68,2911;(d)J. L. Collister and H. 0.Pritchard Cunad. J. Chem. 1978,56,2788; (e)M. Tsuda H. Touhara K. Nakanishi K. Kitaura and K.Morokuma J. Amer. Chem. SOC.,1978 100 7189. 12' (a)L. L. Poulsen G. D. Billing and J. I. Steinfeld J. Chem. Phys. 1978,68,5121; (6)D. J. Douglas and C. B. Moore Chem. Phys. Letters 1978,57,485. 122 (a)B. S. Ault J. Phys. Chem. 1978,82,844; (b)W. Kuchen D. Mootz H. Somberg H. Wunderlich,and H.-G. Wussow Angew. Chem. Internut. Edn. 1978 17 869; (c) B. S. Auk J. Chem. Phys. 1978,68 4012. lZ3 J. Shamir Israel 1. Chem. 1978 17 37. 254 F. A. Hart A. G. Massey P. G. Harrison,and J. H. Holloway molecular halogens upon photolysis in solid matrices has produced the new species XF2 X2F and X2F2 as well as the normally unfavoured members of the series XF (n= 1 3 or 5). The major product of each photolysis is XXF2 analogous to the T-shaped XF (X = C1 Br or I).'24 Electronic structures of CIF ClF2- and ClF3 have been calculated by ab initio methods and the role of d-orbitals has been ana1y~ed.l~' The kinetics of the reaction of H2 with ClF in a flow apparatus126a and the kinetics and mechanisms of the reactions of ClF with H2 1266 and HC1lZ6' have been studied.The first application of rotating-frame n.m.r. to a gas-phase system has been made on CIF and values of the C1 spin-lattice relaxation time and the C1to F spin-spin coupling constant have been derived.12 Interest in the electronic characteristics of diatomic interhalogens is evidenced by studies on ClF* (B3~0+)128a and BrF* (B3~0+).1286-e Electron-diffraction studies on C1F3129n and C1F5'29b have been carried out. The reaction of C1F3 with graphite in NOF,3HF gives C14F,ClF3,3HF,1'o" which is the same product as previously prepared from graphite ClF3 and HF.The reaction of BrF3 with graphite has also been studied. 130b Three solid phases of ClF previously identified by n.m.r. have been characterized by Raman spectroscopy and X-ray and neutron diffraction. The analogy between the structures of the tri- and penta- fluorides of C1 and Br has been Derivation of improved gas-phase structural parameters for BrF5 has been made possible by observation of microwave spectra of BrF5 in excited vibrational states 132a while assignments of the rotational spectra of IF5 are in good agreement with those of CIF and BrF,.132b New vapour-pressure measurements on IF5 and IF and some transition-metal hexafluorides have been made and transition temperatures and enthalpies of vaporization have been calculated and compared with theoretical values.133 It has been shown that IF intercalates with graphite only in the presence of HF. Other interhalogens such as IF, ClF5 ClF3 BrF5 and BrF3 all intercalate with fluorination of the graphite host and in the IF case the intercalated species has been identified as IF5.134 E. S. Prochaska L. Andrews N. R. Smyrl and G. Mamantov Inorg. Chem. 1978,17,970. lZs A. E. Smolyar M. B. Zuev N. M. Klimenko and 0. P. Charkin Zhur. strukt. Khim. 1978,3,387. 126 (a)Yu. I. Petrov F. M. Mukhametshin A. G. Shumikhin and A. D. Stepukhovich Zhur. fiz. Khim. 1978,52,1823; (b)G. P. Zhitneva and S. Ya. Pshezhetskii Kinetika i Kuraliz 1978,19,296;(c) G.P. Zhitneva and S. Ya. Pshezhetskii ibid. p. 292. 12' K.T. Gillen D. C. Douglass and J. E. Griffiths J. Chem. Phys. 1978,69,461. lZ8 (a)R. D. Coombe D. Pilipovich and R. K. Horne J.Phys. Chem. 1978,82,2484;(b)J. A. Coxon and A. H. Curran J. Photochem. 1978,9 183; (c)M. A. A. Clyne and I. S. McDermid J.C.S. Faraday II 1978 74 644; (d)M. A. A. Clyne and I. S. McDermid ibid. p. 664; (e) M. A. A. Clyne and I. S. McDermid ibid. p. 1376. (a)I. M. Myakshin A. B. Al'tman V. F. Sukhoverkhov G. V. Romanov and V. P. Spiridonov 5-Z Vses. Simpoz. Po Khimii Neorgan. Ftoridov. Dnepropetrovsk 1978 190 (Ref Zhur. Khim. 1978 Abstr. No. 17B101;Chem. Abs. 1978,89,224 377); (b)A. B. Al'tman I. N. Myakshin V. F. Sukhoverkhov G. V. Romanov and V. P. Spiridonov Doklady Akad.Nauk S.S.S.R. 1978,241,360. 130 (a)A. S. Nazarov V. G. Makotchenko and I. I. Yakovlev Zhur. neorg. Khim. 1978,23,621;(b)Yu. I. Nikonorov and L. L. Gornostaev 5-Z Vses. Simpoz. Po Khimii Neorgan. Ftoridov. Dnepropetrovsk 1978 206 (Ref. Zhur. Khim. 1978 Abstr. No. 15V66; Chem. Abs. 1978,89 208 379). 13' M. Drifford R. Rousson and J. M. Weulersse Canad. J. Phys. 1978 56 1353. 132 (a)C. Gheorghiou P. N. Brier J. G. Baker and S. R. Jones J. Mol. Spectroscopy 1978,72,282;(6)F. Truchetet R. Jurek and J. Chanussot Canad. J. Phys. 1978,56,601. 133 D. Meixner A. Heintz and R. N. Lichtenthaler Ber. Bunsengesellschuft phys. Chem. 1978,82 220. 134 H. Selig W. A. Sunder M. J. Vasile F. A. Stevie and P. K. Gallagher J.Huorine Chem. 1978,12,397. The Typical Elements Few organic derivatives of interhalogen compounds have been prepared.A few organo-iodine pentafluorides are known but no stable species had been obtained until the recent preparation of periodinane (20) in which stability is ascribed to the H 3cuj" 0 '3' CF3 (20) influence of the five-membered ring.13' This opens up the possibility of the existence of a whole new area of iodine pentafluoride chemistry. Oxyfluoro-compounds of bromine have been reviewed.136 High-resolution spectra and oxygen and bromine isotope shifts for gaseous and matrix-isolated BrF02 have been obtained and thermodynamic properties of BrFOz and ClF02 have been computed.'37" The vibrational spectrum and X-ray and neutron-diffraction data for C1F02 in the solid state have also been obtained.137b 1.r.spectra of gaseous solid and matrix-isolated BrF30 and Raman spectra of solid and liquid BrF30 and its solutions in HF and C1F03 have been interpreted in terms of a pseudo-trigonal-biypramidalstructure of C symmetry and vibrational and n.m.r. data show that in the liquid and solid states there is association through the axial fluorine atoms.138 Improved syntheses of BrF40- and IF40- salts have been developed and their vibrational spectra have been more reliably assigned. The new assignments are supported by normal-co-ordinate analysis and have been compared with those of structurally related species.139 Perchloryl fluoride has been the centre of considerable attention. A new high- resolution Raman spectrum has been ~btained.'~'" Temperature-dependence studies of the 19F n.m.r.lineshape and spin-lattice relaxation time have produced data on reorientation of the solid.'40b The solubility of C103F in water has been measured. It has also been shown that slow reaction occurs to give C104- F- and H'. Rate laws and rate constants for the reactions of ClO,F with I- OH- and NH have been obtained. 1.r. spectroscopy has shown that an incongruently melting compound formed by the reaction of HF with HClO contains HClO linked to an (HF) polymer through weak hydrogen bonds and that some of this species is retained in the liquid.'40d The reaction of C103F with NH,OH at temperatures between -70 and -20°C in EtOH gives rise to (NH,OH)F and the unstable (NH30H)C103 which decomposes to give (NH30H)N03 and C103.140e 13' R. L. Amey and J. C. Martin J. Amer. Chem. Soc. 1978 100 300. 136 R. J. Gillespie and P. H. Spekkens Israel J. Chem. 1978 17 11. 13' (a)K. 0.Christe E. C. Curtis and E. Jacob Inorg. Chem. 1978,17,2744;(6)G. Tantot P. Joubert and R. Bougon Canad. J. Chem. 1978,56 1634. 13* K. 0.Christe E. C. Curtis and R. Bougon Inorg. Chem. 1978 17 1533. 139 K. 0.Christe R. D. Wilson E. C. Curtis W. Kuhlmann and W. Sawodny Inorg. Chem. 1978,17,533. 140 (a) W. F. Murphy and H. Katz J. Raman Spectroscopy 1978,7,76; (b)J. A. Ripmeester S.K. Garg and D. W. Davidson J. Chem. Phys. 1978,69,2265;(c) G. H. Cady J. Fluorine Chem. 1978,11,225;(d)C. Belin and J. Potier Canad. J. Chem. 1978 56 1610; (e)K. V. Titova E.I. Kolmakova and V. Ya. Rosolovskii Zhur. neorg. Khim. 1978,23 1146. 256 F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway Reactions of IF50 with SbF and AsF5 have been investigated by low-temperature 19 F n.m.r. and Raman spectroscopy which have shown that IF50 is bound to AsF, SbF5 or (SbF,) through its 0~ygen.l~~ Vibrational spectra of I(OCOCF,) in the gas phase solid state and in solution in MeCN have been described. 14' The novel compounds FI(OTeF,) and I(OTeF5) have been prepared and have square-pyramidal structures. Dissolution of I(OTeF5)5 in IF5 gives exchange products belonging to F I(OTeF5)5- series. Similar selenium derivatives have also been prepared. lo6 Standard enthalpies of formation of ClNO, Cl20 and C10 have been and the reaction of C102 with S'" has been studied in phosphate and borate buffer solutions in the pH range 8-13.'43b Raman spectra of BrOS02F solutions of BrOSO'F in S205F2 and BrOS0,F solutions of alkali-metal fluorosulphates are indicative of complex formation in the fluorosulphate solutions and various associations of solute and solvent in the rest.144a The synthesis and physical properties of IS02- salts have been reported and an X-ray diffraction study on (PPh3Bz)(IS02) has shown that the structure contains pyramidal ISOz-. 1446 Perchlorate esters are hazardous and structural information is therefore limited. However an X-ray study on p-MeC,H4S02CH20C103 has shown that the per- chlorate moiety is covalently linked to the rest of the molecule.'45a The use of optical second-harmonic generation to study solid-state stereochemical problems is recent but it has been used to show that co-ordination of iodine in hydrated sodium periodate is not tetrahedral (i.e.NaI04,3H20) but octahedral {i.e. NaH,O[IO,(OH),]) as has been previously suggested on the basis of Raman data. 145b 3 GroupVIII A biblography covering the period 1962-76 146a and an analysis of the literature of noble-gas chemistry 14" have been published. Reactions of organic compounds with xenon fluorides have been authoritatively reviewed.14' Arguments for the possible existence of ESF6 and PaF, based partly on knowledge of noble-gas chemistry have been put forward,148a and the nature of bonding in halogen fluorides and inert-gas compounds has been discussed.14*' The green species long familiar to those who have handled XeF' species under reducing conditions has been identified as Xe2' by u.v. visible and e.s.r. spec- troscopy. This is the first observation of a homonuclear diatomic noble-gas cation in 14' M. Brownstein R. J. Gillespie and J. P. Krasnai Canad. J. Chem. 1978 56 2253. 14* E. Lehmann J. Baumanns and D. Naumann 2.anorg. Chem. 1978,444 145. 143 (a)R. Alqasmi H.-D. Knauth and b. Rohlack Ber. Bunsengesellschaft phys. Chem. 1978 82 217; (6)K. Suzuki and G. Gordon Znorg. Chem. 1978,17,3115. 144 (a)W. M. Johnson and J. W. Macklin Znorg. Chem. 1978,17,2283; (6)P. G. Eller and G. J. Kubas ibid. p. 894. 145 (a)J. B. F. N. Engberts H. Morssink and A. Vos J. Amer. Chem.Soc. 1978,100,799; (b)G. C. Crane and J. G. Bergman Znorg. Chem. 1978 17 1613. 146 (a) D. T. Hawkins W E. Falconer and N. Bartlett 'Noble Gas Compounds A Bibliography 1962-1977' Plenum Press New York 1978; (b) D. T. Hawkins J. Chem. Information and Computer Sciences 1978 20 190. 147 R. Filler Israel J. Chem. 1978 17 71. 148 (a)J. F. Liebman Inorg. Nuclear Chem. Letters 1978,14,245;(b)N. M. Klimenko A. E. Smolyar V. G. Zakzhevskii and 0.P. Charkin 5-Z Vses. Simpoz. Po Khimii Neorgan. Ftoridov. Dnepropetrovsk 1978 137 (Ref. Zhur. Khim. 1978 Abstr. No. 16B42; Chem. Abs. 1978,89 206 635). The Typical Elements 257 a condensed phase. 149a The valence-electron energies of Xe2+ Xe2 and XeF have been calculated using recently developed non-relativistic and relativistic effective core potentials.149b Absorption spectra of MF6-Xe (M= Ir Re W Mo or U) at liquid-nitrogen temperature have shown that charge-transfer interactions occur and have provided information on the exceptionally high electron affinities of the hexafluorides. 149c Absolute rate constants for the ionization of highly excited Xe atoms in collisions with CH31 C7F14 C6F6 and CH3Br have been measured and major charge reaction products identified. 149d The use of noble-gas monofluorides in lasers has generated considerable interest and a large number of publications concerned with neon flu~ride,'~' argon fluoride,lsl krypton fluoride 15163c*152 and xenon and related species have appeared. High-resolution 129Xe F.T. n.m.r. studies have been carried out on a comprehen- sive selection of xenon compounds in a variety of oxidation states.This is one of the first extensive n.m.r. studies on a heavy nucleus and has provided a sensitive probe for assessing the degree of ionic character in the Xe-F bond.lS4 The already known adduct KrFSbF has been prepared from Kr F2 and SbF5 in a glow discharge,155a and the structure of XeFAsF has been shown to consist of fluorine-bridged FXeFAsF5 units. 155b A photoionization mass spectrometric study on KrF2 has yielded a value for AHfo*(KrF2) of 64.94kJ m01-1.156n The pure rotational Raman spectrum of XeF has been observed for the first time and more accurate values of the Xe-F bond lengths have been High-resolution ESCA studies of the 3d 4d and valence-band levels of XeF2 and XeF4 have clarified ambiguities in the assignment of valence levels; accurate measurement of the ligand-field broadening of both 3d and 4d xenon core levels and examination of changes in the 4p structure has been possible.156c (a)L. Stein J. R. Norris A. J. Downs and A. R. Minihan J.C.S. Chem. Comm. 1978 502; (b)W. R. Wadt P. J. Hay and L. R. Kahn J. Chem. Phys. 1978,68 1752; (c)J. D. Webb and E. R. Bernstein J. Amer. Chem. Soc. 1978,100,483; (6) G. F. Hildebrandt F. G. Kellert F. B. Dunning K. A. Smith and R. F. Stebbings J. Chem. Phys. 1978 68 1349. lS0 C. F. Bender and H. F. Schaeffer 111 Chem. Phys. Letters 1978,53 27. 151 (a)C. H. Chen and M. G. Payne Appl. Phys. Letters 1978,32,358;(b)J. H. Kolts and D. W. Setser J.Phys. Chem. 1978,82 1766; (c)J. E. Velazco H. E. Kolts and D. W. Setzer NBSSp~ciulPublication 1978,526 359; (d)C. H. Chen J. P. Judish and M. G. Payne J. Phys. 1978,11B 2189. (a)G. P. Quigley and W. M. Hughes Appl. Phys. Letters 1978,32,649; (b)M. R. Flannery and T. P. Yang ibid.,1978,33 574; (c)A. R. Boate J. R. Morton and K. F. Preston Chem. Phys. Letters 1978 54,579. 153 (a)C. H. Becker P. Casavecchia and Y. T. Lee J. Chem. Phys. 1978,69,2377;(b)H. C. Brashears Jr. and D. W. Setser Appl. Phys. Letters 1978,33,821;(c)C. H. Fisher and R. E. Center J. Chem. Phys. 1978,69,2011;(d)J. G. Eden and R. W. Waynant ibid. 1978,68,2850; (e)D. Kligler H. H. Nakano D. L. Huestis W. K. Bischel R. M. Hill and G. K. Rhodes Appl. Phys. Letters 1978,33 39; (f)P. C. Tellinghuisen J.Tellinghuisen J. A. Coxon J. E. Velazco and D. W. Setser J. Chem. Phys. 1978,68 5187; (g) A. L. Smith and P. C. Kobrinsky J. Mol. Spectroscopy 1978 69 1; (h) L. Andrews Ber. Bunsengesellschuft phys. Chem. 1978 82 65; (i) P. B. Armentrout D. W. Berman and J. L. Beauchamp Chem. Phys. Letters 1978 53 255. 154 G. J. Schrobilgen J. H. Holloway P. Granger and C. Brevard Inorg. Chem. 1978 17 980. lS5 (a)V. D. Klimov V. A. Legasov and S. S. Khoroshev Zhur. fiz. Khirn. 1978,52,1790; (b)A. Zalkin D. L. Ward R. N. Biagioni D. H. Templeton and N. Bartlett Inorg. Chem. 1978 17 1318. 156 (a)J. Berkowitz and J. H. Holloway J.C.S. Furaduy ZZ 1978,74,2077; (b)N. J. Brassington H. G. M. Edwards and D. A. Long ibid.,p. 1208;(c)G. M. Bancroft P. A. Malmquist S.Svensson,E. Basiler U. Gelius and K. Siegbahn Inorg. Chem. 1978 17 1595. F. A. Hart A. G. Massey P. G. Harrison and J. H. Holloway The use of XeF as a selective inorganic fluorinating agent has been briefly reviewed157a and its use in the synthesis of Re(C0)6+Re2Fll- has been demonstrated. 157b Raman spectra of complexes of XeF with MF6 (M = Mo W or U) have been published. 157c The use of XeF2 as a mild fluorinating agent for organic species is well documented 147 and BF,-catalysed regiospecific fluorine addition to 1-substituted pentafluorobenzene using XeF2 has been recently demonstrated. 157d The first xenon(Iv) compound in which xenon is bound only to oxygen has been prepared by the reaction of XeF with B(OTeF,)3 at 0 "C in perfluoro-n-he~ane.',~ The structure of XeF6 continues to be of interest and a detailed Raman study has correlated information on XeF,' Xe2F11+ and tetrameric forms of XeF (i.e.[XeF,+F-],) in solution in HF and wF6.159aThe tetrameric nature of XeF6 in solution has also been confirmed by '*'Xe n.m.r. studies. 154~159b The vapour-phase structure has been calculated by minimization of the repulsion energy between electron pairs by locating the lone pair close to the xenon.159' New xenon(v1) adducts XeF6,2A1F3 XeF6,GaF3 and XeF6,1nF3,160a and mXeF6,MF4 (M = Zr or Hf; rn d 6),1606 have been prepared and their vibrational spectra recorded. On the basis of 12'Xe F.T. n.m.r. data it has been suggested that the Xe-F group in FXeN(S02F) may be oxygen-bridged rather than nitr~gen-bridged.',~ In the meantime the reaction of FXeN(SO,F) with AsF has produced [(F02S),NXe]' [A#,]- which decomposes under dynamic vacuum at 22 "C to give a stable compound formulated as [(FO2S),NXel2F' ASF~-.'~' Is' (a)R.C. Burns I. D. Macleod andT. A. O'Donnell J. Inorg. Nuclear Chem. 1977,39,1737;(b)D. M. Bruce J. H. Holloway and D. R. Russell J.C.S. Dalton 1978 1627; (c) V. K. Ezhov and S. S. Khoroshev Zhur. fiz. Khim. 1978,52,1339;(d)S. StavberandM. Zupan J.C.S. Chem. Comm. 1978 969. Is* D. Lentz and K. Seppelt Angew. Chem. Internat. Edn. 1978 17 356. (a)C.J. Adams and N. Bartlett Israel J. Chem. 1978,17 114; (b)K. Seppelt and N. Bartlett Z. anorg. Chem. 1977,436 122; (c)D. L. Kepert Austral. J. Chem. 1978,31 1917. 160 (a)B. Zemva S. Milicev and J.Slivnik,J.Fluorine Chem. 1978,11,519;(6)B. Zemva S.Milicev and J. Slivnik ibid. p. 545. D. D. DesMarteau J. Arner. Chem. Soc. 1978 100,6270.

ISSN:0308-6003    

DOI:10.1039/PR9787500232

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

9 Transition Elements By F. A. HART and P. THORNTON Department of Chemistry Queen Mary College Mile End Road London El 4NS D. A. RICE Department of Chemistry The University of Reading Whiteknights Reading RG6 2AD PARTI Scandium Yttrium the Lanthanides and the Actinides By F. A. Hart 1 Scandium As is usual very little work has been done on scandium this year. The kinetics of ligand exchange of [SC(OP(OM~),}~]~+ in CD3CN solution have been investigated by n.m.r.' A small number of X-ray crystallographic studies have appeared. Thus Sc2(Se04) has Sc nearly octahedrally co-ordinated to six oxygens (Sc-0 =2.106-2.069 A; 0-Sc-0 = 86.1-95.4°).2 When scandium is heated with ScCl at 940- 960 "C in a sealed Ta container for several weeks Sc5C18 is obtained.Its complicated structure contains two types of chain which are interlinked by bridging chlorine atoms. Both types consist of linear arrays of octahedra each linked to the next octahedron at two adjacent vertices. However one chain consists of chlorine atoms with Sc at the centre of each octahedron while the other type consists of scandium atoms some of which are co-ordinated to C1. The bonded Sc-Sc distance is 3.021 A (other greater distances are also present; Sc-Sc is 3.26A in the metal).3 If the experiment is carried out similarly but at 890-9OO0C Sc7ClI2 is obtained. This contains Sc3' ions and sc6c1123- clusters in which Sc-sc distances of 3.204 and 3.234A are ob~erved.~ The structure of Sc(N03),,2N204 shows it to be (NO')2[Sc(N03)5]2-. The metal ion is 9-co-ordinated to four bidentate and one monodentate nitrate ions5 This must represent almost a maximum co-ordination number for Sc3+ as nitrate ions are typically bidentate towards Class A metal ions on which they often confer their highest co-ordination numbers.2 Yttrium and the Lanthanides Much work this year has again centred on lanthanide complexes. Many of these papers deal with X-ray structural determinations and many others deal with the preparation and characterization of a series of new complexes with some particular ligand. Not all of the compounds so investigated are of first-rate importance in D. L. Pisaniello S.F. Lincoln and E. H. Williams J.C.S. Chem. Comm. 1g78 1047. * J. Valkonen Acta Cryst. 1978 B34,1957. ' K. R. Poeppelmeier and J.D. Corbett J. Amer. Chem. Soc. 1978,100,653. J. D. Jorbett R. L. Daake K. R. Poeppelmeier and D. H. Guthrie J. Amer. Chem. Soc. 1978,100,653. ' C. C. Addison A. J. Greenwood M. J. Haley and N. Logan J.C.S. Chem. Comrn. 1978,580. 259 E A. Hart P. Thornton and D. A. Rice themselves but do make some contribution towards filling in the background details of lanthanide co-ordination chemistry the principal features of which are by now well understood. One area in which considerable progress has been made is organo-lanthanides. It is clear now that a very considerable variety of these compounds can be synthesized. They are usually thermally stable but unstable in air and can have catalytic properties. It is now fairly certain that the gaseous monomeric lanthanide trihalides are in general pyramidal and not planar.Previously i.r. evidence had been conflicting while electric deflection of molecular beams had indicated that lanthanide trifluorides were pyramidaL6 Now the MI3 (M = Pr Nd Gd or Lu) have been studied by electron diffraction at around 1050K giving I-M-I in the range 108-115" and M-I in the range 2.904(Pr)-2.7718 (Lu).' On the theoretical side self-consistent charge extended Huckel calculations on lanthanide trihalides show that the pyramidal configuration has lower energy than the planar. Calculated angles and enthalpy differences compared with the planar configuration are MF3 91-2" 5 eV; MC13 101-5" 1eV; MBr3 99-104" < 1eV; MI3 114-9" < 1eV. The stabilization is considered to arise largely from the non-zero overlap of halogen pz with lanthanide dzzwhich arises only in a non-coplanar situation.' These results will have considerable implications for the teaching of stereochemistry.[Nd{N(SiMe3)2}3]has been shown by X-ray to be pyramidal (N-Nd-N = 117.8°),9 thus confirming earlier X-ray evidence that this series of lanthanide silylamides is pyramidal." When Eu2+ions held in Zeolite A are treated with O2or C12 and the product is submitted to X-ray examination there has apparently been an oxidation to Eu4+; thus in the C1,-treated product there is trigonal bipyramidal co-ordination of Eu to three 0(2.31 A triangular) and to two C1(2.52,2.06 A apical).l**l* The occurrence of Eu4' would be surprising and this interpretation has been que~ti0ned.l~ Lanthanide chlorides are of some catalytic synthetic utility in organic chemistry.Thus MC13 (M =La Ce Nd Er Yb) catalyse the acetalization of a wide variety of aldehydes in yields of 80-100°/~ in the presence of trimethyl ~rthoformate.'~ A variety of a,@-unsaturated ketones are reduced to the corresponding allylic alcohols (without reduction of the C=C double bond) in 65-100% yield by methanolic NaBH in the presence of MC13,6H20 (M = Ce or Sm).I5 Lanthanide shift reagents have still attracted some interesting studies although specialist activity in this field has shown a dramatic decline recently as these reagents have become accepted for routine use. The 'H n.m.r. spectra of [M(thd)3L,] (M =Pr Sm Dy Ho Er or Yb; L = 3-picoline 3,5-lutidine; thd =Me3CCOCHCOCMe3) have been interpreted in terms of biaxial magnetic anisotropy.That magnetic axis which is not defined by the molecular symmetry lies in a similar orientation in all the E. W. Kaiser W. E. Falconer and W. Klemperer J. Chem. Phys. 1972,56,5392. 'N. I. Popenko E. Z. Zasorin V. P. Spiridonov and A. A. Ivanov Znorg. Chim. Actu. 1978,31 L371. C. E. Myers L. J. Norman 11 and L. M. Loew Znorg. Chem. 1978,17 1581. R. A. Andersen D. H. Templeton and A. Zalkin Inorg. Chem. 1978,17,2317. J. S. Ghotra M. B. Hursthouse and A. J. Welch J.C.S.Chem. Comm. 1973,669. R. L. Firor and K. Seff J. Amer. Chem. SOC.,1978,100,976. R. L. Firor and K. Seff J. Arner. Chem. Soc. 1978,100,978. l3 C. K. Jorgensen J. Amer. Chem. SOC.,1978,100,5968.I4 J.-L. Luche and A. L. Gemal J.C.S. Chem. Comm. 1978,976. J.-L.Luche J. Amer. Chem. Soc. 1978,100 2226. Transition Elements 261 compounds.16 This study of a 2 :1 adduct contrasts with results for 1:1adducts of shift reagents which show apparent uniaxial symmetry. 'H n.m.r. has been used to investigate dynamic processes occurring in adducts of Pr(fod) (fod= C3F7COCHCOCMe3) with substituted ethylenediamines and the spectra are inter- preted in terms of four different exchange processes.17 In aqueous solution con- ventional P-diketonate shift reagents cannot be used and it is thus of interest that lanthanide complexes of tetra-p-sulphonatophenylporphinhave been shown to be effective in aqueous solution. The shifts are usefully large for anionic neutral and cationic substrates Tm being the most effective ion.18 In the area of lanthanide complexes which incorporate metal-carbon bonds there have been as mentioned above several interesting papers.All the new compounds of trivalent lanthanides are q1 or bridged alkyls although some also contain qs cyclopentadienyl groups. Most are made by conventional methods usually by reaction of organolithium compounds in THF or ether with suitable lanthanide halogen compounds. The compounds [M(CH2SiMe3)3(THF)2] (M = Er Tb or Yb) are an extension to the lanthanide series of the previously known Sc and Y analogues. Remarkably they are stable in air as solids though very air-sensitive in solution. The anions [M(CH2SiMe3)4]- (M = Y Er Yb) were also obtained as salts of complex Li cations as were the chloro-anions [M{CH(SiMe3)2}3C1]- (M =Er or Yb).The latter Yb compound was X-rayed (Yb-C = 2.372-2.391; Yb-Cl = 2.486 &.I9 The simple hexamethyl anions [MMe6I3- (M = Er or Lu) have also been reported as [Li(tmed),]' salts. The pink and the white crystalline compounds are very sensitive to air and moisture and decompose very slowly at their melting points of 179 and 142 "C." The t-butyl derivatives LiM(C4H9),(THF) (M =Sm n =4 dark gold; M = Er n =4 pink; M = Yb n = 3 red-purple) have been obtained and a know- ledge of their structure would be of interest.'l The structure of the bridged dimethyl [(q5-C5H5)2Y(CH3)2A1Me2] has been established (Y-C-A1 = 80.8",Y-Cmethyl= 2.58 A).'' Some electron-deficient alkyl-bridged organolanthanides are active homogeneous ethylene polymerization catalysts.The doubly methyl-bridged species [{M(q5-C5H4R)2Me}2] (M = Y or Er; R =H Me or SiMe3) polymerise ethylene at 100"C at initial activities of 10-200 g mmol-' h-'. The mechanism of deactivation of the catalyst was in~estigated.'~ These systems may well throw new light on the tradi- tional Ziegler-Natta process. When atomic lanthanide vapour reacts with buta-1,3-diene or 2,3-dimethylbuta- 1,3-diene at -196 "C brown solids are obtained from which unusual compounds have been isolated by extraction with thf. The compounds are M(C4H6) (M = Nd Sm or Er) and M(Me2C4H4) (M = La or Er). They are very unstable to oxidation and hydrolysis. The magnetic moments are approximately as expected for M3+ ions I6 R.E. Cramer and R. B. Maynard J. Magn. Resonance 1978; 31 295. D. F. Evans and G. C. de Villardi J.C.S. Dalton 1978 315. W.de W.Horrocks and E. G. Hove J. Amer. Chem. SOC.,1978,100,4386. J. L.Atwood W. E. Hunter R. D. Rogers J. Holton J. McMeeking R. Pearce andM. F. Lappert J.C.S. Chem. Comm. 1978,140. 'O H. Schumann and J. Miiller Angew. Chem. Internat. Edn. 1978,17,276. A. L. Wayda and W. J. Evans J. Amer. Chem. Soc. 1978,100,7119. " G.R.Scollary Austral. J. Chem. 1978,31,411. 23 D.G.H. Ballard A. Courtis J. Holton J. McMeeking and R. Pearce J.C.S. Chem. Comm. 1978,994. 262 F. A. Hart P. Thornton and D. A. Rice except for the La compound which is pararnagneti~.,~ These compounds should repay further study.A similar method of preparation but using cyclo-octatetraene has given the complexes M,(cot),(thf) (M=La Ce Nd or Er). The interesting structure of the Nd compound shows a sandwich Nd(cot) entity with two adjacent carbon atoms of one ring co-ordinated to the second Nd which itself is also bonded to two THFand a q78-~~t.25 Purple-black Yb(C_CPh) has been made by the action of Hg(C_CPh) on metallic Yb in THF. It is stable at room temperature under N2.26 The organo-analogues (CsH5),Yb(SnPh3)(thf) and (C5H5),Er(MPh3) (M = Ge or Sn) have been characterized. They were prepared by the action of LiMPh on (CSHs)2(Yb,Er)Cl. 27 There has been some activity with the currently fashionable crown polyether and cryptate ligands. The series M(N03)3( 15-crown-5) (M = La-Gd) M(N03),(18- crown-6) (M = La-Nd) and {M(N03)3}4(18-crown-6)3 (M= La-Nd) have been characterized.* The 4 :3 complexes are obtained by heating the 1 1complexes28 and are likely to be [M(N03)2(18-crown-6)]3[M(N03)6].The ‘H and I3C n.m.r. paramagnetic shifts of M(C104)3L adducts with H20and OP(OBu) (where L is an 18-crown-6 ligand having two cyclohexane rings fused in an all-cis manner at the 2,3 and 11,12 positions and M=La Pr or Sm) have been interpreted in terms of a biaxial magnetic anisotropy the conformation of the crown ether and the ligand field of the adding ligands.,’ The first two structures have been reported of lanthanide cryptate complexes. Both involve the same ligand N(C2€&OC2H,+OC2H4)3N. In the first structure [La(Crypt)(NO3),],[La(NO,)6],a La ion within the cryptate is also co-ordinated to two bidentate nitrate groups giving a co-ordination number of 1130 In the second [E~(ClO~)(crypt)](C10~)~,MeCN the smaller Eu ion only allows one bidentate perchlorate group to penetrate between two of the diether chains of the cryptate giving lO-~o-ordination.~~ The papers which deal with the synthesis of new lanthanide complexes amplify the well-known principles that lanthanides complex readily with oxygen or nitrogen donors and that co-ordination numbers vary with the size of the cation as far as the latter information can be deduced without X-ray data.Thus complexes M(NCS)3L (L= 2-picoline N-oxide; M = La-Pr n = 5; M = Nd-Eu n = 4; M = Eu-Lu Y n = 3) exemplify nicely the effect of decreasing radius the co-ordination number presumably decreasing from 8 through 7 to 6.They are non-electrolytes in aceto- nitrile.32 A somewhat related series M(3-picoline N-o~ide)~(PF~)~ (M = La-Lu or Y) shows no similar However complexes with the bidentate donor NNN‘N’-tetramethyladipamide ( = L) seem to show the effect again. They are 24 W. J. Evans S. C. Engerer and A. C. Neville J. Amer. Chem. SOC. 1978,100,331. ” C. W. de Kock S. R. Ely T. E. Hopkins and M. A. Brault Znorg. Chem. 1978,17,625. 26 G. B. Deacon and A. J. Koplick J. Organometallic Chem. 1978 146 C43. ” H. Schumann and M. Cygon J. Organometallic Chem. 1978,144 C43. ’* J.-C. G.Biinzli and D. Wessner Helu. Chim. Acta 1978,61 1454. ’’ G.A. Catton M. E. Harman F. A. Hart G.E. Hawkes and G. P. Moss,J.C.S. Dalton 1978,181. 30 F.A. Hart M. B. Hursthouse K. M. A. Malik and S. Moorhouse J.C.S. Chem. Comm. 1978,549. 31 M. Ciampolini P. Dapporto and N. Nardi J.C.S. Chem. Comm. 1978,788. 32 A. M. P. Felicissimo L. B. Zinner G. Vicentini and K. Zinner J. Znorg. Nuclear Chem. 1978,40,2067. 33 G. Vicentini and W. F. de Giovani J. Znorg. Nuclear Chem. 1978,40 1448. * 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclo-octadecane Transition Elements 263 ML,(PF6)3 (M= La-Nd n =4; M= Sm-Lu Y n = 3) and they are 1:3 elec- A trolytes in a~etonitrile.~~ series of complexes of general formula M(H2L)2X3,nH20 (M =lanthanide X =C1 or Br n = 0-2) has been prepared where H2L is the un-ionized form of the base NN’-ethylenebis(salicy1ideneimine)or related bases3’ Other series which have been prepared and studied are ML4(C104)3 [M=Pr Nd Eu Gd Ho Yb or Lu; L=N-(2-pyridyl)a~etamide]~~ and a wide variety of complexes ML,X3 (M =lanthanide; L =a number of substituted ureas; n = 6 or 8; X =C1 NO3 cia, or NCS).37 On the X-ray crystal structure front Th(No3),,5H2O has now been displaced from its position as the only known example of 11-co-ordination by the arrival of two other examples.La(N03)3,6H20 has the structure [La(N03)3(H20)5],H20 with La-OWater=2.662-2.524 A and La-Onitrate = 2.877-2.622 A. Two of the nitrate groups are unsymmetrically bound giving the rather wide range of interatomic distances The anion [Ce(N03)4(H20)2(4,4’-bipyridyl)]-has been X-rayed as its 4,4’-bipyridinium salt and is 11-co-ordinate only one N of the organic ligand of course being co-ordinated (Ce-Owater =2.501-2.601 A; Ce-Onitrate =2.572-2.769 A;Ce-N = 2.832 K2[Er(N03)5] has been prepared by crystallization from a LiN03-KN03 eutectic and shows an irregular 10-co-ordinate polyhedron with Er-0 = 2.392-2.493 The rather rare cubic 8-co-ordination is shown by [La(2,2’-bipyridyl-NN’-dio~ide)~](ClO,)~.~’ Actinide borohydrides have recently aroused considerable interest and now the structure of the yttrium species [Y(B&),(THF),] has been established.It shows approximately meridianal octa- hedral co-ordination of three THF and three BH groups to Y. The central BH group is bidentate (Y-B=2.68& and the other two are terdentate (Y-B= 2.58 A). The total co-ordination number is thus formally 11 again.The Gd analogue is isostr~ctural.~~ In studies of actinide borohydride complexes co- ordination numbers up to 14 have been reported so the BH group is clearly exceptional in its co-ordination behaviour. In the non-complex area the oxosul- phide Ce,0,S3 has been made by allowing Ce02 and Ce2S3 to react in a NaCl-KCl melt. It is of interest in containing discrete Ce3’ and Ce4’ ions. They are both 8-co-ordinated but are distinguished by their interatomic distances (Ce3’-O = 2.42-2.46 A three bonds; Ce3’-S =2.98-3.05 A five bonds; Ce4’-O =2.17-2.38 A four bonds; Ce4’-S =2.79-3.34 A four 3 Actinides The biggest single area of activity this year has been X-ray crystal structure determination of uranium complexes. No important new principles have been discovered but quite a number of the structures are of some interest and are useful 34 R.Isuyama W. de Oliveira and G. Vicentini J. Znorg. Nuclear Chem. 1978,40 1823. 35 J. I. Bullock and H.-A. Tajmir-Riahi J.C.S. Dalton 1978 36. 36 C.Airoldi F. S. Dias G. F. de SB and J. G. Espinola J. Znorg. Nuclear Chem. 1978,40 1537. 3’ A. Seminara A. Musurneci and A. Chisari J. Znorg. Nuclear Chem. 1978,40,269. 38 B. Eriksson L. 0.Larsson,and L. Nunisto J.C.S. Chem. Comm. 1978,616. 39 M.Bukowska-Strzyzewska and A. Tosik Znorg. Chim. Acta 1978,30 189. 40 E. G.Sherry J. Znorg. Nuclear Chem. 1978,40,257. 41 A. R.Al-Karaghouli R. 0.Day and J. S. Wood Znorg. Chem. 1978,17,3702. 42 B. G. Segal and S. J. Lippard Znorg. Chem. 1978,17,844.43 W. Wichelhaus. Angew. Chem. Internat. Edn. 1978 17,451. 264 F. A. Hart P. Thornton and D. A. Rice in filling in the background of uranium chemistry. Another group of papers (which of course partly overlaps with the X-ray group) deals with the synthesis and charac- terization of new complexes usually with oxygen or nitrogen donors. Progress in organo-actinides has been limited. Some of the more interesting papers do not fit into any of these three groups. A review has appeared with 276 references of actinide complexes with carboxylic New values of AH:ublfor actinide metals and of AH AS,“,and Eofor the M3+ ions have been calculated following consideration of previously published experimental data.45 Turning to experimental papers we consider first those few which deal with metals other than uranium or thorium.The occurrence of the +2 oxidation state has been extended by the preparation of violet CfI by H2 reduction of Cf13 at 560 “C (CfBr is already known). There are two crystalline modifications whose crystal structures deduced from powder photographs are CdC1 and Cd12.46 Americium ions in oxidation states +2 to +6 have been studied in aqueous solution. Their spectra and redox rate constants were determined using pulse radiolysis and streak camera technique^.^^ The kinetics of complexation and dissociation of Am3’ with truns-1,2-diaminocyclohexanetetra-acetateion have been measured by stopped-flow and conventional spectrophotometry. The mechanism of complexation involves a rela- tively long-lived intermediate Am3+,HDCTA3-.48 The actinide borohydride series has been extended by the synthesis of orange Pa(BH4)4 dark green Np(BH4), and blue-black Pu(BH4), by the action of Al(BH4)3 on MF without solvent.These liquids are very volatile [Np(BH4), 10mmHg at 25 0C].49 A few papers deal with the chemistry of uranium in its less usual oxidation states of +3 and +5. When UCl is treated with KCl in acetonitrile-propionic acid and the filtered solution reduced with zinc amalgam a violet-purple crystalline precipitate of K2UC15 is obtained. The NH and Rb analogues were also made. These compounds are remarkable in being stable in dry air and their ready synthesis may make them useful precursors in U3’ chemistry.” In an unusual reaction (Bu~N)~UC~~ was treated with SOC1 for 16 hours and dark yellow Bu4NUCl6 was obtained in 67 ‘/o yield.It appears that the SOCl must have been the ~xidant.’~ A ready synthesis has been reported for P-UF5 and hence by action of sodium ethoxide U(OEt),. The P-UF is made by reducing UF6 with CO in the presence of light COF2 being the other The neutron diffraction of UBrS powder shows it to be of the P-UCl5 type containing octahedral dimer~.’~ In dealingwith compounds of thorium(1v) and uranium-(Iv) and -(vI), we note first the application of UF6 as a useful synthetic oxidant for organic compounds. Thus in 44 U. Casellato P. A. Vigato and M. Vidali Coord. Chem. Rev. 1978,26 85. 4s F. David K. Samhoun R. Guillaumont and N. Edelstein J. Znorg. Nuclear Chem.1978,40,69. 46 J. F. Wild E. K. Hulet R. W. Lougheed W. N. Hayes J. A. Peterson R. L. Fellows and J. P. Young,J. Inorg. Nuclear Chem. 1978 40 811. 47 S. Gordon W. A. Mulac K. H. Smidt R. K. Sjoblom and J. C. Sullivan Znorg. Chem. 1978,17,294. 48 J. C. Sullivan K. L. Nash and G. R. Choppin Znorg. Chem. 1978,17,3374. 49 R. H. Banks N. M. Edelstein R. R. Rietz D. H. Templeton and A. Zalkin J. Amer. Chem. Soc. 1978 100,1957. ” J. Droi&yiiski and D. Miernik Znorg. Chim. Acru 1978,30 185. 51 W. H. Beattie W. B. Maier 11 and R. F. Holland J. Inorg. Nuclear Chem. 1978,40 1885. 52 G. W. Halstead P. G. Eller L. B. Asprey and K. V. Salazar Znorg. Chem. 1978,17 2967. 53 J. H. Levy J. C. Taylor and P. W. Wilson J. Znorg. Nuclear Chem. 1978,40 1055. Transition Elements 265 CC12FCC12F solution methyl ethers may be oxidatively cleaved to give aldehydes in good yield.54 The photoelectron spectra of UO,(acac) and U02(CF3COCH- COCF,) have been obtained and indicate that bonding involving 5f covalency is of major importance in the U02,+ entity.Also 5f orbitals dominate the covalency in Th(a~ac)~ There have been few kinetic papers but the ligand and U(a~ac)~.~~ exchange of U02{OP(NMe2)3}4(C104) has been followed in CD2C12 by n.m.r. line- shape studies. The two-term rate law may indicate simultaneous dissociative and associative mechanism^.^^ There has been little work on organo-actinides but some interesting features have emerged. MC4 (M =Th or U) treated with the pentamethylcyclopentadienyl Grignard reagent give MC12(C5Me5)2 which when treated with LiMe give in turn colourless ThMe2(C5Me5)2 and the orange uranium analogue.The air-sensitive monomeric compounds are both converted into MH,(C,Me,) by treatment with H2 at room temperature. The hydrides are believed to be dimeric; the Th compound is stable but the U compound reversibly loses one H2 molecule per dimer.57 When UC1(C5H5) is treated with Li(CH2)2PPh2 in ether {p-(CH)(CH2)PPh2U(C5H5)2}2 is obtained. In the structure of this compound each U is similarly co-ordinated to two q5-C5H5 groups and a bidentate Ph2P(CH)CH2 group the methine carbon of which also bridges across to the second U atom.58 The compounds M(indenyl),I (M =Th or U) have been prepared by the reaction of MI4 with K indenyl 59 and a variety of complexes of UIV bound to one or two C5H5 and other ligands have been reported for example U(C,H,)Br,(THF) and U(C5H5)C13(dimethylacetamide)2.60 An important series of papers has appeared dealing with the synthesis and crystal structures of the volatile ether complexes of UIVborohydride.The complexes like U(BHs)4 itself are notable for very high co-ordination numbers (up to 14). These arise because the steric requirement of tridentate BH is apparently not very great; thus U(B)I4)4(m)2 is quasi-trans-octahedral all the BH groups being terdentate. Where the H atoms are not located by X-ray terdentate and bidentate BH groups can be distinguished by the U-B Actinide complexes of macrocycles attract continued interest. More details have appeared of the dark blue dioxocyclopentakis( 1-iminoisoindolinato)uranium(vI).This complex obtained by reaction of U02C12 with phthalonitrile in DMF at 170"C has a U02 entity surrounded by a buckled pentagonal ligand [one-fifth subunit (l)]. N\ (1) 54 G. A. Olah and J. Welch J. Amer. Chem.SOC.,1978,100. 5396. 55 I. Fragala G.Condorelli A. Tondello and A. Cassol. Inorg. Chem. 1978 17 3175. 56 G.J. Honan S. F. Lincoln and E. H. Williams Znorg. Chem. 1978,17 1855. 57 J. M. Manriquez P. J. Fagan and T. J. Marks J. Amer. Chem. SOC. 1978,100.3939. '* R. E. Cramer R. B. Maynard and J. W. Gilje J. Amer. Chem. SOC.,1978,100,5563. 59 J. Goffart and G. Duyckaerts Inorg. Nuclear Chem. Letters 1978,14,15. 6o K. W. Bagnall J. Edwards and A. C. Tempest J.C.S.Dalton 1978 295. R. R.Rietz A. Zalkin D. H. Templeton N. M. Edelstein and L. K. Templeton Inorg. Chem. 1978,17 653. R. R.Rietz N. M. Edelstein and H. W. Ruben Znorg. Chem. 1978 17,658. 63 A. Zalkin R. R. Rietz D. H. Templeton and N. M. Edelstein Znorg. Chem. 1978,17 661. 266 F. A. Hart P. Thornton and D. A. Rice Reaction with CuC1 or ZnCl gave ring contraction to copper or zinc phthalo- cyanines. The n.m.r. spectra of the 4-methyl-substituted analogue showed that dynamic interconversion occurs between the different configurations.64 Solids which analyse as crown ether complexes of actinides are not always found by X-ray to contain crown ether co-ordinated to the metal. However the complex [UCl,(~rown)]~[UCl~] (crown = cis,syn,cis-dicyclohexyl-18-crown-6) has the uranium atom in the cation co-ordinated with six crown oxygen atoms (U-O= 2.40-2.68 A) and three chlorines (U-Cl= 2.62-2.66 A).This type of U’” complex shows very large ‘H n.m.r. paramagnetic shifts.65 A number of papers describe the preparation of new but fairly conventional actinide complexes. Exam- ples are (a) Th(N03),(pyridine N-oxide)8 and Th(N03)&3 (L= the N-oxides of 2-picoline 4-picoline lutidine and collidine);66 (b) about 20 complexes of the types (X=C1 or NO,; R =C4H9 to CsH17);67 ThX4(R2S0) and U02X2(R2S0)2 (c) a series of compounds [UO,L,L’] and NEt,[UO,kX] where L = e.g. PhCOCHCOPh; L‘ = DMSO orMeOH; X =C1 Br I NO3 or NCS.68 The complexes U(OOCNEt,) and U(SSCNEt,) have been prepared by reaction of CO or CS with Et,NH and UCl,.69 The remaining work almost half of the total consists of X-ray structural deter- minations of uranium and a few thorium complexes none of which introduce any really novel features of structure or bonding.We here select some of them. Complexes of Th4+and U4+.-The catechol complexes Na4[M(C6&o2)4],2 1H20 (M = Th or U) have similar structures intermediate between dodecahedra1 and square antiprismatic (Th-0 = 2.418 2.421 A; U-0 = 2.362 2.389 The complexes [UX,(OP(NMe,),},] (X = Cl or Br) are almost exactly trans-octahedral with U-Cl= 2.615 U-0 =2.23 A U-0-P = 163O (chloride); U-Br =2.78 U-0 =2.18 A U-0-P = 166O (br~rnide).~~ The U4+/Th4+-NO3-0PMe3 systems allow isolation of a wide variety of complexes and the crystal structures of two of these species 10-co-ordinated [Th(N03)3(OPMe3)4]+ and 12-co-ordinated [Th(N03)5(OPMe3)2]-,have been determined.Other related complexes have been chara~terized.~~ The affinity of the phosphoryl group for actinide ions is further exemplified by [UC13( q5-C5H5)(0PPh3),],THF which is pseudo-octahedral with cis-OPPh3 groups and the CSH5 trans to one of them.73 Bis{NN’-o-phenylene- bis(salicyla1diminato))thorium is a distorted square antiprism with Th-0 = 2.304 2.269A and Th-N=2.65 2.66 The octahedral uranium (v) complex (Ph3PCH2Ph)UC16 has U-CI = 2.500-2.534 A.75 64 T. J. Marks and D. R. Stojakovic J. Amer. Chem. SOC.,1978,100,1695. 65 G. C. de Villardi P. Charpin R.-M. Costes G. Folcher P. Plurien P. Rigny and C. de Rango J.C.S.Chem. Comm. 1978,90. 66 C. E. F. Rickard and D. C. Woollard Inorg. Nuclear Chem. Letters 1978,14,207. 67 B. B. Misra S. R. Moharty N. V. V. S. Murti and S. Raychaudhuri,Inorg. Chim. Acta 1978,28,275. G. Marangoni G. Pavlucci R. Graziani and E. Celon J.C.S. Dalton 1978 1618. 69 F. Calderazzo G. dell’hico R. Netti and M. Pasquali Inorg. Chem. 1978,17,471. 70 S.R. Sofen K. Abu-Dari D. P. Freyberg and K. N. Raymond J. Amer. Chem. SOC.,1978,100,7882. J. G. H. du Preez B. J. Gellatly G. Jackson L. R. Nassimbeni and A. L. Rodgers Znorg. Chim. Acta 1978,27 181. ’* N. W. Alcock S.Esperk K. W. Bagnall and H.-Y. Wang J.C.S. Dalton 1978,638. 73 G. Bombieri G. de Paoli A. Del PrB,and K. W. Bagnall Inorg. Nuclear Chem. Letters. 1978,14,359. 74 R. J. Hill and C.E. F. Rickard J. Imrg. Nuclear Chem. 1978,40,2029. 75 M.R. Caira. J. F. de Wet J. G. H. du Preez and B. J. Gellatly Acta Cryst. 1978 B34 1121. Transition Elements 267 Complexes of U022'.-From the many papers we choose a few of the most instructive or least routine. Li2U04 further illustrates the tendency of U'" to preserve the UO:+ entity even when surrounded by oxide ions. Thus in the approximately octahedral structure (0-U-0 = 80.1-95.7 ") U-O,,yl = 1.92 1.97 and U-OOth, = 2.19 Treatment of aqueous U02(N03)2 with U03gives the rather elegantly symmetrical complex [(U02)30(OH)3(H20)6]N03,4H20, the cation of which has three UOZ2+ groups in an equilateral triangle with the U02 axes perpendicular to the plane of the triangle. An 02-ion lies at the centre of the triangle (U-0 = 2.17 A) and an OH-group bridges each pair of U atoms.The pentagonal bipyramidal co-ordination of each U atom is completed by two water molecules each.77 The quinquedentate nitrogen ligand 2,6-pyridino{C(Me) N.NH(2-pyri- dine)}2 (=L) forms a compound [U02(N03)L]2[U02(N03)4] in which the chief interest is the occurrence of unidentate nitrate groups. These are rare for actinides and this complex has one in each cation (U-0 = 2.48 A) and two in the anion (U-0 = 2.45 A). The other two nitrates in the anion are bidentate (U-0 = 2.52 2.54 A).78 Another example of alternative unidentate-bidentate binding is (NHJ2[U02(HC00)4] in which the pentagonal equatorial co-ordination of the U022+ group is completed by one bidentate formate group (U-0 = 2.54 2.51 A) and three unidentate ones (U-0 = 2.28-2.36 In [{U02(CF3COCH-COCF3)2}3] there is unusual bridging by one uranyl oxygen of each U022+ group which bonds across to the equatorial plane of a neighbouring U022+group.This equatorial plane is for each of the three similar U atoms composed of two bidentate CF3COCHCOCF3 ligands and the bridging uranyl oxygen.8o

ISSN:0308-6003    

DOI:10.1039/PR9787500259

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

Transition Elements Part 11 Groups IVA VA and VIA By D. A. Rice 1 Introduction This review of Groups IVA VA and VIA is in a form attempting a wider and necessarily more superficial coverage of the published material than in recent years. Obviously some selection has to be made and although every attempt has been made to be objective some subjectivity is bound to occur. In arranging the material for each group three basic sub-divisions have been used namely simple compounds (those that do not contain carbon except in ions such as BPb-or Et4N+) co-ordination compounds and organometallic chemistry. General reviews containing material relating to Groups IVA VA and VIA concern high co-ordination numbers,’ ligand field parameters for the divalent halides,* and the chalcogenide halides3 ’‘E.Gebert H. R. Hoekstra. A. H. Reis jun. and S. W. Peterson,J. Znorg. Nuclear Chem. 1978,40.65. ” M. Aberg Acta Chem. &and (A),1978,32,101. G. Bandoli D. A. Clemente G. Marangoni and G. Paolucci J.C.S. Chem. Comm. 1978,235. ” B. F. Mentzen J.-P. Puaux and H. Sautereau Acta Cryst. 1978 B34,1846. J. C. Taylor A. Ebtrom and C. H. Randall Znorg. Chem. 1978,17,3285. ’ M. G. B. Drew Co-ordination Chem. Rev. 1977,24 179. D. R. Rosseinsky and I. A. Domty Co-ordination Chem. Rev. 1978,25 31. ’D. A. Rice &-ordination Chem. Rev. 1978,25 199. E A. Hart P. Thornton and D. A. Rice 2 GroupIVA Simple Compounds.-Halides. The chemistry of the halides of zirconium has been extended by a new synthetic route to ZrX3 (X = C1 Br or I) involving the reduction of the tetrahalide by the m~nohalide.~ It is claimed this route avoids contamination as seen when zirconium is the reductant.Phase limits for the three halides have been determined [2.94(2)Q C1 Zr Q 3.03(2) (440 "C) 2.87(2)d Br :Zr d 3.23(3) (435 "C) 2.83(5) (775 "C)Q I :Zr Q 3.43(5) (475 "C)]. The previously reported variation in the colour of 'ZrBr3' is attributed to changes in the Zr :Br ratio and the so called a-ZrC13 has been identified as ZrCL4 From zirconium-halogen mixtures at 800-1000 "C samples of Zr12 and ZTC~~.~ have been isolated and shown to be cluster compounds of the type Zr6II2 and (Zr6C112)Cl,.S In the iodide an octahedron of zirconium atoms exists in which each edge is bridged by an iodine atom (1).Also bound exo to each zirconium atom is an I I iodine atom from the edge of another cluster. Thus half the iodine atoms are uniquely associated with one cluster while the others are involved in two clusters. Previous failures to isolate cluster halides of group IVA are attributed to kinetic rather than thermodynamic factors. The AH? (298)of ZrI,(g) (-128.9f6.3 kJ mol-') ZrI,(g) (136.4* 16.7 kJ mol-') and ZrI(g) (402.9f11.7 kJ mol-') have been determined by mass spectrometric techniques.6 The acceptor properties of MCl (M =Zr or C1) have been compared by the measurement of the enthalpy change for the reaction K2MC16(, 2KC1(,,+ MC14(",.7 An unusual structure has been observed for the Zr2F12- ion which consists of two eight co-ordinated zirconium atoms.The co-ordination sphere is built up by sharing of atoms between two monocapped trigonal prisms (2).8 An interesting development has been the use of extended X-ray absorption fine structure (EXAFS)to measure the Ti-Cl distance in TiCI3 [2.22( 1) A]. The authors R. L. Daake and J. D. Corbett Inorg. Chem. 1978,17 1192. J. D.Corbett R. L. Daake K. R. Peoppelmeier andD. H. Guthrie,J. Amer. Chem. Soc. 1978,100,652. P.D. Kleinschmidt D. Cubicciotti and D. L. Hildenbrand,J. Electrochem. Soc. 1978,125,1543. 'G. J. Kipouros and S. N. Flengas Cunud.J. Chem. 1978,56,1549. J. P.Laval R. Papiernik and B. Frit Acra Cryst. 1978,B34,1070. 269 Transition Elements 0 -F -F-Zr-state that their work illustrates the practical use of EXAFS to structural problems.' A review of particular interest to the inorganic chemist describes how TiC14 can accelerate numerous organic reactions and in particular those involving carbon- carbon bond formation." 0x0-anions.0x0-anions of Group IVA receive far less attention than those of the next two groups. A range of tetratitanates Ti4092- have been prepared by the reaction of T12C03 and TiO,; further reaction of the product T12Ti409 with MCl (M = Group IA) has lead to the isolation of a whole range of tetratitanates." Intercalation studies with TiS2 are discussed together with those formed by Group VA chalcogenides (p. 273). Co-ordination Compounds.-Compounds with co-ordination number eight have been studied in a number of contexts.' The photoelectron spectra of Zr(2,4- diketone) complexes have been compared to those of the related square anti- prismatic UIVand ThIV species.l' A nearly dodecahedral ZrOs polyhedron has been found in Zr(C7Hs02)4(CHC13>z.75 [Zr-0 2.17(7) All3 (C7H502=tropolonato).A mixed oxygen-sulphur M04S4(M = Zr or Ti) co-ordination sphere has been found for the NN-dialkylmonothiocarbamates(R,MTC) of type M(R2MTC)4.'4 The n.m.r. spectra of the compounds indicate a cis structure with all the oxygen atoms on one side of the co-ordination sphere. The suggested structure was confirmed for M(Et2MTC)4 (M =Ti or Zr) where both species have a dodecahedral arrangement of donor atoms. l5 J. Reed P. Eisenberger and J. Hastings Inorg. Chem. 1978,17.481. "' T. Mukaiyama Angew.Chem. Internat. Edn. 1977,16 817. '' M.Dion Y. Piffard and M. Tournoux J. Inorg. Nuclear. Chem. 1978,40,917. l2 I. Fragala G. Condorelli A. Tondello and A. Cassol Znorg. Chem. 1978 17 3175. l3 A. R.Davis and F. W. B. Einstein Acta Cryst. 1978 B34 2110. S. L. Hawthorne A. H. Bruder and R. C. Fay Inorg. Chem. 1978,17 2114. W.L.Steffen and R. C. Fay Inorg. Chem. 1978,17 2120. E A. Hart P. Thornton and D. A. Rice The synthesis and stereochemistry of 2,3,7,8,12,13,17,18-octaethylporphinato-peroxotitanium(1v) has been reported.16 The titanium atom is bonded to both oxygen atoms [Ti-0 1.827(4) 1.822(4) A] and n.m.r. studies show the 0,ligand undergoes exchange between two equivalent sites in which it eclipses a pair of nitrogen atoms. A qualitative theoretical model has been proposed to account for the bonding mode adopted by O2in the titanium porphyrin.” Evidence for the formation of five-co-ordinate titanium(1v) in solution has been revealed by n.m.r.measurements on [TiX3(2,4-diketone]. I* The titanium(II1) species [Ti(salen)(THF)12 [ZnCL] is formed when Ti(salen)2C12 reacts with zinc. Metal-metal interaction is proposed as the magnetic moment is p = 0.96 BM. Reaction of the dimer with pyridine gives [Ti(salen)Cl(py)]THF where C1 and py are trans.” Two studies of the six-co-ordinate titanium(II1) are the structure of TiC13(CH30CH2CH20CH2CH20CH3) which is a fac octahedron,20 and TiC12(2,4- diketone),2THF. Organometallic Compounds.-Compounds containing only u-Metal-Ligand Bonds. The kinetics of the dissociation of CH3TiC13 in ethereal solution have been studied and while no energy of activation for Me-Ti bond rupture is given it has been shown that in ethereal solution below 0 “C the decomposition is second order in CH3TiC13 the products being C2H6 and CH3CH0 while above 0°C C2H4 and CH3Cl are formed.” The extension into Group IVA of the phosphorus ylides as synthetic reagents in forming M-C bonds has led to the determination of the crystal structure of (CH30)6Ti2[(CH2)2P(CH3)2]2 (3).23Noteworthy in the structure is the ylide bridge and its asymmetric nature (Ti-C 2.30 and 2.19 A).Me Me /\ Me Me l6 R. Guilard J. M. Latour C. Lecomte J. C. Marchon J. Protas and D. Ripoll Inorg. Chem. 1978,17, 1228. ’’ Y. Ellinger J. M.Latour J. C. Marchon and R. Subra Znorg. Chem.. 1978,17,2024. l8 A. Somogyvari and N. Serpone Canad. J. Chem. 1978,56316. l9 M. Pasquali F. Marchetti A. Landi and C. Floriani,J.C.S. Dalton 1978 545. 2o M. G.B. Drew and J. A. Hutton J.C.S. Dalton 1978 1176. F. L. Bowden and D. Ferguson Inorg. Chim. Acfa..1978,26,251. ’* D. Dong S. C. V. Stevens and J. D. MdJowan Ihrg. Chim. Acta. 1978,29,L225. 23 W.Scharf D. Neugebauer U. Schubert and H. Schmidbaur Angew. Chem. Inrenraf. Edn. 1978,17 601. Transition Elements 271 The chemistry of [Ti(OPh)2C12]2 was studied to ascertain if it had w-bonded PhO groups and thus resembled the formally isoelectronic [Ti(q5-CsHs)2C12].24 It was shown that [Ti(OPh)2C12]2 has cr-bonded PhO groups but from it a number of interesting compounds were isolated namely [Ti(OPh)2(CH2SiMe3)2] [by reaction with Me3SiCH2)2Mg] [Ti(OPh)2Me] (by reaction with Me2Mg).Two hydrides H[Ti(OPh),] (by reaction with two moles of K under Ar) for which a Ti3H ring is postulated and [Ti(OPh)2]2(N2)H where the N2 group symmetrically bridges two Ti atoms were also obtained. A titanium(II1) alkyl Ti{CH(SiMe3)2}3(g = 1.968) is formed when LiCH(SiMe3)2 is allowed to react with either TiC13,2NME3 or TiC14. No reduction takes place with MCI (M=Zr or Hf) MCI{CH(SiMe3)2}3 being formed.25 Ti(C6H4-2-CH2NMe2)2(2,4-diketone) has been isolated from the reaction of TiCI2(2,4-diketone,2THF with LiC6H4-2-CH2NMe2.26 A similar reaction with LiCH2C6H4-2- NMe yielded Ti(CH2C6H4-2-NMe2),(2,4-diketone).Both species are six-co-ordinate. Dibenzyltitanium has been prepared from the reaction of Ti(7 5-CSHs)2(CH2Ph)2 with LiCH2Ph. A similar reaction substituting Ph for CH2Ph led to the formation of TiPh,. Both titanium(I1) compounds show magnetic interaction [p = 0.59 BM (R=Ph) and p =0.83 BM (R =CH2Ph)] the phenyl being polymeric and the benzyl dimeric in benzene Compounds containing the CsHs Fragment. The structure of tetra(cyc1o-pentadieny1)zirconium has been determined and conclusively shown to contain one CT and three T bonded rings.28 The compound being Z~(V~-C~H~)~ (q1-CsH5) is thus formally a twenty electron system however the Zr-C bonds to the pentahupto rings while showing considerable variation are on average of such a length (2.58 A) that it is argued each carbon can be considered to be donating only 0.9 of an electron thus giving an 18 electron shell.The structure of what is claimed to be the first organometallic compound with co-ordinated water [{Ti(q5-CsHs)2(H20)}20]S206 has been determined.29 Studies with M"'(q5-C5H5) (M=Ti or Zr) have been reported. The first zirconium(II1) dinitrogen compound Zr(q -C5H5)2N2{CH(SiMe3)2} has been formed by reducing [Zr(qs- C5Hs)2(C1){CH(SiMe3)2}] with Na-Hg under nitrogen" (cf.ref. 24). The dimeric species [Ti(q5- C5H5)2(pyrazole)2] in which the pyrazole molecules act in a q2mode is formed when the sodium salt of pyrazole is allowed to react with Ti(q5-C5H5)2Cl. The and e.s.r. of the bridged species including that of a trimer cyanuaratotris(bis-q5-cyclopentadienyl)titanium(~~~) have been fully analy~ed.~~ 24 A.Flamini D. J. Cole-Hamilton and G. Wilkinson J.C.S. Daffon 1978,454. 25 G. K. Barker M. F. Lappert and J. A. K. Howard J.C.S. Dalton 1978,734. 26 L. E. Manzer Inorg. Chem. 1978,17 1552. 27 K. H. Thiele A. Roder and W. Morte 2.anorg. Chem. 1978,441 13. R. D. Rogers R. V. Bynum and J. L. Atwood J. Amer. Chem. Soc. 1978,100.5238. 29 U. Thewalt and G. Schleussner,Angew. Chem. Internat. Edn. 1978,17,537. 30 M. J. S. Gynane J. Jeffrey and M. F. Lappert J.C.S. Chem. Cbmm. 1978,34. 31 B. F. Fieselmann and G. D. Stucky Inorg. Chem. 1978,17,2074. 32 B. F. Fieselmann D. N. Hendrickson and G. D. Stucky Inorg. Chem. 1978,17,2078. 33 B. F. Fieselmann D. N. Hendrickson and G.D. Stucky Inorg. Chem. 1978.17 1841. F. A. Hart P. Thornton and D. A. Rice Studies of solution structure and dynamics of M{qSCsMe5)N2}N2(M Ti or Zr) = show that the two terminally bonded nitrogen molecules undergo exchange with dissolved nitrogen.34 Titanium heterocycles are formed when Ti(q5-CsHs)2Ph2 is allowed to react with alkynes the products being indole type compounds with titanium present in the five membered ring (4).35 (4) R' = Ph R2 = SiMe3 or R' = R2 =Ph 3 GroupVA Simple Compounds-Hulides. An interesting development in cluster chemistry is the preparation of mixed tantalum-molybdenum clusters from the reaction of TaCIS-MoCIS with aluminium in NaAIC14-AIC13.36 Three'anions have been charac- terized [(Ta~MOC112)C16]~- and [(T~,MoC~,,)C~~]~-.[(Ta4M02Cl12)C16]2- Oxides and 0x0-anions. The kinetics of the reactions of [v&z8]6-continue to be of considerable interest. The rate of isotopic oxygen exchange is first order in [Vlo028]6- the rate constant being invariant between pH 4.0and 6.3.37The pro- tonation of the same species has been studied by "V n.m.r. spectroscopy and contrary to previous reports the first protonation is suggested to take place at an out of plane apex oxygen atom.38 The decomposition of [v10028]6-in neutral or weakly basic media is dependent on the first power of [Vlo028]6- and of [HVlo029]7-(this later species being formed by OH-attack on de~avanadate).~~ Among other 0x0-anions to be studied are V2074-,whose i.r. and Raman spectra have been p~blished;~' the manganese salt of Ta2062- has columbite structure and its vibrational structure has been e~amined;~' finally five- and six-co-ordinate Ta atoms are found in RbTaO, which is better formulated as being derived from Ta40808/2.42 The molecule V4O10 with the P4OI0 structure has been isolated by matrix techniques thus confirming that the V4010'ion seen in the mass spectrum of V,Os does arise from gaseous v4010.~~ 34 J.M. Manriquez D. R. McAlister E. Rosenberg. A. M. Shiller K. L. Williamson S. I. Chan and J. E. Bercaw J. Amer. Chem. SOC.,1978,100 3078. 35 J. Mattia M. B. Humphrey R. D. Rogers J. L. Atwood and M. D. Rausch Inorg. Chem. 1978 17 3257. 36 J. L.Meyer and R. E. McCarley Inorg. Chem. 1978,17 1867. 37 R.K.Murmann and K. C. Giese Inorg. Chem. 1978,17,1160. 38 0.W.Howarth and M. Jarrold J.C.S. Dalton 1978 503. 39 F.Corigliano and S. dipasquala J.C.S. Dalton 1978 1329. 40 E.J. Baron I. L. Botto J. B. Pedregosa and P. J. Ayminono Monatsh 1978 109,41. 41 E.Husson Compt. rend. 1978,286 377. 42 M. Serafin and R. Hoppe Angew. Chem. Internat. Edn. 1978,17,354. 43 I. R. Beattie J. S. Ogden and D. D. Price Znorg. Chem. 1978 17 3296. Transition Elements Sulphide Sulphido-anions and their Use in Secondary Batteries. The sulphide v2sS has been prepared by the thermal decomposition of (NH4)3VS4. The sulphide contains a VS6 co-ordination sphere and has a disordered CdI ~tructure.~~ The current major research interest in early transition metal layer sulphides is the study of their use as secondary battery cathodes in conjunction with lithium anodes.The cell reaction involves the movement of lithium from the anode to form at the cathode Li,MS2 (M = Ti V Nb or Ta). The drive to find new battery materials has led to the isolation of new dichalcogenides some being formed first as the lithium species Li,MY2 (Y = chalcogenide) (M = IVA or VA metal) and the lithium being removed electrolytically. Two recent reviews provide a comprehensive introduction to the The current range of interests is illustrated by the report of a Li-VSe2 battery47 and a new low temperature route to Group IVA and VA disulphides by the reaction of their halides with M2S (M=Li Na or NI-LJ.48 Co-ordination Compounds.-Halide Adducts. Kinetic studies of the attack of L upon MXS,L (L = R,PO or R3PS M = Nb or Ta X = F or C1) have shown that when X = C1 the reaction is dissociative and first order in NbC15,L while for X = F it is second order and a seven-co-ordinate stage is The n.m.r.spectra and X-ray crystal structure of [NbC13(0CHMe2)2,L] show the metal to be six co-ordinate with the chloride atoms adopting a mer configuration with the ligand L = OP(NMe2)3 trans to an alkoxy-group.sO A useful route to a niobium(II1) chloro adduct is the reduction of niobium(v) chloride with magnesium in CH2C12 containing PMe2Ph. The product [NbC13,2PMe2Ph] is thought to be a chlorine bridged dimer.51 A related tantalum(Ir1) dimer is [(Ta2&),3THT] [X = C1 or Br; THT = tetrahydrothiophene] which is formed by sodium amalgam reduction of the tantalum(v) halide.52 N.q.r.studies have been carried out on the related niobium species and they fully correlate with the X-ray structure of [M2Br6 3THTl (M = Nb or Ta) which consists of two octahedra sharing a face made up of the sulphur atom from one THT molecule and two bromine atoms [Ta-Ta 2.710(2) A Nb-Nb 2.728(5) A] (5).53 44 E. V. Dieman and A. Miiller 2.Anorg. Chem. 1978,444 181. 45 J. Rouvel Recherches 1978 9 274. 46 M. S. Whittingham Progr. Solid-state Chem. 1978 12 41. '' M. S. Whittingham Material Research Bulletin 1978 13 959. 48 R. R. Chianelli and M. B. Dines Inorg. Chem. 1978 17 2758. 49 C. M. P. Favez and A. E. Merbach Helv. Chim. Acta.. 1977,60,2695. '' L. Hubert-Pfalzgraf A. A. Pinkerton and J.G. Riess Inorg. Chem. 1978,17,663. 51 L. Hubert-Pfalzgraf and J. G. Riess Inorg. Chim. Acta. 1978,29 L251. 52 J. L. Templeton and R. E. McCarley Znorg. Chem. 1978,17 2293. 53 J. L. Templeton W. C. Dorman J. C. Clardy and R. E. McCarley Inorg. Chem. 1978 17 1263. F. A. Hart P. Thornton and D. A. Rice with Reduction of [TaC12,2(Me2PCH2CH2PMe2)] [Na{H2Al(OC2H40Me)2}] yielded [Ta{H2Al(O&&OMe)2},2(Me2PCH2CH2PMe2)]2. The product has two tantalum atoms which are bridged by H2Al(OC2H40Me)-p(OC2&OMe)2-Al(OC2H40Me)H2(6).54 (6) R = OC2H40Me Bridging H atoms between Ta and A1 omitted. Compounds with a Nitrogen Co-ordination Sphere. The structure of the potassium salt of [V{H2B(p~)2}3]-has bcen determined and the metal atom is in a slightly distorted six nitrogen octahedral environment.” A five nitrogen environment is seen in (Me2N)3M=NCMe3 (7) (M=Nb or Ta) where the Ta=N distance CMe, I N II Me,N//Ta\NMe NMe (7) [1.77(2) A] is the longest yet recorded.The reaction of (Me2N)3M=NCMe3 with ROH R2C0 and CS2 showed insertion took place into the single bonds with retention of the Ta=N A similar insertion reaction takes place between Ta(NMe2) and C02 to yield Ta(NMe2)2(02CNMe2)3, which is seven-co-ordinate with two bidentate and one monodentate carbamato ligand~.’~ An unusual seven-co-ordinate geometry was found for tri-p-0x0-bis[ 1,5,9,13 tetraphenylporphinatoniobium(v)] where the niobium atoms are above the hetero- cyclic rings and are linked to each other by three bridging oxygen The Nb-0 distances show considerable variation such that each metal atom forms one long one short and one intermediate Nb-0 distance.Reaction of Nb203 (porphyrin)2 with dry HX yields Nb(porphyrin)X3 (X= CI or Br).” Attempts to replace the chloride atoms by H or R groups failed but [Nb-(porphyrin)(MeCOCHCOMe)O] was synthesized from Nb(porphyrin)C13. Compounds with a Group VIB Co-ordination Sphere. The seven-co-ordinate TaS(S2CNEt2) has a distorted pentagonal bipyramidal structure with one of the 54 T. J. McNeese S. S. Wreford and B. M. Foxman J.C.S. Chem. Comm. 1978,500. 55 P. Dapporto F. Mani and C. Mealli Inorg. Chem. 1978,17 1323. 56 W. A.Nugent and R. L. Harlow,J.C.S. Chem. Comm. 1978,579. 57 M. H. Chisholm F.A. Cotton and M. W. Extine Inorg. Chem. 1978,17 2000. ” J. F.Johnson and W. R. Scheidt Inorg. Chem. 1978 17 1280. ” M. L. H. Green and J. J. E. Moreau Inorg. Chim. Am. 1978,31,L461. Transition Elements 275 axial positions filled by the terminally bonded sulphur atom.60 The Ta=S stretching frequency is reported as 905 cm-' which is rather high compared to other reported M=S stretching frequencie~.~ The 2,4-diketone complexes of vanadium still receive considerable attention. The zero field splitting of V(MeCOCHCOMe) is 7.7 cm-1,61 and replacement reactions on V(MeCOCHCOMe)3 (CF3COCHCOCF3 for MeCOCHCOMe) are both first and second order in the fluoro compound62 while rearrangement reactions of V(2,4-diket0ne)~ are intra- rather than inter-m~lecular.~~ OrganometallicCompounds.-Species With a a-Metal-Carbon Bond.A number of vanadium(II1) alkyls and aryls have been isolated. The trimethylsilylmethyl compound V(CH2SiMe3)3 was formed when LiCH2SiMe3 was allowed to react with VCL,.@ The product exhibited no e.s.r. signal and its thermal decomposition is -thought to involve the transient formation of VC(SiMe3)VC(SiMe3).@ The chelating aryl derivative V(C6H4-2CH2NMe2)(Me3CCOCHCOCMe3) has a magnetic moment of 2.75 B.M. indicative of the presence of two unpaired elec- Similar vanadium(II1) compounds VAr3 (Ar= C6H3-2,6-Me2 or C6H2-2,4,6- Me3)65 and VArC12 (Ar = C6H3-2,6-Me2 C6H2-2,4-6-Me3 or C6Me5) were obtained as tetrahydrofuran adducts by arylation of vanadium(II1) chloride with Grignard reagents.66 In the vanadium(1v) species V(C6H2-2,4,6-Me3) the metal atom is in a distorted tetrahedral environment [CVC angles 96.41 to 117.81" V-C distances 2.071(8) to 2.095(7) A].67 A study of the photoelectron spectrum of TaMe has shown four bands below 11.5 eV and the order proposed for the Ta-C molecular orbitals is a; < a; < e' < a:." Alkylidene and Alkylidyne Compounds of Niobium and Tantalum.A number of alkylidene and alkylidyne complexes of niobium and tantalum have been formed by the deprotonation of the cy -carbon atom of an alkyl group bound to the metal. Two related routes involving cationic early transition metal alkyls are shown below LiR AgBF4 [M(V5-C5Hs)2C121-[M(V 5-C5H5)2R21 / -[M(V5-CsHs)&1'BF4-GI{* [M(v '-CSH5)2CH(SiMe3)R] (R = CH2SiMe3; M = Nb or Ta; Ref.69) 6o E. J. Peterson R. B. Van Dreele and T. M. Brown Znorg. Chem. 1978 17 1410. A. K. Gregson D. M. Doddrell and P. C. Healy. Znorg. Chem. 1978 17 1216. 62 A. J. C. Nixon and D. R. Eaton Canad. J. Chem. 1978,56,1012. 63 A. J. C. Nixon and D. R. Eaton Canad. J. Chem. 1978,56,1005. 64 A. K. Bagdasar'yan V. M. Gorelik G. N. Bondarenko and B. A. Dolgoplosk Doklady [English Translation] 1977 236 570. 6s W. Seidel and G. Kreisel 2.anorg. Chem. 1977,435 146. 66 W. Seidel and G. Kreisel 2. anorg. Chem. 1977,435 153. 67 T. Glowiak R. Grobelny B. Jezowska-Trzebiatowska G. Kreisel W. Seidel and E. Uhlig J. Organometallic Chem. 1978 155 39. J. C. Green D. R. Lloyd L. Galyer. K. Mertis and G. Wilkinson.J.C.S. Dalton 1978 1403. F. A. Hart P Thornton and D. A. Rice [T~(V~-C,H~)~(CH~)CH~] (Ref.70.) Spectroscopic studies on the products of the two reactions indicate that the methylene hydrogen atoms of the TaCH2SiMe3 fragment are not equivalent in the n.m.r. and that in Ta=CH2 there is no rotation on the n.m.r. time scale.” Alkylidene compounds have been formed without the C5H5 group being present. From the reaction of Ta(CH2CMe3),C12 with Li(CH2CMe3) the initial product is said to be Ta(CH2CMe3)4CI which by two routes both involving further reaction with Li(CH,CMe,) yields [Ta(CH,CMe,) (CHCMe3)].71 Structural studies on three alkylidene ccmplexes [Ta(q5- C,H,),(CH,Ph)- (CHPh)] [Ta=C 2.07(1) A; Ta=C-Ph angle 135.2(7)”],72 [T~(T~-C~H,)~(C~)- (CHCMe,)] [Ta=C 2.030(6)A; Ta=C-CMe angle 150.4(5)0],3 and [Ta(CHCMe3),(C6H,-2,4,6-Me3),2PMe3] [(Ta=C 1.955(7) to (1.9322(7)A; Ta=C-CMe angles 154.0(6) and 168.9(6)0]74 reveal for the last two compounds surprisingly large angles at the formally sp2 alkylidene carbon atoms and in the later molecule an almost T-shaped geometry is observed.The last structure is that of a bis alkylidene; similar bis alkylidenes are formed by the deprotonation of [M(CH,CMe,>,(CHCMe,)] (M =Nb or Ta) by reaction with L(L =PMe or PMe,Ph) when CMe4 and M(CH2CMe3) (CHCMe3),,L are formed.’ Alkylidyne compounds have been isolated by the deprotonation of an alkylidene. The reaction of [Ta(q5-C,H,)(C1)2CHCMe3] with PMe3/Ph3P=CHMe or Li(CH2CMe)/PMe3 yields [Ta(q5-C5H5)(CI)(CCMe3),2PMe3].76 The structure of [Ta(q’-C,Me,)(C1)(CPh)2PMe3]has been determined [TaGC 1.849(8)A; Ta-C-Ph angle 171.8(6)0].76 (M =V Nb or Ta) and Nb(q6-C6HnMen-6)2(n Studies with M(q5-C5H5),C12 = 6,5 or 3).Synthesis of zero valent bis-areneniobium complexes (arene = C6H6 C6H,Me or C6H3Me3) has been achieved by co-condensing a stream of niobium atoms from an electron gun with the a~ene.~~ Good yields of the paramag- netic compounds were reported and for the methylbenzene derivatives e.s.r. spectra were obtained. Numerous studies have appeared on M(q5-C5H5)2C12. The reaction of Ta(q5-C,H,),CI with RMgCl (R=Pr” Pi Bu” Bus and n-C5H11) gives [Ta(q5- 69 M. F. Lappert and C. R. C. Milne J.C.S. Chem. Comm. 1978,925. 70 R. R.SchrockandP. R. Sharp J. Amer. Chem. SOC.,1978,100,2389. 71 R. R. Schrock and J. D. Fellmann J. Amer. Chem. SOC.,1978,100,3359. 72 R. R. Schrock L. W. Messerle C. D. Wood and L. J. Guggenberger.J. Amer. Chem. Soc. 1978,100 3793. 73 M. R. Churchill and F. J. Hollander Znorg. Chem. 1978,17 1957. M. R. Churchill and W. J. Youngs J.C.S. Chem. Comm. 1978,1048. J. D.Fellmann G. A. Rupprecht C. D. Wood and R. R. Schrock. J. Amer. Chem. Soc. 1978,100 74 75 5964. 76 S.J. McLain C. D. Wood L. W. Messerle R. R. Schrock F. J. Hollander W. J. Youngs and M. R. Churchill J. Amer. Chem. SOC.,1978,100,5962. 77 F.G. N.Cloke M. L. H. Green and D. H. Price J.C.S. Chem. Comm. 1978,431. Transition Elements C,H5)2(alkene)H].7s These compounds are useful starting materials for the synthesis of [Ta(qS-C5Hs)2H3] and the related [Ta(q’-C5H,),(H)PEt3].Studies into the use of V(qS -C,H,)2Clz/AlC12Et mixtures as polymerization catalysts have prompted the synthesis of V(q5-C5H5),R2 by the reactions of V(q5- C,H,),Cl with LiR (R =Et or CHzSiMe3). The compounds so prepared have been characterized by e.s.r. spectroscopy thus their presence or formatiog during poly- merization by V(q 5-C,H5)2Clz/AlC12Et can now be detected. 4 GroupVIA Simple Compounds.-Halide-containing Species. The oxofluoride MoF2O2 has been prepared by the reaction of MoC1202 with anhydrous HF or by fluorination with a stoicheiometric amount of XeF2. The tungsten analogue WF202 was obtained by controlled hydrolysis of WF40.Both compounds on reaction with an excess of XeF yield XeF2MF40 (M=Mo or W).80 The chromium compound CrF202 with N0,F and NOF gives N02CrF30 and NOCrF30 respectively.” The selenofluoride W4Se has been prepared from WF and Sb2Se3 and the W=Se vibration observed at 366 cm-1.82 The structures of [W2F6O4I3- and [W,Fg04]’- have been reported. The former consists of an oxygen bridged dimer [W-W 2.620(2) A] (8)while the latter contains the w304 moiety [W-W 2.514(2) A] (9)” [cf. (lS)]. F / ‘-F \ F OorF For0 (8) (9) CW3F904I3-The mixed wv/wv’ion [w408c18(H20)4]2-consists of a near square planar arrangement of tungsten atoms a bridging oxygen atom being between each metal atom and the whole structure being composed of WC1203,H20 octahedra 0 0’ (10) [W4Ch@s(H20)4l2-0‘=50%0; 50% H20 78 A.H. Klazinga and J. H. Teuben. J. Organometallic Chem. 1978,157,413. 79 A. G. Evans J. C. Evans D. J. C. Espley P. H. Morgan and J. Mortimer J.C.S.Dalton 1978 57. 80 M. J. Atherton and J. H. Holloway J.C.S. Chem. Comm. 1978 254. P. J. Green and G. L. Gard Znorg. Nuclear. Chem. Letters 1978,14 179. 82 M. J. Atherton and J. H. Holloway Znorg. Nuclear. Chem. Letters 1978,14 121. R. Mattes and K. Mennemann 2.anorg. Chem. 1978,437,175. 8d Y. Jeannin J. P. Launay J. Livage and A. Nel Znorg. Chem. 1978,17,374. E A. Hart P.Thornton and D. A. Rice A new type of structure containing three chains of octahedra that share corners is seen in CsCrF (ll).85 I I -1 F I (11) CsCrF4 The cluster Mo4IIl2- has been synthesized by attack of HI on Mo~(O~CM~),~~ and by I2 oxidation of Mo(CO)~I~-.~' The anion consists of an Mo tetrahedron in which there are four Mo-I terminal bonds bridging iodine atoms on five edges of the tetrahedron and twoiodine atoms that each bridge a face.A u~T~(T*)~ ground state is suggested for the Mo2Br6- ion [obtained by HBr attack on Mo2(02CMe),] and thus it has a Mo-Mo bond order of 2.5.86 Reaction of Ph2PCH2CH2PPh2(dppe) with Mo41112-and Mo2Br6- yields [Mo416,2dppe] and [M0,Br,,2dppe],'~ the iatter compound being also obtained from Mo2Br4(PPh3),." The heteronuclear anion MoWC1,H- has the Mo2XsH- structure and by measurement of the i.r. spectrum of the latter and its deuterium analogue Mo-H distances of 1.90 (cation =Rb' X =C1) and 1.93 A (cation =Cs' X =Br) together with Mo-H-Mo angles of 77.6" (cation = Rb') and 78.3" (cation = Cs') were determined.89 Irradiation at 254 nm of Mo2Cls4- has also led to the formation of Mo2ClsH3-.90 Further studies on Mo2Xs4- have included X-ray emission spectroscopic studies on the quadrupole bond (X = Cl)91 and resonance Raman measurements (X = Br) which led to the 18 000 cm-' absorption being assigned to S* +-S.92 y-irradiation of [MO~CI,]CL gave rise to two e.p.r.active materials [Mo,CI,]~' and [Mo~CI,]~' to which A and T ground states respectively have been assigned.93 A new synthesis of MoC13N [from Mo(CO)~ and NCl3I9 and the structure of [MoNC~~,POC~~],~~ have been reported. In the structure the (MoN) ring consists of alternate long [2.150(5) and 2.167(5)A)] and short [1.659(15) and 1.661(5)A] Mo-N bonds.The Oxides and Oxo-anions. The oxide W03- has been used for some time as an electrode material in photoelectrolysis; a recent advance is the use of W03-,F 85 D. Babel and G. Knoke 2.unorg. Chem. 1978,442,151. 86 H. D. Glicksmann and R. A. Walton Znorg. Chem. 1978,17,3197. " S. Stensvad B. J. Helland M. U'. Babich R. A. Jacobson and R. E. McCarley J. Amer. Chem. SOC. 1978,100,6257. S.A.Best T. J. Smith and R. A. Walton Inorg. Chem. 1978 17 99. 89 V. Katovic and R. E. McCarley Znorg. Chem. 1978,17 1268. 90 W. C. Trogler D. K. Erwin G. L. Geoffroy and H. B. Gray J. Amer. Chem. Soc. 1978,100,1160. 91 D. E.Haycock D. S. Urch C.D. Garner I. H. Hillier and G. R. Mitcheson,J.C.S. Chem. Comm. 1978 262. 92 R. J. H. Clark and N. R. D'Urso J. Amer. Chem. SOC.,1978,100,3088. 93 J. F.Gibson and P. 0.W. Meier J. Chem. Res. (S),1978,66. 94 K.Dehnicke U. Weiher and J. Struhle 2.Nuturforsch. 1977 32 1484. 95 J. U.Weiher and K. Dehnicke 2.Nuturforsch. 1977 33 1347. Transition Elements 279 (prepared from KHF and W03) which is more stable than the pure oxide in electrolysis The reaction of Ti(q 5-CsHs)C13 with a[BU"~N]~[H,PW, ,O,,] yields LY [(Bu"),N],[(q5-C5H,)Ti(PW which is the first poly-0x0-anion supported organometallic complex. The ion which is related to the well characterized [PW12040]3- ion the difference being the replacement of [Wv10]4' by [Ti(q- C,HS)l3' has been studied by 170 n.m.r.spectroscopy and a structure Three of the 0x0-anions whose crystal structures have been reported are cS6w11036(which consists of Wo6 octahedra linked by corners to give [(w11036)6-]a layers),98 [(P~As),Mo,~,,H,]~- (which consists of six Moo6 octahedra in a ring with one octahedron sharing a face two sharing corners three sharing edges with two PhAs03 tetrahedra above and below the ring),99 and [HzMo8028]6- (which consists of Moo6 edge sharing octahedra with the hydrogen atoms at two of the apices)."' The many solution studies on 0x0-anions have revealed evidence for [W6024&]4- in the acid polymerization of W042-,101 the base catalysed exchange of oxygen between water and M042- (M=Mo or W),lo2 and the base decomposition of [PW12040]3- [BW12040]'- and [W12040H2]6-.103*104 An 170n.m.r.study of V2W4Ol9"- has shown the vanadium atoms to be cis in the six metal and the [MO,O~,H]~- anion has been synthesized by the reaction of Mo207'- with water.lo6 The chirality of P2M0180626- has been provedlo7 and 'polytungsten Y' shown to be [W10032]4-.108 Sulphides and Sulphido-anions. The disulphides and diselenides of molybdenum have been studied as anode materials in electrochemical solar cells involving couples of the type Fe3'/Fe2' 12/I-.lo9 S-Au-S s 1 ' /s W s/ 'S-Au-S A number of compounds which can be considered to contain MS4,- (M = Mo or W) as a ligand M(WS4) (M = Zn or CO)"~*"' and [Au2(WS4)I2 (the latter containing % C. E. Derrington W. S. Godek C. A.Castro and A. Wold Inorg. Chem. 1978 17,977. 97 R.K. C. Ho and W. G. Klemperer J. Amer. Chem. SOC.,1978,100,6772. 98 K. Okada F. Marumo and S. Iwai Acta Cryst. 1978,34B,50. 99 K. Y. Matsumoto Bull. Chem. SOC.Japan 1978,51,492. loo M. Isobe F. Marumo T. Yamase and T. Ikawa Acta. Cryst. 1978,34B 2728. lol D.L.Keppert and J. H. Kyle J.C.S.Dalton 1978,133. H. von Felten B. Wernli H. Gamsjager and P. Baertshi J.C.S. Dalton 1978 496. Io3 D. L. Keppert and J. H. Kyle J.C.S. Dalton 1978 137. Io4 D. L.Keppert and J. H. Kyle J.C.S. Dalton 1978 1781. lo' W.G.Klemperer and W. Shum J. Amer. Chem. SOC.,1978,100,4891. '06 M. Filowitz W. G. Klemperer and W. Shum J. Amer. Chem. SOC.,1978,100,2580. J. F.Garvey and M. T. Pope Inorg. Chem. 1978,17,1115. log S.C. Termes and M. T. Pope Inorg. Chem. 1978,17,500. '09 H. Tributsch Ber. Bunsengesellschaft Phys. Chem. 1978,82 169. 'lo I.Paulat-Boschen B. Krebs A. Miiller E. Koniger-Ahlborn H. Dornfield and H. Schulz Inorg. Chem. 1978,17,1440. A.Muller N.Mohan and H. Bogye 2. Naturforsch 1978,33 978. F. A. Hart P. Thornton and D. A. Rice Au-S-W-S- Au-S-W-S ring),'" (12) have been the subject of structural studies. An ion containing six S2 units two of which bridge two molybdenum atoms is [(Sz)zMo(Sz)2Mo(S2)2]2-(13) [Mo-Mo 2.827(4)A] this113 and the cluster anion [Mo~(S~)~S]~-~'~ have both been obtained by the reaction of with ammonium polysulphide (synthesis of the latter species also requiring the addition of NH*OH,HCl). In the trinuclear species there is an Mo triangle on each edge of the Mo3triangle is an S2 unit and above the centre of the triangle is an S atom thus giving the MO,(S~)~S moiety seen in some molybdenum chalcogenide halides (14).3 The final compound in this series (W2SsAa),4PPh3 contains a cubic arrangement of W2S8Ag (15).'15 S /I .;/ S I *I2 A.Muller H. Dornfield G. Henkel B. Krebs and M. P. Viegers Angew. Chem. Internat. Edn. 1978 17,52. 'I3 A. Muller W. 0.Nolte and B. Krebs Angew. Chem. Internat. Edn. 1978 17 279. A. Muller S. Sarkar R. G. Bhattacharyya S. Pohl and M. Dartmann Angew Chem. Internat. Edn. 1978,17 534. 'Is A. Muller H. Bogge and E. Kroniger-Ahlborn J.C.S. Chem. Cumm. 1978,739. Transition Elements 28 1 PPh The Chevrel compounds rhombohedra1 ternary molybdenum chalcogenides of the formula (M,Mo6Y8) (Y = S or Se) have been studied because of their super- conductivity.' ' 6,1l7 Co-ordination Chemistry.-In view of the vast amount of material published on the co-ordination compounds in Group VIA only selected topics can be covered.The stereochemistry exhibited by chromium has been reviewed."8 Complexes containing Two Mo Atoms Linked by an Oxygen or Sulphur Bridge. The oxygen atoms in [Mo204(S2CNEt2),] have been successively replaced and the whole series of compounds through to Mo2S4(S2CNEt2) isolated P4S10 being required to form the full sulphur species. The sulphur bridged species can be made to undergo one electron red~ction.''~ The structures of the syn and anti isomers of [Mo,S~(S~C~H,),]~-have Mo=S distances of 2.085(3)-2.129(3) A120 which are longer than the values previously reported for [MO~S~(S,CN(C~H~)~}~] and thus the structure determination of [Mo2S4(S2CNEt2)2] [Mo=S 2.090(3)-2.094(4) All2' was carried out to provide further evidence.Related to the diatom-bridged species is the triply bridged [p-(2-mercapto- ethanolato-SO,)-p-sulphido-bis{oxo-(NN-diethy1dithiocarbamato)molybdenum-(v)}]'~* whose structure has been reported. A trans O=Mo-0-Mo=O unit has been found in M0~0~(2-mercaptopyridine),'~~ and in [Mo203{CH3N-(CH2CH2S)2)21.'24 l6 R. Flickiger R. Baillif and E. Walker Material Research Bulletin 1978 13 743. 11' M. Sargent R. Chevrel C. Rossel and 0.Fischer I. Less-Common Metals 1978 58 179.'18 I. D. Brown Co-ordination Chem. Rev. 1978,26 161. 11' F. A. Schultz V. R. Ott D. S. Rolison D. C. Bravard J. W. McDonald and W. E. Newton Ztiorg. Chem. 1978,17 1758. 120 G. Bunzey and J. H. Enemark Inorg. Chem. 1978,17,682. 12' J. T. Huneke and J. H. Enemark Inorg. Chem. 1978,17 3698. lZ2 J. T. Huneke K. Yamanouchi and J. H. Enemark Znorg. Chem. 1978,17,3695. 12' F. A. Cotton P. E. Fanwick and J. W. Fitch Znorg. Chem. 1978,17 3254. Y. P. Tsao C. J. Fritchie and H. A. Levy J. Amer. Chem. Soc. 1978 100,4089. F. A. Hart P. Thornton and D. A. Rice Macrocyclic Ligand Complexes. The linear form of the Mo203 fragment discussed in the previous section is seen in p-oxo-bis(oxotetrapheny1-phorphinatomolyb-denum(v)} and single crystal e.p.r.studies indicate the unpaired electrons are in the dxyorbitals on the two Mo atoms and there is little interaction between them.125 Two molybdenum compounds containing the 1,5,9,13-tetrathiacyclohexadecane molecule (hd) have been isolated. In one compound {HSMo(hd)},(CF3S03) there is a Mo-S-Mo-S ring in which each sulphur atom belongs to an intact macrocycle co-ordinated in the endo form.lZ6 Also co-ordinated to the molybdenum atom is an SH group (Mo-S 2.486A). An SH group was also found in the monomeric molybdenum(rv) compound [OMoSH(hd)]' in which the ligand co-ordinates in a planar manner.'" Comparable to the O=Mo=SH group is the O=Mo-OH group seen in [OMoOH,2Ph2PCHzCHzPPh2]+. 12' Binding of N2,Other Small Molecules and the N=NR Groups. All aspects of nitrogen fixation up to September 1978 have been comprehensively reviewed.129 Two important areas giving real advances in knowledge into nitrogen fixation research are extended X-ray absorption fine structure-measurements (EXAFS)and studies on Fe-Mo-S cage structures.The feasibility of EXAFS as a tool in molybdenum chemistry was shown by measurements on a whole range of well characterized compounds. It is possible using EXAFS to distinguish between mono- and di-nuclear Mo sites the presence of S compared to 0 as donor atoms and the occurrence or absence of terminal 0x0-groups. 130 With this background the molybdenum-iron protein of Clostridium pasteurianum was in~estigated'~~ and it was shown that in the 'resting' state no Mo=O moieties are present and the molybdenum has a sulphur ligand environ- ment; oxidation produces Mo=O groups.The molybdenum atom is believed to be associated with another metal atom (probably iron) in an Mo-S-Fe cluster. Similar results were obtained with the Mo-Fe cofactor from Azotobacter vinelandii.13' Crystal structures of two molybdenum-iron-sulphur clusters [p-S-(p-SEt),- {(EtSFe)3M~S4}2]3-and [(p-SPh)3{(PhSFe)3MoS4}2]3-133 134 have been reported. They both consist of two Fe3S4Mo cubes linked by a triple sulphur (or SR) bridge (16).Also terminally bound to each Fe atom is an SR group. The main structural difference between the two compounds is in the bridge; for R = Et the bridge consists of an S atom and twQ SEt groups while for R = Ph the bridge consists of three SPh groups.The EXAFS of the cluster with R = Et has been measured and compared to those of an Mo-Fe-pr~tein'~' and a Mo-Fe c~factor.~~* It is asserted while the cluster in its entirety cannot be designated as a direct analogue of a site in nitrogenase it is the closest analogue yet known.133 Cyclic voltammetry on the cluster R = Ph lZ5 R. G. Hayes and W. R. Scheidt Znorg. Chem. 1978,17,1082. lZ6 J. Cragel V. B. Pett M. D. Glick and R. de Simone Znorg. Chem. 1978 17,2885. R. E. Desimore and M. D. Glick Znorg. Chem. 1978,17,3574. lZ8 M. R. Churchill and F. J. Rotella Inorg. Chem. 1978,17,668. lZ9 J. Chatt J. R. Dilworth and R. L. Richards Chem. Rev. 1978,78,589. S. P. Cramer K. 0.Hodgson E. I. Stiefel and W. E. Newton J. Amer. Chem. SOC.,1978,100,2748.13' S. P. Cramer K. 0.Hodgson W. 0.Gillum andL. E. Mortenson,J. Amer. Chem. SOC., 1978,100,3398. 13' S. P. Cramer W. 0.Gillum,K. 0.Hodgson L. E. Mortenson,E. I. Stiefel J. R. Chisnell,W. J. Brill and V. K. Shah J. Amer. Chem. SOC.,1978,100,3814. 133 T. E. Wolff,J. M. Berg C. Warrick K. 0.Hodgson R. H. Holm and R. B. Frankel,J. Amer. Chem. SOC. 1978,100,4630. 12' Transition Elements 283 RSFe S S FeSR (16) (RSFe),Mo(p -SR)Mo(Fe3SR)3 R = Et R‘ absent R=Ph R’=Ph shows redox behaviour which differs from [Fe4S4(SR),I2- but the cluster which has a magnetic moment of 4.1 f0.1 BM exhibits no e.p.r. activity at room The molybdenum(1v) compound MoO(S,CNE~~)~ in CH2C12 solution reversibly binds C2H2. The n.m.r. spectrum of the adduct is consistent with the formation of MoO(S2CNEt2)2C2H2with the C2H2 molecule cis to the Mo=O group.136 The reaction of the same compound with HN gave MOO~(S~CNE~~)~ N2 and NH3 uia,it is suggested the unstable MOO(NH)(S~CNE~~)~.~~~ This suggestion is supported by the reaction of [MOO(S,P(OE~)~}~] with HN3 which does yield a bridging NH group in ~-O-(~-NH)[MOO{SZP(OE~)~}]Z.138 The chemistry of [M(N2)2,2Ph2PCH2CH2PPhz](M =Mo or W) is of con-tinuing interest. A new route to ~~U~S-MO(N~)~,~P~~PCH~CH~PP~~ is by the reduction of molybdenum(v) chloride with Na-Hg in THF solution under N2.13’ Flash photolysis studies (M =W) indicate that the two nitrogen molecules are lost simultaneously but that re-formation of [W(NZ)2,2Ph2PCH2CH2PPh2] is a two-step process.140 The intermediate [W(N2),2PhPCH2CH2PPh] reacts with RX to give [WX(N2R),2PhPCH2CH2PPh]. Indeed the formation of [M(Nz),2Ph2PCH2CH2PPh2] is the rate determining step in the reaction of [M(N2)2,2Ph2PCH2CH2PPh2]with RX being followed by the rapid forma-tion of [M(N2)(RX),2Ph2PCH2CH2PPh2] that rearranges to yield [MX(N2R),2Ph2PCH2CH2PPh2].141 A general route to [MF(N2=CRR),2Ph2-PCH2CH2PPh2](BF4)is by the reaction of [M(N2)2,2Ph2PCH2CH2PPh2] with HBF when [MF(NNH2),2Ph2PCH2CH2PPh,](BF4) is formed which with RCHO or RR‘CO gives the product [MF(Nz= CRR) 2Ph2PCH,CHzPPh2]. 14’ Bis(organodiazenid0) complexes of molybdenum of the type MO(N~R)~(S~CNR~), are formed when Mo02(S2CNR2) is allowed to react with RNHNH,,HCl. Structures of three Mo(NZR)(S2CNRR1) complexes have been reported where R =Ph,14 2-PhN02 and ~arbethoxy.~~~ 134 G.Christou C. D. Garner F. E. Mabbs and T. J. King J.C.S. Chem. Comm. 1978,740. 13’ G. Christou C. D. Garner and F. E. Mabbs Znorg. Chim. Acta. 1978 29 L189. 13‘ E. A. Maatta R. A. D. Wentworth. W. E. Newton J. W. McDonald and G. D. Watt. J. Amer. Chem. SOC.,1978,100 1320. 13’ E. A. Maatta and R. A. Wentworth Znorg. Chem. 1978,17,922. 13* A. W. Edelblut B. L. Haymore and R. A. D. Wentworth,J. Amer. Chem. SOC.,1978,100 2250. 139 T. A. George and M. E. Noble Inorg. Chem. 1978 17 1678. 140 R. J. W. Thomas G. S. Laurence and A. A. Diamantis Znorg. Chim. Acta. 1978 30 L353. 14’ J. Chatt R. A. Head G. J. Leigh and C. J. Pickett J.C.S. Dalton 1978 1638. 14’ M.Hadia Y. Mizobe M. Sato T. Kodama and Y. Uchida J. Amer. Chem. SOC. 1978,100 5740. 143 G. Butler J. Chatt and G. J. Leigh J.C.S. Chem. Comm. 1978 352. 144 G. Butler G. J. Leigh A. R. P. Smith and G. A. Willis Znorg. Chim. Acta. 1978 28 L165. 14’ G. Butler J. Chatt W. Hussain and G. J. Leigh Znorg. Chim. Acta. 1978 30 L287. 284 F. A. Hart P. Thornton and D. A. Rice Simple Adducts of Chlorides. Two adducts of MOC130 namely [MoCI,O(SPP~,)]'~~ which is five-co-ordinating and [MoC~~O(OPP~~)~,~~' have been the subject of X-ray crystal and e.p.r. studies. A cis-0x0 structure has been established for [WC1202,(OPh,)2],'48 and the related compounds WC1,Y (Y = 0,S Se or NC2C15) have been shown capable of selectively monodealkylating chelating ethers the products being RCl and WCl,Y(OCH,CH,OR) (R = alkyl group).'49 A seven-co-ordinate (capped octahedral) geometry has been established for [MoCI,(PM~C~,)~].50 Metal-Metal Bonded Species. Reviews concerned with the discovery of metal-metal bond ~pecies,~~'*~~~ and the chemistry their electronic spectra and photo~hemistry,'~~ of the metal-metal triple bonds formed by molybdenum and have appeared this year. Fundamental studies have included the bond dissociation energy a of Mo2(g) (406*20 kJ m~l-'),'~~ reassignment of the P.E. spectrum of Mo,(O~CH)~,"~ flash kinetic spectra of Mo2(02CCFJ4 involving a u27r4S17rx' triplet configurati~n,'~~ and ab initio calculations on a range of M2(02CH) (M =Cr or Mo) and [M2ClSl4- (M =Cr or Mo) corn pound^.'^^ In view of the recent reviews a detailed coverage of the published material is not merited and only a few selected aspects will be highlighted.Some discussion of halo-metal-metal bonded compounds is in Section (p. 277). Species with Bridging RC02-or MeS0,-Anions. Studies with M2(02CR)4,2L (M = Cr or Mo)"~-'~~ have shown different behaviour between the two metals of the M-M quadruple bond towards the inductive effect of R and the nature of L. Thus the Mo-Mo distance is largely unchanged by variation of R and L'59 while the Cr-Cr bond length does vary with change in R and L;I6' an observation attributed by theoretical studies to a shallow potential function for the Cr-Cr The metal-metal distance in [MoW(O~CCM~,)~] (2.080A) 163 is shorter than the Mo-Mo distance [2.088(1) A] in the analogous molybdenum compound 159 and the molybdenum compounds with bridging CH,SO,- groups are useful starting materi- als for other species containing M024+ core.164 146 C. D. Garner N. C. Howlander F. E. Mabbs P. M. Boormann and T. J. King J.C.S. Dalton 1978 1350. 14' C. D. Garner N. C. Howlander F. E. Mabbs A. T. McPhail and K. D. Onan J.C.S.Dalton 1978,1848. 14' J. F. de Wet M.R. Caira and B. J. Gellatly Acta Cryst. 1978 34B,762. G. W. A. Fowles D. A. Rice and K. J. Shanton J.C.S. Dalton 1978 1658. J. I. Bullock F. W. Parrett M. L. Post and N. J. Taylor J.C.S. Dalton 1978 1536. F. A. Cotton Accounts Chem. Res. 1978,11,225. H. Vahrenkamp Angew. Chem. Internat. Edn. 1978,17 379. IS3 W. C. Trogler and H.B. Gray Accounts Chem. Res. 1978,11,232. lS4 M. H. Chisholm and F. A. Cotton Accounts Chem. Res. 1978 11 356. 155 S. K. Gupta R. M. Atkins and K. A. Gingerich Inorg. Chem. 1978,17 3211. I. H. Hillier C. D. Garner G. R. Mitcheson and M. F. Guest J.C.S. Chem. Comm. 1978,204. lS7 V. M. Miskowski A. J. Twarowski R. H. Fleming G. S. Hammond and D. S. Kliger Znorg. Chem. 1978,17,1056. 15* M. Bernard J. Amer. Chem. Soc. 1978 100 2354. lS9 F. A. Cotton M. W. Extine and L. D. Gage Inorg. Chem. 1978 17 172. 160 F. A. Cotton and G. W. Rice Inorg. Chem. 1978 17 2004. 16' F. A. Cotton M. W. Extine and G. W. Rice Inorg. Chem. 1978 17 176. 16* F. A. Cotton and G. W. Rice Inorg. Chem. 1978,17,688. V. Katovic and R. E. McCarley J. Amer. Chem. SOC.,1978,100 5586.164 E. Hochberg and E. H. Abbott Znorg. Chem. 1978 17 506. 14' Transition Elements 285 Species with a Heterocyclic Bridge. Reaction of [Mo&I~(PE~~)~] with 7-aza- indole (az) yields [Mo,C~,(~Z)~(PE~~)~] where the az ligands symmetrically bridge the Mo unit [Mo-Mo 2.125(1) A]? The sodium derivative of 2-hydroxy-6-methylpyridine (hmp =anion) with M,(0,CCH3) (M =Cr or Mo) and W(CO) gives M,(hmp) (M =Cr Mo or W) in which the ligands bridge two metal atoms (on any one metal atom the co-ordination sphere is two oxygen and two nitrogen atoms) [M-M; 1.889(1)A (Cr); 2.065(1) A (Mo); 2.161(1) A (W); M-M stretch from Raman spectra; 556 cm-' (Cr); 425 cm-'(Mo); 295 c~-'(W)].'~~ In the mixed compound MoW(hmp) the M-M distance is 2.091(1)A and the stretching mode is at 384~m-l.'~~ An interesting variation on the above is the isolation of M2(amp) where amp is the anion derived from 2-amino-6-methylpyridine.The M-M distances [1.870(3)8 (Cr); 2.070(1) A (Mo); 2.164( 1)8 (W)] are appreciably shorter than those in the compar- able M,(hmp) compounds.168 Metal-Metal Bonded Species containing Metal-Carbon Bonds.The reactions of the CH,SiMe3 group lead to the formation of two types of bridge the electron deficient one with CH2SiMe3 as the bridging and the alkylidyne bridge that incorporates CSiMe3.171 The chromium compound [Cr2(CHzSiMe3),(PMe3),1 contains two bridging CH2SiMe3 groups [Cr-Cr2 1007(5)A] that each form one long and one short Cr-C bond and it has been suggested the Cr-Cr bond is bent and suitable d-overlap integrals have been eva1~ated.l~~ The alkylidyne bridged [W2(CSiMe3)2(CH2SiMes)4] has a planar W-C-W-C ring and a W-W distance [2.521(2) 2.549(4); two independent units in cell] indicative of a single bond17' (compare ref.192). By overcoming the considerable difficulties presented by the air and moisture sensitivity of the compounds the structures of [W,(Me)8,(Et,0),]4-and [W,(Me),C18-,,(THF)4]4- have been determined. 17' The W2(Me)8 moiety has D4h symmetry [W-W 2.264(1) A] and the four associated Li cations each bridge three methyl groups and are also bound to an ether molecule. A series of chromium compounds involving chromium-phenyl bonds have been characterized in which the 2-position of the ring is occupied by an oxygen atom that is bonded to a second chromium atom.The anion [Cr,(2-o-C6H4),Br,]"-is formed from LiC6H4-2-OLi and Cr,(O,CMe) [Cr-Cr 1.830(4) Other examples concern phenyls with an alkoxy-group in the 2-position namely Cr,(2-Me0-5-MeC6H4) '74 [Cr-Cr F. A. Cotton D. G. Lay andM. Millar Znorg. Chem. 1978 17 186. 166 F. A. Cotton P. E. Fanwick R. H. Niswander and J. C. Sekutowski J. Amer. Chem. SOC.,1978,100 4725. 167 F. A. Cotton and B. E. Hanson Znorg. Chem. 1978,17,3237. 16' F. A. Cotton R. H. Niswander and J. C. Sekutowski Znorg. Chem. 1978,17,3541. 16' R.A. Anderson R. H. Jones and G. Wilkinson J.C.S. Dalton 1978,446. 170 M. B.Hursthouse K. M. A. Malik and K. D. Sales J.C.S. Dalton 1978 1314. 17' M. H. Chisholm F. A. Cotton M. W. Extine and C.A. Murillo Znorg. Chem. 1978,17,696. 17* D.M. Collins F. A. Cotton S. A. Koch M. Millar and C. Murillo Znorg. Chem. 1978 17 2017. 173 F. A. Cotton and S. A. Koch Znorg. Chem. 1978,17,2021. 174 F.A. Cotton S. A. Koch and M. Millar Znorg. Chem. 1978,17 2084. 286 F. A. Hart P. Thornton and D. A. Rice 1.828(2)A] and Cr2{2,6-(MeO),C6H,}4175 [Cr-Cr 1.847(1) A]; the molybdenum compound of the latter phenyl also being characterized [Mo-Mo 2.064( 1) A]. Reactions of Metal-Metal Bonded Species and their Formation from Mo(NMe2) and The reaction of MO(NM~~)~ CT(NE~~)~. with ROH (R =Me Et Pr' or But) yields [Mo(OR),] 176 and when R =Pr' the product is dimeric and contains two bridging Pr'O groups and a Mo-Mo distance of 2.523(1) A that indicates the presence of a double b0nd.l" The structure of the starting material Mo(NMe,), has virtual DZd symmetry with the MoN unit a near perfect tetrahedron (Mo-N 1.926 A).178 The Mo-NC2 fragment is essentially planar and the P.E.spectra indicates two electrons to be in dX2-,,2orbital with the rest of the d-orbitals being empty. The reaction of CO with Cr(NEt2) gives the chromium(II1) species [Cr2(02CNEt2)4p(NEt2)2] [Cr-Cr 2.948(2) 813 which is paramagnetic and [Cr,p (02CNEt2)4(HNEt2)2] [Cr-Cr 2.384(2) The reaction of Mo,(OR)~ with C02 yields Mo,(OR),(O2COR) (R = Me,Si Me3C Me2CH or Me3CCH2). The structure of the species with R =Me3C consists of four terminally bonded Me,CO groups and two bridging 02COCMe3 fragments [Mo-Mo 2.241( 1)A].*'' Nitric oxide adds to Mo,(OP~')~ to give M02(OPri)6(NO)2 in which the two Mo atoms are bridged by two OPr' groups the Mo-Mo distance is so large [3.355(2) A)]that there can be no metal-metal interaction.lgl The alkoxides Mo~(OR)~ react with C0,1'2 the products being Mo(OR),CO (R =Pr' or Me3CCH2 the Pr' product being tetrameric).All the products readily lose CO and the product formed with Mo,(OBu'), namely Mo,(OBU')~CO easily reverts to the starting material. The structure of Mo,(OBU')~CO contains two molybdenum atoms bridged by two OBu'groups and a CO molecule with each metal atom bound terminally to a further two OBu' groups. The Mo-Mo bond is believed to be a double bond [2.498(1) A]. The first example of two four-co-ordinate molybdenum atoms joined by a triple bond without any bridging groups is (Me3Si0)3(Me2HN)MoM~(Me2HN) (Me,SiO) [Mo-Mo 2.242(1)81],lg3 which is formed by ligand attack on the alkoxide.A Mo=Mo triple bond has been observed in Mo2R2(NMe2) (R =Me)'' while the species having R = Et reacts with two moles of CO to give Mo2(02CNMe2) and thus a Mo-Mo triple bond is transformed into a quadruple bond via reductive elimina- tion. 185 Trinuclear Clusters. The reaction of W(CO)6 with carboxylic acids yields a [W302(0,CR)6]2' unit to which three donor groups (H,O or RCO,-) are co- 17' F. A. Cotton S. A. Koch and M. Millar Inorg. Chem. 1978,17,2087. 176 M. H. Chisholm. W. W. Reichert and P. Thornton J. Amer. Chem. SOC.,1978,100,2744. M. H.Chisholm F. A. Cotton M. W. Extine and W. W. Reichert Inorg.Chem. 1978,17 2944. M. H.Chisholm F. A. Cotton and M. W. Extine Inorg. Chem. 1978,17 1329. M. H.Chisholm F. A. Cotton M. W. Extine and D. C. Rideout Inorg. Chem. 1978,.17,3536. M. H.Chisholm F. A. Cotton M. W. Extine and W. W. Reichert J. Amer. Chem. Soc. 1978,100,1727. M. H.Chisholm F. A. Cotton M. W. Extine and R. L. Kelly J. Amer. Chem. Soc. 1978,100,3354. lS2 M. H. Chisholm R. L. Kelly F. A. Cotton and M. W. Extine J. Amer. Chem. Soc. 1978,100,2256. M. H. Chis!iolm F. A. Cotton M. W. Extine and W. W. Reichert J. Amer. Chem. SOC.,1978,100,153. lS4 M. H.Chisholm F. A. Cotton M. W. Extine and C. A. Murillo Inorg. Chem. 1978,17 2338. lS5 M.H. Chisholm D. A. Haitko and C. A. Murillo J. Amer. Chem. Soc. 1978,100 6262. Transition Elements 287 ordinated (17).186The W302moiety is a trigonal bipyramid the tungsten atoms forming an equilateral triangle of W-W single bonds (average W-W 2.75 A).RR t L Each edge of the triangle is bridged by two RCO groups and as each metal is also co-ordinated to a donor the metal atoms are nine-co-ordinated. A trinuclear molybdenum(1v) cluster [MO~O~(C~O~)~(H~O)~]~-has been isolated from aqueous The Mo304core (18) has Mo-Mo distances [2.486(1) A] indicative of the presence of single bonds. To each metal atom is also bound a chelating C2042-ion and a water molecule. The core of this species forms an interesting contrast with the Mo~(S~)~S fragment (p. 279). 0 0 0 0 \ / \ 0/c-c 7-"\ / \/>O<\Y =H20 M(\o//Mo\/ 0' \/ /h;u\o O' / 0:-c\ 0 186 A.Bino F. A. Cotton Z. Dori S. Koch H. Kuppers M. Millar and J. C. Sekutowski Inurg. Chem. 1978,17,3245. 187 A Bino F.A. Cotton and Z. Dori J. Amer. Chem. Suc. 1978,100 5252. 288 F. A. Hart P. Thornton and D. A. Rice Organometallic Chemistry.-a-Bonded Species. A chromium(r1) alkyl Cr(CH2SiMe3)2 is formed when CrC13 is reduced by Li CH2SiCMe3. The product which is also reported to be formed directly from CrC12 is stable under argon at room temperature for weeks.'" The structure of the chromium(II1) alkyl{Cr[CH(SiMe3)2]3} shows the chromium atom to be 0.3 A above the plane of the three carbon atoms to which it is A unique reaction is that of Mg(CH2SiMe3)2 and MoCl,(THF) in the presence of PMe,.The product MoC~(CH~S~M~~)~(PM~~) [Mo-C 2.110( 16) A] has a pseudo- trigonal bipyramidal structure with C1 and PMe filling the axial The compound reacts with CO to give a diamagnetic Mo" compound [MoC~(CO)~(~~-COCH2SiMe3)(PMe,)],. An interesting series of mixed molyb- denum(I1) methyl-arene species Mo(v~-A~)M~~(PR,)~ was prepared by allowing MoC13(PR3)(THF) to react with an excess of MgMe2 in a mixed arene-THF solvent.190 The bond dissociation enthalpy for M-Me (M =Mo or W) has been determined by calorimetric measurements on M( q5-C5H5)2Me2. The values obtained were 19' 154.7 f4.5kJ mol-' (M= Mo) and 148.2 f4.5 kJ mol-' (M =W) the latter value being useful to compare to values obtained for WMe (156 kJ mol-'). The reaction of LiCH2CMe and WC16 (6 :1molar ratio) in Et20 at 25 "C yielded W(CCMe3)(CH2CMe3)3 a similar product being obtained with MOCI~.'~~ The molybdenum compound was shown to be dimeric while the tungsten compound had a molecular weight 75% of that required by a dimer.These measurements coupled with the results of n.m.r. spectroscopy suggest a dynamic system involving two metal atoms linked by two bridging CCMe3 groups. The tungsten compound forms W(CCMe3) (CHCMe3)(CH2CMe3)(PMe3)2 when it is allowed to react with PMe3. The v(W=C) occurs at 1313( k2) cm-' in W(CCD,)(CO),Br.'93 The crystal structure of Cr(CPh=CMe2) shows the metal to be in a tetrahedral environment with one C-Cr-C angle being 116.2" the rest being 106.2°.'94 Species With C5H5or Arene Ligands. The ability of a range of compounds containing the W(V~-C~H~)~ moiety to activate sp2 and sp3 C-H bonds has been investigated and a series of rules evolved for predicting the regioselectivity of nucleophilic addition on 18-electron organo-transition metal cations containing polyene ligands.195 General studies involving M(q5-C5H5) (M =Mo or W) abound.The structure of the thionitrosyl C~(V~-C,H,)(CO),(NS)'~~.'~~ [N-S 1.551(3)A] has been reported I. F. Gavrilenko N. N. Stefanovskaya E. I. Tinyakova and B. A. Dolgoplosk Doklady (English Edition) 1978 239 155. E. C. Guzman G. Wilkinson J. L. Atwood R. D. Rogers W. E. Hunter and M. J. Zaworotho J.C.S. Chem. Comm. 1978,465. 190 E. Carmona-Guzmann and G. Wilkinson J.C.S. Dalton 1978 1139. 19' J. C. G. Calado A.R. Dias J. A. M. Simones and M. A. V. R. de Silva J.C.S. Chem. Comm. 1978,737. 192 D. N. Clark and R. R. Schrock J. Amer. Chem. SOC.,1978,100,6774. 193 E. 0.Fischer N. Q. Dao and W. R. Wagner Angew. Chem. Internat. Edn. 1978 17 50. lg4 C. J. Cardin D. J. Cardin and A. Roy J.C.S. Chem. Comm. 1978 899. 19' M. L. H. Green Pure Appi. Chem. 1978,50 27. 196 B. W. S. Kolthammer and P. Legzins J. Amer. Chem. SOC., 1978 100 2247. 19' T. J. Goodenough B. W. S. Kolthammer D. Legzdins and J. Trotter J.C.S. Chem. Comm. 1978,1036. Transition Elements and as have those of [Cr2(CO)(q5-C5H5)2(PhC2Ph)2]'98 [Mo2(q5-C5H5)2{(Me02CC2C02Me)HC2H(Me02CC2C02Me)2}].198 two com-The last pounds were obtained by allowing alkynes to react with [M(q5-C5H5) p(CO)2M(qS- CSH5)2] (M=Cr or Mo) and they are of interest as the chromium compound contains the PhC=CPhCPh=CPh chain while the molybdenum species has the RC=CR-CH=CH-CR=CR-CR=CR (R = 02CMe) series.Extensive investigations into the chemistry of Mo(C5H5)J(NO) have given evidence for the existence in solution of Mo(qs-C5H5)(q1-C5H5)I(N0),199 this suggestion being supported by the compound's reactions with RCOOH2" while with RCGCR (R = CF,) and (NC)2C = C(CN)2 Diels-Alder addition takes place to one of the C5H5 rings.2o1 Interesting compounds are those containing the C5H4 group which bridges two metal atoms being pentahapto to one metal and monohapto to the other the compounds are {[(q5-C5H5)p(q5:q'-C5H4)]Mo}2 and {[(q5-C5H5)p(q5: ql- C5H4)]M~H}2.202 Co-condensation of tungsten atoms from an electron gun with C6H6 MeC6H5 or 1,3,5-Me3C6H3 has resulted in the isolation of W(q6-C6H3R3) which are protonated by acids2'

ISSN:0308-6003    

DOI:10.1039/PR9787500267

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

Transition Elements Part 111 Groups VIIA VIIIA and IB By P. Thornton 1 General The Angular Overlap approach to bonding in transition metal compounds has been reviewed] readably and another review2 deals with the method’s applications to d-d spectra and indicates future use in circular dichroism e.s.r. and magnetism. A survey3of ligand field parameters of halides of divalent first row metals exposes many errors hitherto as ‘unscathed as Dorian Gray’. In a review4 of complexes of tertiary phosphines it is said that the role of r-bonding may be overstated in analyses of bond lengths and n.m.r. spectra. The stereochemistry of bis(tridentate) complexes has been predicted from cal- culations of electron pair repulsions the mer-isomers normally being more stable but for ligands with small bites the unsymmetrical fuc-isomer will distort to a rectangular bipyramid or trigonal prism.’ 19’ S.A. R. Knox R. F. D. Stansfield F. G. A. Stone M. J. Winter and P. Woodward,J.C.S. Chem. Comm. 1978,221. 199 M. M. Hunt W. G. Kita B. F. Mann and J. A. McCleverty J.C.S. Dalton 1978,467. *O0 M. M. Hunt W. G. Kita and J. A. McCleverty J.C.S. Dalton 1978 475. M. M. Hunt and J. M. McCleverty J.C.S. Dalton 1978,480. ’02 M. Berry S. G. Davies and M. L. H. Green J.C.S. Chem. Comm. 1978 99. ’03 F. G. N. Cloke M. L. H. Green and G. E. Morris J.C.S. Chem. Comm. 1978,72. J. K. Burdett Adv. Inorg. Chem. Radiochem. 1978,21 113. D. W. Smith Structure and Bonding 1978,35 87. D. R. Rosseinsky and I. A. Dorrity Coord. Chem. Rev. 1978 25 31.R. Mason and D. W. Meek Angew. Chem. Internat. Edn. 1978,17 183. M. C. Favas and D. L. Kepert J.C.S. Dalton 1978,793. F. A. Hart P. Thornton and D. A. Rice A thorough molecular orbital study of electron transfer reactions finds among other conclusions that inner sphere processes can be of two types with smooth electron transfer when a bridging ligand is transferred or a sudden electron jump in which no atom transfer is necessary.6 The electrochemical oxidation of metals provides a convenient route to halides7" or complexes of anionic bidentate oxygen The first solid complexes of the nucleosides uridine and thymidine have been isolated with divalent Mn Fe Co Ni and Cu the former ligand probably co-ordinating through a C=O unit and some- times also the ribose residue but the latter only through the ribose unit,8 (see also refs.72 and 153). 2 Manganese and Rhenium The weakly antiferromagnetic cations [Mn2(tren)2(NCX)2]2' (X = 0 or S) contain trigonal bipyramidal units linked by hydrogen bonds described as 'outer sphere dimers'. The magnetism and complex e.s,.r. spectra of these compounds have been described as has the e.s.r. of Mn-doped [Zn(Me6tren)I]+ whose high value of 0.20 cm-' for D is attributed to the trigonal bipyramidal structure.' A further e.s.r. study of 0 adducts of Mn" porphyrins showed that the 0 co-ordinates in the symmetrical bidentate configuration as O2 -,with the metal in oxidation state 1v.l' The polymeric imidazolate complex [Mn(im)TPP] [TPP = tetraphenylporphyrinate] is believed to contain alternate high- and low-spin Mn"' atoms with long (2.275 A) and short (2.181A) bonds to N(irn)." The antiferromagnetic cations [Mn2L4O2I3+ [L = bipy or phen] gre shown by e.s.r.and magnetochemical measurements to have distinct Mn"' and Mn'" Another report lZc of these e.s.r. spectra is shown"" to contain a Mn" impurity but that paper describes other reactions of these structures and indicates the possibility of such species as photosystem I1 exhibiting tautomerism as in equation (1) 0 0 0 An octahedron of six Re atoms is found13 in the Re6S8 clusters of Cs4Re6S13 and M4Re6Slz [M = Na or K]. These also contain S and S units and are made by 13" the reaction of Re with KRe04 (or ReS2) M2CO3 and S or by 136 the reaction of Re with M2C03 and H2S.The red crystals become black over a period of weeks with no change in the cell parameters possibly by oxidation as an S-S bond break^.'^" J. K. Burdett Inorg. Chem. 1978,17 2537. ' (a)J. J. Habeeb L. Neilson and D. G. Tuck Inorg. Chem. 1978,17,306;(6)J. J. Habeeb D. G. Tuck and F.H.Walters J. Coord. Chem. 1978,8 27. * M. Goodgame and K. W. Johns J.C.S. Dalton 1978 1294. E.J. Laskowski and D. N. Hendrickson Inorg. Chem. 1978,17,457. lo B. M.Hoffman T. Szymanski T. G. Brown and F. Basolo J. Amer. Chem. SOC.,1978,100,7253. l1 J. T. Landrum C. A. Reed K. Hatano and W. R. Scheidt J. Amer. Chem. SOC.,1978,100,3232. (a) S. R. Cooper G. C. Dismukes M. P. Klein andM. Calvin J. Amer. Chem. SOC.,1978,100,7248;(6) M. Inoue Bull.Chem. SOC.Japan 1978,51,1400;(c)M.M.Morrison and D. T. Sawyer Inorg. Chem. 1978 17 333. l3 (a)S. Chen and W. R. Robinson J.C.S. Chem. Comm. 1978,879;(b)M. Spangenberg and W. Bronger Angew. Chem. Internat. Edn. 1978,17 368. Transition Elements 291 3 Iron Ruthenium and Osmium Iron vapour reacts with MeN(PF2) to form [Fe{MeN(PF2)2}4] in which one of the ligands is bidentate giving the iron atom five-co-0rdinati0n.l~ The singlet-quintet spin equilibria of Fe" compounds are becoming more clear. A Mossbauer study of [Fe,Zn(l-,,(2-pic)3]C12-EtOH, [2-pic = 2-picolylamine (1); x 0.151 showed that with more dilute samples the change of spin state occurred at a lower temperature and the slope of the conversion function was less steep the conclusion reached being that the spin change was a cooperative pro~ess.'~ Contrary to earlier reports salts of [Fe(pyim)J2' [pyim = 2-(2-pyridyl)-imidazole (2)] and its benzimidazole analogue do show spin equilibria in solution laser Raman tempera- ture-jump kinetics giving the rates for the forward and reverse processes.QC",-NH2 (1) (2) Comparison with other Fe" spin equilibria shows that steric effects on ligands may hinder the reorganization occurring during the spin change and retard the process. 16a Mossbauer spectra of the benzimidazole analogue indicate that the structure of the lattice changes with temperature.16' A pulsed ultrasonic study of two other complexes showing singlet-quintet equilibria shows that the quintet state is up to 22 cm2 mol-' larger than the singlet and the authors propose that the change in volume determines the rate of spin-state isomerizations.l7 These results agree with crystallographic findings that for Fe'' complexes of sexadentate ligands such as (3) the Fe-N bonds are 0.17 A and the Fe-0 bonds 0.04 8 shorter in the low spin hydrated C1- and NO3- salts than in the high spin PF6- salt.18 -X.CR:N*C2H4.NH.C2H4*NH*C2H4.N: CR*X-(3) X = CH:CMe.O or CCl:CMe.O R = Me (4) X = 0-C6H40 R =H Extended X-ray absorption fine structure (EXAFS) measurements confirm" that at pH 1.2 the chief FeI" aquo species is [(H20)4Fe(g-OH)2Fe(OH2)4]4+, with an Fe-Fe separation of 2.91 A and FeOFe angle of 101". The antiferromagnetic pyridinium salt of the [C13FeOFeC13]2- anion is the first FeI'I complex in which all the non-bridging ligands are monodentate and the first Fe-0-Fe system with tetra- hedral co-ordination of the Fe atoms.The J value of -92 cm-' is similar to that given in other FeOFe complexes which show five- or six-co-ordination.20 The magnetic susceptibilities and Mossbauer spectra of some iron(II1) fluorinated monothio-P- diketonates could only be explained by temperature-dependent crystal field l4 P. L. Timms and R. B. King J.C.S. Chem. Comm. 1978,898. Is P. Gutlich R. Link and H. G. Steinhauser Znorg. Chem. 1978 17 2509. l6 (a) K. A. Reeder E. V. Dose and L. J. Wilson Znorg. Chem. 1978,17,1071;(6)R. L. Martin I. A. G. Roos D. M. L. Goodgame and A. A. S. C. Machado Austral. J. Chem. 1978,31,437.J. K. Beattie R. A. Binstead and R. J. West J. Amer. Chem. SOC.,1978 100 3044. l8 E. Sinn G. Sim E. V. Dose M. F. Tweedle and L. J. Wilson J. Amer. Chem. SOC., 1978,100,3375. 19 T. I. Morrison A. H. Reis G. S. Knapp F. Y. Fradin H. Chen and E. Klippert I.Amer. Chem. SOC. 1978,100,3262. 20 M. G. B. Drew V. McKee. and S. M. Nelson. J.C.S. Dalton. 1978. 80. 292 F. A. Hart P. Thornton and D. A. Rice parameters.21 The magnetic anisotropy of some iron(II1) dithiocarbamates shows that the trigonal distortion parameter has the opposite sign to that previously expected and that it is necessary to include a parameter representing the ratio of the partition functions of the doublet and sextet states.22 Ultrasonic relaxation studies of [Fe(sa12trien)]N03-$H20, (sa12trien= (4)] show that the doublet-sextet relaxation time is shorter than for the Fe" spin equilibria probably because the d5complexes have mixing of states at the crossover points.23 Haem Proteins and Porphyrin Complexes.-The single crystal polarized electronic spectra and the c.d and m.c.d.spectra of oxy- and deoxy-haemoglobin show 7 and 4 transitions respectively between 4000 and 33 000 cm-'. These were correlated with Huckel MO calculations on corresponding [Fe(porphyrin)(imidazole)] complexes.24 There have been many exciting developments in the chemistry of 'picket-fence' porphyrin complexes. In [Fe(TpivPP)(OH2)].tht [TpivPP = (5a); tht = tetrahydro-thiophene] Fe atoms are co-ordinated by the four porphyrin nitrogens a water molecule and one oxygen of a peptide link from a neighbouring picket fence to give a polymeric ~tructure.~~ A footnote to this paper gives the crystallographic result that O2 is monodentate in [Fe(TpivPH)(tht)(02)].2tht,a model for cytochrome P,, camphor hydroxyla~e.~' The full X-ray crystallographic determination of the structure of [Fe(TpivPP) (1-Meim) (02)].&,H6.$( 1-Meim) [1-Meim = l-methyl-imidazole] has been reported (R =0.109).Dioxygen is monodentate but with two crystallographically independent sites for the terminal 0atom the 0-0 distance is given as 1.15 and 1.17 A and the FeOO angle as 133 and 129". The Fe atom is 0.03 8 out of the N plane toward the O2ligand.26 The X-ray determination of the structures of [Fe(TpivPP) (2-Meim)]-EtOH and its O2 adduct provide the first comparison in similar model complexes for oxy- and deoxy-haems.In this complex the O2adduct shows an 0-0distance of 1.22 Aand an FeOO angle of 129",but the Fe atom is 0.086 toward the 2-Meim ligand not the 02.This system is thought to be a good model for the T state of haem~globin.~~ Under some conditions solid R R (5) a; R = o-C6H4"H.C0.CMe3 b; R = o-C~H~.NH.CO.(&~~) 21 M. Das,R. M. Golding and S. E. Livingstone Transition Metal Chem. 1978 3 112. 22 P. Ganguli and V. R. Marathe Znorg. Chem. 1978 17 543. 23 R. A. Binstead J. K. Beattie E. V. Dose M. F. Tweedle and L. J. Wilson J. Amer. Chem. SOC.,1978 100.5609. 24 W. A. Eaton L. K. Hanson P. J. Stephens J. C. Sutherland and J. B. R. Dunn I.Amer. Chem.SOC. 1978,100,4991. " G. B. Jameson W. T. Robinson J. P. Collrnan and T. N. Sorrell Znorg. Chem. 1978 17,858. 26 G. B. Jameson G. A. Rodley W. T. Robinson R. R. Gagne C. A. Reed and J. P. Collman Znorg. Chem. 1978,17,850. 27 G. B. Jameson F. S. Molinaro J. A. Ibers J. P. Collman J. I. Brauman E. Rose and K. S. Suslick J. Amer. Chem. SOC.,1978,100,6769. Transition Elements 293 [Fe(TpivPP)L] complexes [L is a substituted imidazole] show cooperative effects in their reaction with 02,in the manner of haemoglobin.28 Some new picket fence porphyrins have been synthesized. Ligand (5b) contains four pyridine groups and these can co-ordinate another metal atom to give complexes of the pairs of metal atoms Cu-Cu Ni-Ni Ni-Cu Fe"'-Cu Fe"'-Fe"' and Cu-Co"'.The Cu-Cu complex has the e.s.r. spectrum of a triplet state and the Cu-Cu separation derived from the spectrum agrees with that given by a molecular The 'clamshell' biporphyrin (6)has been prepared. Its FeII and Mn'I complexes (7) are magnetically dilute suggesting that the strongly antifer- romagnetic cytochrome oxidase does not have the imidazolate bridge of the model complex. A new ligand contains an imidazolate group which coordinates to a second Fe atom to give a polymeric structure (8). A number of derivatives of this type were made by substitutions at the peptide N atom and in the imidazolate ring in order to vary the strain on the Fe-im bond. This gave different effects on the affinity of the complexes for 0 and C0.30 -?N <:J+HN u \ CO / N-N (N W N* NiN = tetraphenylporphyrinate residue (P4 N u (6) The 'H n.m.r.spectrum of the Fe"' porphyrin complex [Fe(TPP)I] shows this is five-co-ordinate but addition of Me2S0 gives the first high spin six-co-ordinate iron porphyrin. The authors suggest that the behaviour of metalloporphyrins is strongly influenced by non-bonding interactions between the porphyrin and any additional li~ands.~' The oxidation of ascorbic acid by the Fe"' complex [Fe{(4Me-~y)~por}- (hiSt)ZI [(4Me-~y)~por = 5,10,15,20-tetrakis-(4-N-methylpyridyl)porphine] follows the same rate law as oxidation by ferricytochrome c with the process first involving dissociation of one histidine ligand.32 The preparation and structure determinati01-1~~" ofthe complex [Fe(L)(H,O)] (BF4)2 (L= (9)]shows that high spin Fe" can fit into a hole the size of a porphyrin cavity but the larger Mn2' ion cannot.33b *' J.P. Collman J. I. Brauman E. Rose and K. S. Suslick Proc. Nut. Acud. Sci. U.S.A. 1978 75 1052. 29 D. A. Buckingham M. J. Gunter and L. N. Mander J. Amer. Chem. SOC.1978,106,2899. 3" J. Geibel J. Cannon D. Campbell and T. G. Traylor J. Amer. Chem. Soc. 1978 100,3575. 31 M. Zobrist and G. N. La Mar J. Amer. Chem. SOC.,1978,100 1945. 32 J. C. Oxley and D. L. Toppen Inorg. Chem. 1978,17,3119. 33 (a) M. M. Bishop J. Lewis T. D. O'Donoghue P. R. Rsithby and J. N. Ramsden J.C.S. Chem.Comm. 1978 828; (b) M. M. Bishop J. Lewis T. D. O'Donoghue and P. R. Raithby ibid. p. 476. F. A.Hart P. Thornton and D. A. Rice / /\ IY I1 I1 N N / \ Me Me-N 6-d (9) Iron-Sulphur Proteins and Model Complexes.-The m.c.d. spectra of Fe4S4-containing proteins vary with the oxidation state of the cluster but not with the nature of the protein. The authors claim m.c.d. spectra are better able to distinguish Fe2S2 clusters from Fe4S4 clusters than electronic absorption or c.d. The magnetism and e.s.r. and Mossbauer spectra of tetra-alkylammonium salts of the [Fe4S4(SR),I3- anions are similar to those of reduced ferredoxins. The X-ray determination of the structure of the (Et,NMe)' salt shows the Fe4S4 cube has a Dad deformation but is elongated whereas the dianion is compre~sed.~~ Polarography of [Fe4S4(SR)4]6- [R = C2H4C02- or C3H6C02-] gives similar results to ferredoxins suggesting that the presence of a charge close to the Fe4S4 core does not change the redox properties but there are changes when the hydrogen-bonding power of the solvent changes so that hydrogen-bonding needs to be considered in analyses of the chemistry of ferredoxin~.~~ P.J. Stephens A. J. Thomson T. A. Keiderling,J. Rawlings K. K. Rao and D. 0.Hall Proc. Nut. Acad. Sci. USA.,1978,75 5273. 3s E.J. Laskowski R. B. Frankel W. 0.Gillum G. C. Papaefthymiou,J. Renaud J. A. Ibers and R. H. Holm,J. Amer. Chem. Soc. 1978,100 5322. 36 R. Maskiewin and T. C. Bruice J.C.S. Chem. Comm. 1978,703. Transition Elements Synthetic studies of model complexes continue. All combinations of [Fe4)d(YPh)4]2-,[X Y = S Se] have been prepared.37 An X-ray determination shows the X =Se Y = S ion has the expected Fe4Se4 cube so that if Se occurs in Fe proteins it is thought more likely to be in an Fe4Se4 cubic structure than in a cysteine-type The 'H n.m.r.spectrum suggests the Fe4Se4 cube is larger than the Fe4S4 The [Fe4S4(SR)4]2- anions react with electrophiles to give eartial or complete substitution of SR groups by C1 02CMe 02CCF3 or 03SCF3 groups these reactions being relevant to possible roles of these clusters in hydro- genase or nitrogena~e.~' A dramatic advance in our understanding of nitrogenase comes from the syntheses and X-ray characterization of two model complexes (10) in which three sulphur ligands bridge two [Fe3S4(SR),Mo] The physical properties of these complexes have been described the EXAFS of (lOa)"" being similar to that of nitrogenase.(lO)a;X=SEt,Y=S b;X=Y=SPh A welcome development in this area comes from kinetic studies of the oxidation of reduced Fez ferredoxins by various familiar Co"' complexes in order to discover the specific reaction sites and the effects of charged reagents. Positively charged oxidants react at the same single site but this is different from the probably different sites attacked by [C~(acac)~] and [C~(edta)]-.~' Iron Transport Proteins (Siderophores).-Stability constants of FexxK complexes with various catechols have been measured leading to the conclusion that the tricatechol enterobactin the siderophore for Fe in enteric bacteria has a formation constant of at least lo4' for Fe.4'a In contrast to results from hydroxamate-based siderophores electrochemical studies show the enterobactin complex cannot be directly reduced by biological reducing agents and the reduction must proceed by prior hydrolysis of the enter~bactin.~'~ 37 (a) M.A. Bobrik E. J. Laskowski R. W. Johnson W. 0.Gillum J. M. Berg K. 0.Hodgson and R. H. Holm Znorg. Chem. 1978,17 1402; (b)G. Christou B. Ridge and H. N. Rydon J.C.S. Dalton 1978 1423. 38 R. W. Johnson and R. H. Holm J. Amer. Chem. Soc. 1978,100,5338. 39 (a)T. E. Wolff J. M. Berg C. Warrick K. 0.Hodgson R. H. Holm and R. B. Frankel J. Amer. Chem. SOC.,1978 100,4630; (b)G. Christou C. D. Garner and F. E. Mabbs Inorg. Chim. Acta 1978,28 L189; (c) G. Christou C.D. Garner F. E. Mabbs and T. J. King J.C.S. Chem. Comm. 1978 740. 40 F. A. Armstrong and A. G. Sykes J. Amer. Chem. Soc. 1978,100 7710; F. A. Armstrong R. A. Henderson M. G. Segal and A. G. Sykes J.C.S. Chem. Comm. 1978,1102. 41 (a) A. Avdeef S. R. Sofen T. L. Bregante and K..N. Raymond J.Am& Chem. Soc. 1978,100,5362; (b)S.R. Cooper J. V. McArdle and K. N. Raymond Proc. Nut. Acad. Sci. USA. 1978.75 3551. F. A. Hart P. Thornton and D. A. Rice crystal log rap hi^^^" and magnetic and electr~chemical~~~ studies of hydroxamate and thiohydroxamate complexes again show how the replacement of 0by S confers greater stability for Fe" over Fe"'. Ruthenium and Osmium.-Interest in ruthenium chemistry has centred round the ammines especially in polynuclear complexes with mixed oxidation states and in photochemical processes.During the reduction of [Ru(NH3),(py)l3' by [Fe(CN)6I4- a new absorption band at 915 nm was attributed43 to the outer-sphere intervalence transition of the ion pair [Ru"(NH3)5(py).Fe"'(CN)6]-. The photolysis of aqueous [Ru(NH3)J2+ gives substitution of NH by H20 for irradiation of d-d transitions and oxidation to RU"' when excitation is to the charge-transfer-to-solvent (CTTS) state. The ions [Ru(NH3),(H20)J2+ and [R~(en)~]~' were also studied and it was found easier to establish the mechanism here than in phenanthroline complexes where the CTTS bands are obscured by other absorption^.^^" Similar results were for [OS(NH,),(N,),]~' and [OS(NH,),(N,)]~'. Dimeric complexes [Ru2L2]"+ [L is the macrocyclic ligand (11);n = 0-21 have been prepared and physical and chemical studies suggest the complexes contain Ru-Ru bonds without bridging ligand~.~' 4 Cobalt and Rhodium The new binuclear complex (12a) contains a new As3 equilaterally triangular bridging group.Magnetochemical measurements show the presence of one unpaired electron on each Co. An Ni analogue has been prepared.46 Cobalt (11) Compounds.-Ca[Co(edta) (H20)]-4H20contains six-co-ordinate Co in contrast to the seven-co-ordinate FeIrl and Mn" analogues. The five co-ordinating donor atoms of edta are up to 2.23 8 distant from the Co atom; the 'unco-ordinated' 0 atom is 2.72A from Co. The chelate rings adopt unusual conformation^.^^ Chlorine reacts with a Co-containing Na zeolite to give a remarkable Co-C12 complex with a C1-Cl bond length of 2.52 A [cf.1.99 A in C12(g)J.The absence of a 42 (a) K. S. Murray P. J. Newman B. M. Gatehouse and D. Taylor Austral.J. Chem. 1978,31,983;(b) K. Abu-Dari S. R. Cooper and K. N. Raymond Znorg. Chem. 1978 17 3394. 43 J. C. Curtis and T. J. Meyer J. Amer. Chem. SOC. 1978 100 6284. 44 (a) T. Matsubara and P. C. Ford Znorg. Chem. 1978 17 1747; (b)T. Matsubara M. Bergkamp and P. C. Ford ibid.,p. 1604. 45 L. F. Warren and V. L. Goedken J.C.S. Chem. Comm. 1978,909. 46 M. Di Vaira S. Midollini L. Sacconi and F. Zanobini Angew. Chem. Znternat. Edn. 1978,17,676. 47 A. I. Pozhidaev Ya. M. Nesterova T. N. Polynova M. A. Porai-Koshits and V. A. Logvinenko J. StructurulChem. U.S.S.R..1977,lS.329. Transition Elements p p =MeC(CH2PPh2)3 (12)a; M =Co X =As b; M=Ni X=P colour change was taken to show no oxidation to CoT1I had The five- [nnp = Et2NC2H4NHC2H4PPh2], co-ordinate complex [CO(~~~)(NCS)~] known to show a doublet-quartet spin equilibrium changes structure from its high tempera- ture trigonal bipyramidal configuration towards a square pyramidal shape at 120K.49 It is interesting to compare this result with this year's developments in understanding Fe" spin equilibria. Polynuclear Co" complexes continue to fascinate magnetochemists. A new theory of magnetic exchange in high spin Co" dimers has been developed"" and appliedSob to [C0,(4Me-quin)~(O,CPh)~] using measurements of anisotropy of susceptibility. Another five-co-ordinate but trigonal bipyramidal Co" dimer [Co2L6F2] (BF4)2 L I /L F -CO L\ I I \L LL (13) (13),[L = 3,5-dimethylpyrazole] is barely antiferr~magnetic.~~ A heterobimetallic complex (14a) containing Co has been studied.In one reportS2" the Cu atom is given as four-co-ordinate and the Co as six-co-ordinate but in the other reports2' the positions are exchanged. As the magnetic properties fit for low-spin Co" the latter assignment may be correct unless the samples are isomers. The complex is strongly ferromagnetic as Cu" and low-spin Co" have orthogonal magnetic orbitals. In other conditions (not given) a contribution from a CO"~-CU~ configuration is suggested with a claim that conversion to this form is given by heating in vacuum (to an unspecified temperature).s2b An improved synthesis of the picket fence porphyrin complex [Co(TpivPP)] has been found giving the isomer with all the 'pickets' on the same side of the porphyrin.The values of AHeand AS* for the reaction of O2with [Co(TpivPP)(N-Meim] are like those for Co myoglobin and it is suggested that the picket fence affects the 48 V. Subramanian K. Seff and T. Ottersen J. Amer. Chem. SOC.,1978,100,2911. 49 D. Gatteschi C. A. Ghiiardi A. Orlandini and L. Sacconi Inorg. Chem. 1978 17 3023. 50 (a) P.D. W. Boyd M. Gerloch J. H. Harding and R. G. Woolley Proc. Roy. SOC.,1978 A360,161; (b) P. D. W. Boyd J. E. Davies and M. Gerloch ibid. p. 191. 51 J. Reedijk J. C. Jansen H. van Koningsveld and C. G. van Kralingen Znorg. Chem.1978,17 1990. 52 (a) M.Mikuriya H. Okawa S. Kida and I. Ueda Bull. Chem. SOC.Japan 1978,51,2920;(6)0.Kahn R. Claude and H. Coudanne J.C.S. Chem. Comm. 1978 1012. E A. Hart P. Thornton and D. A. Rice (14) a; M = CU(H~O)~, M' =Co or M = CO(H~O)~, M' = Cu b; M =VO M' =Cu(Me0H) solvation of the c~mplex.'~ The new picket fence porphyrin (5b) is reported54 to form only a 1:1complex with Co2+ in which remarkably only the four pyridine rings co-ordinate in contrast to the bimetallic complexes described el~ewhere.~~ Elec-tronic spectral and 'Hn.m.r. relaxation studies on Co bovine carbonic anhydrase show the Co atoms to have pseudotetrahedral co-ordination from one water molecule and three nitrogen donors. Some inhibitors replace the water molecule others form five-co-ordinate com~lexes.~~ Cobalt(II1) Compounds.-The reaction of CN- ions with [(NH3),Co(NCMe)l3' gives the new complex (15).The ligand is easily converted to alanine so this may be a general method for synthesis of amino-acids from nitriles and of labelling a carboxy- group.56 Kinetic studies of Co"' complexes abound. The aquation of trans-[CO(~~)~(NO~)(NCM~)]~+ is accelerated by the addition of 18-crown-6 with which MeCN forms a complex.57o The photochemistry of [Co(NH3),(NCR)l3' [R =Me or Ph] gives a clear demonstration of the variety of products which can be obtained when different transitions are irradiated.57b The reduction of Co"' complexes by Eu" or Cr2+ is accelerated by the addition of 2,4-pyridinedicarboxylicacid which is believed to be reduced to a radical by Eu*+ this radical then reacting with the Co"' complex; for reductions by Cr2+ the active intermediate is a radical bound to Cr'11.57c 53 J.P. Collman,J. I. Brauman K. M. Doxsee T. R. Halbert S. E. Hayes and K. S. Suslick,J. Amer. Chem. SOC., 1978,100,2761. 54 C. M. Elliott J.C.S. Chem. Comm. 1978,399. 55 I. Bertini G. Canti C. Luchinat and A. Scozzafava J. Amer. Chem. SOC., 1978,100,4873. 56 I. I. Creaser S. F. Dyke A. M. Sargeson and P. A. Tucker J.C.S. Chem. Comm. 1978,289. " (a) G.L. Blackmer M. I).Nordyke T. M. Vickrey R. A. Bartsch and R. A. Holwerda Inorg. Chem. 1978,17,3310;(6)A. W.Zanella K. H. Ford and P. C. Ford ibid. p. 1051;(c)Y.-T. Fanchiang J. C.-K. Heh and E. S. Gould ibid. p.1142. Transition Elements The electronic spectra of metal-0 complexes have been reviewed with emphasis on Co'" complexes.58o Raman and i.r. spectra of 0,-and OZ2-bridged binuclear complexes give clear indications of bonding in the 0-0 and Co-0 units,586 as do resonance Raman The i.r. and U.V. spectra of [C~(bipyridylamine)~(O~)] (clod)suggests the amine and 0,'-are each bidentate; it is unusual to find a monomeric Co"' -0,complex in the peroxide form.58d Rbodium.-SCF-Xa-SW calculations on [Rh2(02CH)4] and [Rhz(OzCH)4(H20)2] suggest the Rh-Rh bond is a single one with a short Rh-Rh distance being related to a long Rh-OH bond because the cr and dr Rh-Rh orbitals are antibonding for Rh-OH2.59a During an electrochemical study of various [Rh2(02CR)4] compounds a stable Rh~""' dimer was found.values were correlated with the Taft CT parameter of the R group and the donor power of the 5 Nickel Palladium and Platinum Nickel.-The new binuclear complex (12b) contains the new P3 equilaterally tri- angular bridging group. Magnetochemical measurements show the presence of one unpaired electron per dimer.60 The single crystal e.s.r. spectrum6' of the Nix*" complex [Ni2Brz(napy),]' (BPhJ [napy = 1,8-naphthyridine (16)] shows this to be strongly ferromagnetic with J greater than 300 cm-'. A new Ni" bridged complex (17),containing an equilateral triangle of planar Ni atoms bridged by two S atoms (S-S =2.70 A) has been characterized.62 An X-ray /-I / 'PEt, Et,P Et,P Et,P i.r. and 31P n.m.r. study of [MTMePPh,) (NCS)J complexes [M=Ni Pd or Pt] suggests that for Ni electronic effects require N-co-ordination of NCS- that Pt is S-co-ordinated unless steric effects prevent this but that for Pd steric and electronic '* (a) A.B. P. Lever and H. B. Gray Accounts Chem. Res. 1978,11,348;(6)T.Shibahara and M. Mori Bull. Chem. Soc.Jupan 1978,51,1374;(c) C.G. Barraclough G. A. Lawrance and P. A. Lay Znorg. Chem. 1978,17 3317; (d) W.L.Johnson and J. F. Geldard ibid. p. 1675. 59 (a) J. G. Norman and H. J. Kolari J. Amer. Chem. Soc. 1978,100,791;(b)K. Das,K. M. Kadish and J. L. Bear Znorg. Chem. 1978,17,930. 6o M. Di Vaira C. A. Ghilardi. S. Midollini and L. Sacconi J. Amer. Chem. Soc. 1978 100 2550. A. Bencini D.Gatteschi and L. Sacconi Znorg. Chem.. 1978 17 2670.62 C.A. Ghilardi S.Midollini and L. Sacconi Znarg. Chim. Acra 1978.31. L.431. 300 E A. Hart P. Thornton and D. A. Rice effects are balanced. In solution all 6 isomers of the Pd and Pt compounds were detected with the cis-NCS form predominating for Pd and the trans-mixed form predominating for Pt but in the solid state the Ni complex is trans-N-bonded the Pd complex is trans-S-bonded and the Pt complex is ~is-N-bonded.~~ The polarized single crystal electronic spectrum at 8 K of [Ni( 1,5-diazacyclo- o~tane)~]~+ shows the planar Ni" atom to have about 20% of 4s character in the '3&' orbital.64 X-Ray determination of the structure of the Ni" complex of y-camphor- quinonedioxime (18) shows that the ligand unusually for a dioxime co-ordinates through one N and one 0 atom.65 The thermochromic salts [R,NH~4-.,]z'[NiC14]2- have been described.They change from yellowish octahedral polymers to blue tetrahedral monomers at 70-230 "C higher transition temperatures being given with larger R groups and lower values of n when there are more hydrogen bonds to break.66 Varying the carboxylate anion in aqueous solutions of [Ni(en)3]2'[RC02]z- affects the conformational equilibria of the chelate rings as shown by 'H n.m.r. the anion effects being attributed to H-bonding in ion The X-ray-deter- mined structure of the BPh4- salt (as the 3Me2S0 solvate) shows the cation to have the A66A configuration the configuration of lowest energy but which is rarely found as hydrogen-bonding normally stabilizes other conformation^.^^^ Oxidation of Ni" oligopeptide complexes gives Ni"' species; the authors believe bispeptide Ni'" complexes would form readily to give a relatively stable reservoir of biological oxidizing power.68 Controlled potential electrolysis studies of [Ni(TTP)] led to discussion of electron transport in haem proteins with the conclusion that electron changes in the porphyrin .rr-system were imp~rtant.~~ Ni and Cu complexes of porphyrins have been prepared in which a nitrene unit is inserted between one pyrrole nitrogen and the metal; the X-ray-determined structure of the Ni complex shows the Ni to be out of the N4 porphyrin plane by 0.21 A with the extra nitrogen 0.94 A from the plane on the same side as the Ni atom.The plane of the pyrrole ring bonded to the extra nitrogen makes a large dihedral angle of 40.5"with the porphyrin N4 plane." Palladium.-Conductance and 'H n.m.r.studies have analysed equilibria in the substitutions of phosphines (L')for other phosphines (L)or halides (X) in [PdL2X2].71 63 J. J. Macdougall,J. H. Nelson M. W. Babich C. C. Fuller and R. A. Jacobson Inorg. Chim. Actu 1978 27 201. 64 M.A.Hitchman and J. B. Bremner Inorg. Chim. Actu 1978 27 L61. M.S.Ma R. J. Angelici D. Powell and R. A. Jacobson J. Amer. Chem. SOC.,1978,100,7068. " J. R.Ferraro and A. T. Sherren Inorg. Chem. 1978 17,2498. '' (a) R. E. Cramer and J. T. Huneke Znorg. Chem. 1978 17,64; (b) ibid.. p. 365. A. G. Lappin C. K. Murray and D. W. Margerum Znorg. Chem. 1978,17 1630. " E. C. Johnson T.Niem and D. Dolphin Cunud. J. Chem. 1978,56,1381. 70 H.J. Callot B. Chevrier and R. Weiss J. Amer. Chem. Soc. 1978 100,4733. 71 W.J. buch and D. R. Eaton Znorg. Chim. Actu 1978,30 243. Transition Elements 301 Many nucleoside complexes [PdLClJ have been isolated; in aqueous solution they react with other nucleosides (L') to form [PdL(L')3]2+ or [PdL(L')C12] and dimerise at pH 9-10 with the nucleoside becoming bide~~tate.~~ Oxidative addition of Cl2 to [PdCl4I2- has been found to proceed first by oxidation to Pd'" followed by slow substit~tion.~~ Platinum.-According to i.r. and n.m.r. spectra acetylacetonate is a monodentate ligand in [Pt(~ip)~(acac)~], [pip =piperidine] and bidentate and anionic in [Pt(pip)2(acac)]+(acac)- formed from the former on crystallization from The X-ray-determined structure of [Pt(p-H) (SiEt3){P(C6H,l)3}]2 shows the SiPtP planes have a dihedral angle of 21"; the H atoms Were not located in the X-ray work nor found at the expected region in the 'H n.m.r.spectrum but deuteration and bridge-cleavage reactions suggest that the PtH2Pt bridges are ~nsymrnetrical.~~ In [Pt2X2(p-H)(p-Ph2PC2H4PPh2)2]+, [X=H or Cl] i.r. and 'H and 31P n.m.r. spectra suggest Pt H--Pt bonding with the prediction of unusual chemical and catalytic The resonance Raman spectra of the solid miried-valence salts [Pt(EtNH2)4X2]2+ [Pt(EtNH2)4]2+ 4Y-,[X Y =C1 Br or I] gave information on the lengthening of the PtIV-X bond in the excited The structures of M2[Pt(CN)4]Clo.3 (M =Rb or NHJ determined by neutron diffraction show unequal alternating distances in the Pt-Pt linear chain; larger cations give greater expansion of the lattice and lower electric Raman and Raman difference spectroscopy have been used to study complexes of deprotonated 5'-guanosine monophosphate with compounds containing cis-or tran~-[(NH~)~Pt"] units and a variety of co-ordination patterns were found for this7'" and other 79b nucleotides.Linear and circular dichroism studies show that [Pt(en)(bipy)12+ forms complexes with B-form DNA in which the plane of the cation is parallel to the planes of the bases but [Cu(bipy),12+ is co-ordinated by a nitrogen from the bases." The X-ray photoelectron spectrum (XPS) of a cis-PtCl,-'sitting atop' porphyrin a possible intermediate in metalloporphyrin synthesis shows Pt is co-ordinated to two adjacent not opposite nitrogens.8' 6 Copper Silver and Gold Copper.-The X-ray determination of the structure of Li2Cu5(Si2O7) has led to a recalculation of the effective ionic radii of Cu2+ in various geometries.82 The direct thermochemical determination of the enthalpy of formation of Cu and Zn complexes 72 N.Hadjiliadis and G. Pneumatikakis J.C.S. Dalton 1978 1691. 73 R. J. Mureinik and E. Pross J. Coord. Chem. 1978,8 127. 74 S.Okeya F. Egawa Y. Nakamura and S. Kawaguchi Inorg. Chim. Acta 1978,30 L319. 75 M.Ciriano M. Green J. A. K. Howard J. Proud J. L. Spencer F. G. A. Stone and C. A. Tsipis J.C.S. Dalton 1978 801. 76 M. P. Brown R. J. Puddephatt M. Rashidi and K.R. Seddon J.C.S.Dalton 1978 516. 77 R. J. H. Clark and P. C. Turtle fnorg. Chem. 1978,17 2526. 78 J. M. Williams P. L. Johnson A. J. Schultz and C. C. Coffey fnorg. Chem. 1978,17,834;P. L.Johnson A. J. Schultz A. E. Underhill D. M. Watkins D. J. Wood and J. M. Williams ibid. p. 839. 79 (a)G. Y. H. Chu S. Mansy R. E. Duncan and R. S. Tobias J. Amer. Chem. Soc. 1978,100,593;(b)S. Mansy G.Y.H. Chu R. E. Duncan and R. S. Tobias ibid. p. 607. B.NordCn fnorg. Chim. Acta 1978 31 83. 81 J. P. Macquet M. M. Millard and T. Theophanides J. Amer. Chem. SOC.,1978,100,4741. K.Kawamura A.Kawahara and J. T. Iiyama Acta Cryst. 1978 B34 3181. F. A. Hart P. Thornton and D. A. Rice with tetra-aza macrocyclic ligands has shown that the macrocyclic effect is caused by a combination of a favourable entropy term with an enthalpy term which is normally favourable but depends on the size of the metal ion and the aperture in the ligand.83 There has again been much magnetochemical work on polynuclear Cu" complexes.Two groups have published angular overlap treatment of Cu" dirner~.~~ [Cu(N-salgly)(H,O)] (19) which is known to form a polymeric structure by co-ordination of the 'free' glycine 0 atom to a neighbouring Cu exhibits spin cou- pling through hydrogen bonds to neighbouring polymer chains rather than within a polymer chain; the authors predict long-range magnetic ordering in strong applied fields and unusual adiabatic Like its Co analogue complex (14b) has unpaired electrons in orthogonal orbitals and is therefore ferromagnetic.86 The type I11 copper proteins are believed to contain two interacting Cu" atoms and groups of model compounds have been prepared.Complex (20) is the first to show two sequential one-electron transfers at identical potentials." The dimeric cation [Cuz(Me4dien)z(im)(C104)2]+, [Me4dien= 1,1,7,7-tetramethyldiethylene-triamine; im =imidazolate] shows similar magnetic and e.s.r. properties to bovine erythrocyte superoxide dismutase in which Zn is replaced by Cu; X-ray studies show the Cu atoms to be square pyramidally co-ordinated with (C104) as the axial ligand."" Many binuclear Cu" complexes with bridging imidazolate bi-imidazolate or their derivatives have been studied as models for superoxide dismutase the exchange varying with the ligands bond angles and nature of the ground state.886 83 A.Anchini L. Fabbrizzi P. Paoletti and R. M. Clay J.C.S. Dalton 1978 577. 84 A. Bencini and D. Gatteschi Znorg. Chim. Acta 1978,31,11;M.Gerloch and J. H. Harding Proc. Roy. Soc.. 1978,Am,211. W.E.Estes and W. E. Hatfield Znorg. Chem. 1978,17 3226. 86 0.Kahn P. Tola J. Galy and H. Coudanne J. Amer. Chem. SOC., 1978,100,3931. " D. E. Fenton R. R. Schroeder and R. L. Lintvedt J. Amer. Chem. SOC.,1978,100,1931;D.E. Fenton and R. L. Lintvedt ibid. p. 6367. (a) C.-L.O'Young J. C. Dewan H. R. Lilienthal and S. J. Lippard J. Amer. Chem. SOC.,1978,100 7291;(b)M.S.Haddad and D. N. Hendrickson,Inorg. Chem. 1978.17.2622. Transition Elements 303 A series of papers studies the role of Cu” complexes in the treatment of rheumatoid arthritis concluding that mixed complexes with histidinate and cystinate are important and that uncharged complexes must be formed in order to pass through cell membranes.*’ The dimer [Cu(S’-ump) (dpa) (Hz0)]2-5Hz0 [5’-ump = uridine 5‘-monophosphate; dpa =dipyridylamine] is antiferromagnetic though the authors had expected ferr~magnetism.’~“ X-Ray determination of its structure shows the bridging nucleotide to form Cu-0-P-0-Cu bridges with no inter- action between Cu and the pyrimidine group.However the analogous cytosine complex may have co-ordination by the base and n.m.r. and pK studies suggest ump may co-ordinate through its base as well as its phosphate group in other Cu compIexe~.’~~ This has been a good year for copper proteins.There have been particularly dramatic advances in type I (blue e.s.r.-active) proteins. The X-ray determination of the structure of plastocyanin shows the single Cu atom is co-ordinated in a distorted tetrahedron by S atoms from cysteine thiol and methionine thioether groups and by N atoms from two histidine groups.” A similar conclusion is reached by the X-ray study of a~urin.’~ Thus there is no co-ordination by deprotonated peptide groups as previously proposed. Consistent with these results the EXAFS spectrum of oxidized azurin shows the ‘blue’ site to contain a short Cu-S (thiolate) bond (2.10 A) and two Cu-N (imidazole) bonds (1.97 A),and there may be a Cu-S (methionine) interaction at a longer distance.” The resonance Raman spectra of various CuII complexes with SR-or SRz ligands indicate the presence of Cu- methionine bonds in blue copper proteins but stellacyanin which contains no methionine may have co-ordination by a disulphide group.94 A welcome start has been made on kinetic studies of the reactions of oxidized or reduced plastocyanin with common reducing or oxidizing agent^.'^ The e.s.r.spectrum of ceruloplasmin and its derivatives in which the type I sites are bleached suggests that the type I1 sites (e.s.r.-active but not ‘blue’) contain a Cu atom co-ordinated by 3 (or possibly 4) N in a tetragonal environment; this site may co-ordinate up to two F-ions probably in axial position^.'^ The e.s.r. and electronic absorption spectra of complexes of half -oxidized haemocyanin containing Cu’ and CU” with CN- NOz- 02CMe- or N3- suggest the ligands and presumably also 02 co-ordinate in an equatorial site.” The X-ray-determined structure of [Cu(1-Meim)(HzNCzH4SCzH4NH2)]2’ shows this cation already known to have a similar d-d-spectrum to the type I1 protein galactose oxidase to have distorted 89 G.E. Jackson P. M. May and D. R. Williams,J. Inorg. NuclearChem.,1978.40,1189 and five following papers. 90 (a)S. L. Lambert T. R. Felthouse and D. N. Hendrickson,Inorg. Chim.Actu 1978,29,L223; (b)B. E. Fischer and R. Bau Inorg. Chem. 1978 17 27. 91 P. M. Colman H. C. Freeman J. M. Gus,M. Murata V. A. Norris J. A. M. Ramshaw and M. P. Venkatappa Nature 1978,272 319. 92 E. T. Adman R. E. Stenkamp L. C. Sieker and L. H. Jensen J.Mol. Bid 1978,123 35. 93 T. D. Tullius P. Frank and K. 0.Hodgson Proc. Nut. Acad. Sci.U.S.A. 1978,75,4069. 94 N. S. Ferns W. H. Woodruff D. B. Rorabacher,T. E. Jones and L. A. Ochxymowyn,J. Amer. Chem. Soc. 1978,100 5939. 95 M. G. Segal and A. G. Sykes J. Amer. Chem. SOC.,1978,100,4585. % J. H. Dawson D. M. Dooley and H. B. Gray Proc. Nat. Acad. Sci. U.S.A. 1978,75,4078. 97 R. S. Himmelwright N. C. Eickman and E. I. Solomon Biochem. Biophys. Res. Comm. 1978,81,237. F. A. Hart P. Thornton and D. A. Rice square pyramidal co-ordination for CU.~~~ However kinetic and e.s.r. studies on galactose oxidase have been interpreted as showing this to be a Cu"' species and the authors suggest Cu"' may be involved in other enzyme reactions.98b Silver.-When Ag absorbed on an Ar matrix at 10-20K is irradiated on the 2S1/2+zP3/2,1/2 transition clusters of Ag atoms of known size (Ag2-Ag,) can be prepared; the technique is called 'cryophotoclustering'.The electronic spectra of the clusters show a progression from molecular to bulk properties as the size of the PPh / Ph,P (21) cluster increases.99 A new cluster structure [(Ph3P)4Ag4(WS4)2] (21) has been identified in which WS4*- acts as a tridentate 1igand.l" Gold.-The first example of Au' stabilized by two N-donors has been described. The imido ligand (22) is probably labile in vivo and may be useful in inserting Au' into proteins in such applications as anti-inflammatory chemotherapy.l0la Other Au' and Au"' amino-acid complexes have been studied to further this topic.lOlb The Moss-bauer spectra of [Au,,(PR,)~X,] [R =Ph or 4-C1C6&; X = SCN I or CN] can be curve-fitted to show the three different Au sites; improved preparation of these complexes by evaporation of Au metal is described."* 7 Appendix Papers not Treated in Detail The table which follows summarizes important papers for which space limitation precludes detailed discussion.98 (a) J. F. Richardson and N. C. Payne Inurg. Chem. 1978,17,2111; (b)G.A. Hamilton P. K. Adolf J. de Jersey G. C. Du Bois G. R. Dyrkacz and R. D. Libby J. Amer. Gem. SOC.,1978,100,1899. 99 G.A. Ozin and H. Huber fnorg. Chem. 1978,17,155. loo A. Muller H. Bogge and E. Koniger-Ahlborn J.C.S. Chem. Comm. 1978,739. (a)N. A. Malik P. J. Sadler S.Neidle and G. L. Taylor J.C.S. Chem. Cumm. 1978 711; (b) D. H. Brown G. C. McKinley and W. E. Smith J.C.S. Dalton 1978 199. lo* F.A. Vollenbroek P. C. P. Bouten; J. M. Trooster J. P. van den Berg and J. J. Bour Inorg. Chem. 1978 17 1345. Transition Elements Compound General Metalloporphyrins Macrocyclic complexes Square planar complexes SO complexes NO3- complexes Spin labels Rhenium Re,Cl,(diphos) Re2X4(PR3)4 (X= halogen) K&F Re203(py)4C12 Iron [Fez(N0)6]2+*2PF6-[Fe(CN),(diamine)]'-cis-Fe( hen),(NCBPh,) [FeL,+.2N03-[L =(23)l Fe2S.3 Fe20L2(Hz0)4 (L= 4-CI-pyridine-2,6-dicarboxylate) 305 Comments Reference Short reviews 103 Short review especially on Co and Ni 104 Review of substitution mechanisms 105 Pt metals short review comparison with NO 106 Pt metals review 107 Review on bioinorganic and e.s.r.aspects 108 3-co-ordinate Mn 109 Mn equivalent oxidation state &I3 110 Reversibly binds 0,in Me,SO 111 Really [(NC),Mn0Mn(CN),l6- 112 Staggered triple Re=Re bond 113 Mechanisms of electrochem. oxidations 114 Compressed [ReFJ4- octahedron 115 Revised structure 116 Fe=Fe double bond 117 C.d. assignment of low spin Fe" 118 Simultaneous spin and structure change; 'H n.m.r. 119 Singlet %quintet shows hysteresis 120 First pure preparation 121 Fe-0-Fe angle does not affect magnitude of antifer-122 romagnetism H aN '03 J. W. Buchler Angew. Chem. Internat. Edn. 1978,17,407;J. W. Buchler W. Kokisch and P.D. Smith Structure and Bonding 1978 34 79. '04 D. H. Busch Accounts Chem. Res. 1978,11,392. R. J. Mureinik Coord. Chem. Rev.. 1978,25 1. D. M. P.Mingos Transition Metal Chem. 1978,3 1. lo' P. B. Critchlow and S. D. Robinson Coord. Chem. Rev. 1978,25,69. S. S. Eaton and G. R. Eaton Coord. Chem. Rev. 1978,26,207. '09 D. C. Bradley M. B. Hursthouse K. M. A. Malik andR. Moseler TransitionMetal Chem. 1978,3,253. A. R. E. Baikie M. B. Hursthouse D. B. New and P.Thornton J.C.S. Chem. Comm. 1978,62. '11 K. D. Maggers C. G. Smith and D. T. Sawyer J Amer. Chem. SOC. 1978,100,989. '12 G. Trageser and H. H. Eysel Znorg. Nuclear Chem. Letters 1978,14,65. '13 F. A. Cotton G. G. Stanley and R. A. Walton Inorg. Chem.. 1978,17 2099. '14 P. Brant D. J. Salmon and R.A. Walton J. Amer. Chem. SOC. 1978,100,4424. '15 G. R. Clark and D. R. Russell Acra Cryst. 1978. B34 894. 'I6 C. J. L. Lock and G. Turner Canad. J. Chem. 1978,56,179. '" M. Heberhold and R. Klein Angew. Chem. Internat. Ed. 1978,17,454. '" M. Goto M. Takeshita and T. Sakai Inorg. Chem.. 1978 17 314. K. F. Purcell and J. P. Zapata J.C.S. Chem. Comm. 1978,497. G. Ritter E. Konig W. Irler and H. A. Goodwin Znorg. Chem. 1978,17 224. lZ1 A. H. Stiller B. J. McCormick P.Russell and P. A. Montano J. Amer. Chem. SOC.,1978,100,2553. lZ2 C. C. Ou R. G. Wollmann D. N. Hendrickson J. A. Potenza and H. J. Schugar J. Amer. Chem. Soc. 1978,100,4717. 306 E A. Hart P. Thornton and D. A. Rice Compound Comments Reference Iron-cont. Fe porphyrins EXAFS spectra on natural and synthetic compounds 123 Fe(TpivPP)(1-Meim)O Resonance Raman spectrum shows vFe-0 at 124 568cm-' (cf oxyhaemoglobin 567cm-I) indicates multiple Fe-0 bonding Fe"' porphyrins Mossbauer spectra clarified; 125 X-ray structures 5-or 6-co-ordinate 126 Fe(TPP)CI Forms [Fe(TPP)(im),]+ with imidazoles before spin 127 (TPP = tetraphenylporphyrin) changes Fe"'-haem Reaction with CN- studied by n.m.r.128 Fe"'-porphyrin-Models for haemoglobin mutants 129 phenoxide complexes Fe-S proteins I9F n.m.r. analysis of core extrusion reactions; milk 130 xanthine oxidase contains 2Fe,S units Protein (111) of Azotobucter uinelundii contains 1 Fe,S 131 and 1 other unit not identified [Fe,S,(SR),]"-(n = 2,3) Thorough 'H n.m.r. study and comparison to oxidised 132 [Fe,S,X412-(X =C1,Br; n = 2,4) and reduced ferredoxins Preparation and properties 133 Oxyhemerythrin Single crystal polarized electronic spectrum shows 0 134 monodentate to 1 of 2Fe"' Protocatechuate 3,4-dioxygenase Resonance Raman spectrum indicates Fe-tyrosine bond 135 Fe-bipyrimidine-Cu complex Model for cytochrome oxidase 136 Fez(rd3 Hydroxamate siderophore; unusual A absolute 137 [ra =rhodotorulate,(24)] configuration 00 (24) Fe H-C-NMe Fluopsin siderophore X ray structure shows A 138 ( sI :--',0I )3 absolute configuration Ruthenium NO complexes Review one of group in memory of A.D. Allen 139 bidentate SO complex 140 [RuCl(NO)(SO,)(PPh,),].CH,CI Second (SO) S.P.Cramer J. H. Dawon K. 0.Hodgson and L.P. Hager J. Amer. Chem. SOC., 1978,100,7282. J. M. Burke J. R. Kincaid S.Peters R. R. Gagne J. P. Collman and T. G. Spiro J. Amer. Chem. Soc. 1978,100,6083. D. H. Dolphin J. R. Sams T. B. Tsin and K. L. Wong J. Amer. Chem. SOC.,1978,100 1711. lZ6 F. W. B. Einstein and A. C. Willis Inorg. Chem. 1978,17,3040;M. E. Kastner W. R. Scheidt T. Mashiko and C. .A. Reed J. Amer. Chem. SOC.,1978 100 666; T. Mashiko M. E. Kastner K. Spartalian W. R. Scheidt and C. A. Reed ibid. p. 6354. R. F. Pasternack B. S.Gillies and J. R. Stahlbush J. Amer. Chem. SOC.,1978 100,2613. J.-T. Wang H. J. C. Yeh and D. F. Johnson J. Amer. Chem. Soc.,1978,100,2400. E.W. Ainscough A. W. Addison D. Dolphin and B. R. James J. Amer. Chem. SOC.,1978,100,7585. D. M.Kurtz G. B. Wong and R.H. Holm J. Arner. Chem. SOC.,1978,100,6777. 13' B. A.Averill J. R. Bale and W. H. Orme-Johnson J. Amer. Chem. SOC.,1978,100,3034. 132 J. G. Reynolds E. J. Laskowski and R. H. Holm J. Amer. Chem. Soc. 1978,100,5315. 133 G.B. Wong M. A. Bobrik and R. H. Holm Inorg. Chem. 1978,17,578. 134 R. R. Gay and E. I. Solomon J. Amer. Chem. SOC.,1978,100 1972. 135 Y.Tatsuno Y. Saeki M. Iwaki T. Yagi M. Nozaki T. Kitigawa and S. Otsuka J. Amer. Chem. SOC. 1978,100,4614. 136 R. H. Petty and L. J. Wilson J.C.S. Chem. Comm. 1978,483. 137 C. J. Carrano and K.N. Raymond J. Amer. Chem. SOC.,1978,100,5371. 13* K.S.Murray P. J. Newman and D. Taylor J. Amer. Chem. SOC.,1978,100,2251. 139 F. Bottomley Coord. Chem. Rev. 1978,26 7. R. D. Wilson and J. A. Ibers Inorg. Chem.1978,17,2134. Transition Elements 307 Componad Comments Reference Rutheninm-cont. [Ru3L3O(OzCMe),I+ Preparation properties redox chemistry reaction with 141 (L =dmf py or derivatives) HZ Diketonatecomplexes Convenient preparation. Also for Os Ir 142 Dithiocarbamate complexes Redox chemistry 'H n.m.r. oxidations with BF 143 [(NH3)5Ru(SMe3)13+ First sulphonium ion complex 144 NH3. pyrazine and bipy complexes Short review of electron transport reactions 145 cis-Ru(bipy),Cl Improved synthesis 146 Porphyrin complexes Reversible reactions with 0 in ambient conditions 147 RPF complexes Preparations 'H I9F 31P n.m.r. catalysis 148 (R=F NMeJ [{(NH,)sRu}zLIS' Unpaired electron in (d,, dyz)on Ru'"; e.s.r. n.m.r. 149 (L=pyrazine) magnetochemistry Polynuclear pyrazine complexes Pyrazine bridges up to 6[Ru(NH,) J units; electronic 150 spectra Intervalence transition at high energy and solvent- 151 [{(~~PY)~(PY)R~}~(~.~'-~~PY)I'+ insensitive [Ru2Br9I3-Ru-Ru bond proposed; may be same as earlier repor- 152 ted [Ru,Br,,]'- complexes Nucleoside probably co-ordinates through exocyclic N; 153 [(NH,)5R~]3+-nucleoside redox studies [RU(~~PY)~(PY)OI~' Formed in oxidation of [R~(bipy),(py)(OH,)]~' by Ce4' 154 Osmium OSO Reactions with catechols,'ssa dienes and alkyne~,"'~ 155 relevant to staining plant tissue OsO,(quinuclidine) Trigonal bipyramidal Oswr' but long 0s-N (2.37A) 156 3 bridging MeN(PF,),; Co-Co 2.740A 157 Have P equilateral triangle as ligand 60, 158 First paramagnetic Co nitrosyl 159 First preparation unsolvated 160 Resonance Raman data as basis for studying Zn proteins 161 when Zn replaced by Co S.A. Fouda B. C. Y. Hui and G. L. Rempel Inorg. Chem. 1978,17 3213; J. A.Baumann D. J. Salmon S.T. Wilson T. J. Meyer and W. E. Hatfield ibid.,p. 3342. M. A. M. Queir6s and S. D. Robinson Znorg. Chem. 1978,17 310. S.H.Wheeler B. M. Mattson G. L. Miessler and L. H. Pignolet Inorg. Chem. 1978 17 340. 144 C. A. Stein and H. Taube J. Amer. Chem. SOC.,1978,100,336. T.J. Meyer Accounts Chem. Res. 1978,11,94. R. A. Krause Znorg. Chim. Actu 1978,31.241. N. Farrell D. H. Dolphin and B. R. James J. Amer. Chem. SOC.,1978,100 325. 14* R. A. Head and J. F. Nixon J.C.S. Dalton 1978,885and 5 following papers. B. C. Bunker R.S. Drago D. N. Hendrickson R. M. Richman and S.L. Kessell J. Amer. Chem. SOC. 1978,100,3805. A. von Kameke G. M. Tom and H. Taube Znorg. Chem. 1978,17,1790. '" M. J. Powers and T. J. Meyer Inorg. Chem. 1978 17 1785. '" J. E.Fergusson and A. M. Greenaway Austral. J. Chem. 1978,31,497. M. J. Clarke J. Amer. Chem. SOC.,1978,100 5068. lS4 B. A. Moyer and T. J. Meyer J. Amer. Chem. Soc. 1978,100 3601. (a) A. J. Nielson and W. P. Griffith J.C.S. Dalton 1978,1501;(6)M.Schroder and W. P. Griffith ibid. p. 1599. 156 W. P. Griffith A. C. Skapski K. A. Woode and M. J. Wright Inorg. Chim. Acta 1978,31 L413. '" M. Chang M. G. Newton R. B. King and T. J. Lotz Inorg. Chim. Actu 1978,28 L153. F. Cecconi P.Dapporto S.Midollini and L. Sacconi Znorg. Chem. 1978,17,3292.B. T.Huie P. Brant and R. D. Feltham. Znorg. Chim. Acm 1978,29,L221. S.V.hginov 2.K. Nikitina and V.Ya. Rosolovskii Russ. J. Znorg. Chem. 1978,17 178. 16' S.Salama and T. G. Spiro. J. Amer. Chem. SOC.,1978 100 1105. 14' 308 F. A. Hart P. Thornton and D. A. Rice Compound Comments Reference Cobalt-cont. [WPY i2(saWl+ Controlled potential reduction in py with LiCIO +0 162 [salen = 0.C6H,CN:NC,H,N:CH-traps 0,-as LiO C6H401 Co”-thioiminate tetradentates Energetics of reversible absorption of O2 studied with 163 varying ligand solvent added base Co” Co”’ complexes with dien Redox properties of geometrical isomers 164 Porphyrin complexes In Me,SO found Me-S-CH,-Co unit 165 I 0 [CO(L-as para gin ate)(^-aspartate)] X-ray structure shows amide group of asparaginate 166 H20 co-ordinates as -C=N-Co II OH H [Co(phen)( meso-tartrate)]’ All 4 isomers prepared 167 [Co(NH,),13+-S donor Correlation between Co-N lengthening trans to S and 168 rate of substitution by NCS- ICo(C0,),l3-Reduction by N2H preceded by substitution 169 ~co(NH,)sx12+ Reduction by Cr” V2+ or Ru(NH,),” is outer-sphere 170 (X = amino-acid anion) process but precursor complex formed [c~(en)~(NO~),l’ Catalyst for NO +RNH +N +N,O 171 Rhodium Rh(Bu‘,P),ClH Trigonal bipyramidal Rh short Rh-H (1.36A) high 172 4Rh-H) (2205 2220 cm-I) reduced hydrogenation catalytic power Nickel Nil-phosphine complexes Formed by reduction of Ni” with NaBH in presence of 173 ligand’ Ni”-cyclic triamine complexes Small ring size gives greater Dq and formation constant.174 Also for Cu [Ni(6,6’-dihydrazin0-2,2’-bipyridyl)]’’ Complexes of new tetradentate ligands by reaction with 175 diketones Neutron diffraction shows cis-bridged regular PdF 176 octahedra Resonance Raman spectra gave mixed valence tran- 177 sitions and v(M-X) Platinum Pf2(PR3)4 MO study of reactions and formation from Pt(PR,) 178 Pt(8-oxyquinolinate) Long-lived excited state emission spectrum 179 ‘62 A. Puxeddu N. Marisch and G. Costa J.C.S. Chem. Comm. 1978 339. 163 L. S.Chen M. E. Koehler B. C. Pestel and S. C. Cumrnings J. Amer. Chem. SOC.,1978 100 7243. 164 A. M. Bond F. R. Keene N. W. Rumble G. H. Searle and M. R. Snow Inorg. Chem. 1978,17,2847. ’” P.Boucly J. Devynck M. Perree-Fauver and A.Gauderner J. Organometallic Chem. 1978,149 65. 166 M. Sekizaki Bull. Chem. SOC. Japan 1978 51 1991. A. Tatehata Inorg. Chem. 1978 17 725. 168 R.C. Elder M. J. Heeg M. D. Payne M. Trkula and E. Deutsch Inorg. Chem. 1978,17,431. 169 S. P. Tanner Inorg. Chem. 1978,17,600. C. S. Glennon J. D. Edwards and A. G. Sykes Inorg. Chem. 1978 17 1654. 17’ S. Naito J.C.S. Chem. Comm. 1978 175. 172 T.Yoshida S. Otsuka M. Matsumoto and K. Nakatsu Inorg. Chim. Acta 1978 29 L257. 173 D. G. Holah A. N. Hughes B. C. Hui and C.-T. Kan Canad. J. Chem. 1978 56,2552. 174 L. J. Zornpa Inorg. Chem. 1978,17,2531. 175 J. Lewis and K. P. Wainwright J.C.S. Dalton 1978,440. 176 A. F. Wright B. E. F. Fender N. Bartlett and K. Leary Inorg. Chem. 1978,17,748.177 R.J. H. Clark and P. C. Turtle J.C.S. Dalton 1978 1622. 17’ A. Dedieu and R. Hoffmann J. Amer. Chem. SOC.,1978,100,2074. 179 R.Ballardini M. T. Indelli G. Varani C. A. Bignozzi and F. Scandola Znorg. Chim. Actu 1978,31 L423. Transition Elements 309 Compound Comments Reference Platinum-cont. Pt4(OzCMe)s Pt square all 0,CMe bridging 2 crystal forms 180 Pt"-lW-methionineS-oxide} comdex Dimeric bridging RNH groups 181 [(Ph;P);Pt(OH)(0,)F't(PPh3jz]+ -First O,'-/OH- bridge system 182 [Pt(CN)4]"-(1c n s2) Extended Hiickel calculations gave band structure 183 Ptn-2,2'-bipyrimidine complexes Layers in columnar structures brought closer in hydrates 184 by H-bonding Propose Pt'" in columnar structure 185 Unusually high ox. state in phosphine complex 186 Copper Na,[Cu(CN),.3H20 First discrete [CU(CN),]~- planar 187 Planar Cu,; L has 3 modes of co-ordination 188 Cu' cluster complexes MO studies conclude no Cu-Cu bonds 189 Cu180z(OSiMe3)14 Spherical molecule 18 Cu in centre with OSiMe groups 190 on surface H,C=C(Me)CNCuBr Two types of 4-co-ordinate Cu 191 cu'om XPS spectrum shows 1Cu'+ 2Cu2' improved prep- 192 Cu,(HzO)z(SO&z, 'Chevreul's salt' aration 'N=C Rate of ligand exchange with en increases as structure 193 becomes non-planar II RH (R= H,Me,Pr" Pr' But) CuInCI Resonance Raman spectrum suggests CICu(p-CI),InCI 194 cc~,L2(co3)12+ Has Cu-0-CU bridging unit 195 (L = tridentate macrocycle) Cu(OC,H,NPr,)(NCO) Structures of dimer (antiferromagnetic) and tetramer 196 (magnetically normal) M.A. A. F. de C. T. Carrondo and A. C. Skapski Acta Cryst. 1978 B34,1857,3576. W. A. Freeman L. J. Nicholls and C. F. Liu Inorg. Chem. 1978,17,2989. 182 S. Bhaduri P. R. Raithby C. I. Zuccaro M. B. Hursthouse L. Casella and R. Ugo. J.C.S. Chem. Comm. 1978,991. 183 M.-H. Whangbo and R. Hoffmann J. Amer. Chem. SOC.,1978,100,6093. P. M. Kiernan and A. Ludi J.C.S. Dalton 1978 1127. H. Endres H. J. Keller H. van de Sand and V.Dong 2.Naturforsch. 1978,33b 843. lS6 C. Crocker P. L. Goggin and R. J. Goodfellow J.C.S. Chem. Comm. 1978 1056. 18' C. Kappenstein and R.P. Hugel Inorg. Chem.. 1978 17 1945. D. M. L. Goodgame G. A. Leach A. C. Skapski and K. A. Woode Inorg. Chim Acta 1978,31 L375. lS9 A. Avdeef and J. P. Fackler Znorg.Chem. 1978 17 2182; P. K. Mehrotra and R. Hoffmann ibid. p. 2187. 190 T. Greiser 0.Jarchow K.-H. Klaska and E. Weiss Chem. Ber. 1978,111,3360. 19' M. Massaux G. Ducreux R. Chevalier and M.-T. Le Bihan Actu Cryst. 1978 B34 1863. 192 P. Brant and Q. Fernando J. Inorg. Nuclear. Chem. 1978,40,235. 193 G. R. Dukes and S.R. Loveday J.C.S. Chem. Comm. 1978,583. C. W. Schlapfer and C. Rohrbasser Znorg. Chem. 1978,17 1623. A. R. Davis F.W. B. Einstein N. F. Curtis and J. W. L. Martin J. Amer. Chem. SOC.,1978,100,6258. 196 L. Merz and W. Haase Acta Cryst. 1978 B34 2128. 19' 19' F. A. Hart P. Thornton and D. A. Rice Compound Comments Reference Copper-cont. N-N-N \ Has Cu/ Cu bridging unit and \ / N-N-N large zero field splitting [CuZ(tren),Ll4+ First aromatic diamines to transmit magnetic exchange 198 Cu( S'CNEt) Resonance Raman spectrum finds 14cu-S) at energy 199 for blue Cu proteins Laccase Magnetochemistry revised type I I1 sites normal type 200 I11 strongly coupled Oxytyrosinase Resonance Raman spectrum suggests (Cu-imidazole) 201 and 0,'-present; type I11 protein Cu" bovine carbonic anhydrase 'H n.m.r.in H,O suggests 5-co-ordinate Cu with one site 202 more distant [Cu(glycylglycylhistaminate)]~2Hz0 From Cu(OH) + glyglyhis first product of oxidative 203 decarboxylation to remain co-ordinated; X-ray struc- ture X-ray structure 204 Polynuclear structures 205 Unusual cluster structure. Also for Cu 206 Found in zeolite Ag bonded to 6Ag' 207 Preparation and redox chemistry in NH3(I) 208 Redetermined Ee for Au +Au' + e-209 X-ray structure rather long Au-Au (3.104A) 210 Preparation and X-ray structure.WS4'-bidentate 211 bridging 19' 19* T. R. Felthouse and D. N. Hendrickson Inorg. Chem. 1978 17,444. T. R.Felthouse E. N. Duesler and D. N. Hendrickson J. Amer. Chem. SOC.,1978,100,618. 199 L.Tosi and A. Gamier J.C.S. Dalton 1978 53. 'O0 D. M.Dooley R. A. Scott J. Ellinghaus E. I. Solomon and H. B. Gray Proc. Nut. Acad. Sci. U.S.A. 1978,75,3019. N. C. Eickmann E. I. Solomon J. A. Larrabee T. G. Spiro and K. Lerch J. Amer. Chem. SOC.,1978 100,6529. I. Bertini G.Canti C. Luchinat and A. Scozzafava J.C.S. Dalton 1978 1269. '03 P. de Meester and D. J. Hodgson Znorg. Chem. 1978,17,440.P. Meyer A. Rimsky and R. Chevalier Acta Cryst. 1978 B34 1457. ,05 (a) A. A. M. Aly D. Neugebauer 0. Orama U. Schubert and H. Schmidbauer Angew. Chem. Internat. Edn. 1978 17 125; (b)H.Schmidbauer A. A. M. Aly and U. Schubert ibid. p. 846. '06 I. G. Dance Austral. J. Chem. 1978,31 2195. ,07 Y.Kim and K. Seff J. Amer. Chem. SOC.,1978,100 175. ''13 W. J. Peer and J. J. Lagowski J. Amer. Chem. SOC.,1978 100 6260; T. H.Teherani W. J. Peer J. J. Lagowski and A. J. Bard ibid.,p. 7768. '09 P. R. Johnson J. M. Pratt and R. I. Tilley J.C.S. Chem. Comm. 1978 606. W. S. Crane and H. Beall Inorg. Chim. Actu 1978,31 L469. 211 A. Miiller H. Dornfeld G. Henkel B. Krebs and M.P. A. Viegers Angew. Chem. Internat. Edn. 1978 17,52.

ISSN:0308-6003    

DOI:10.1039/PR9787500289

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

10 Organometallic Chemistry By A. J. DEEMING Department of Chemistry University College London London WClH OAJ and J. EVANS Department of Chemistry The University Southampton SO95NH This chapter covering the literature received between January and December 1978 is divided into two parts. In the first one 0-bonded carbon ligands are of primary interest whilst in the second the complexes of q-bonded ligands are classified according to their hapticity. Some general items are presented below. A new system of designation of co-ordination sites has been presented in which the letter s1 is used to define co-ordination." Texts of the plenary lectures of the 8th International Conference on Organometallic Chemistry at Kyoto in September 1977 have been publishedb and papers produced at a workshop on homogeneous catalysis at Shiga Japan in 1977 are also available.' Reviews on the following have appeared matrix isolation studies on transition metal carbonyls,d use of organo-aluminium compounds in organic synthesis,' reactions of electrophiles with tran- sition metal alkyls,' organo-lanthanide complexes,g olefin metathesis," clusters' and their rearrangements and relation with surface science,k the formation of ally1 and diene complexes from cyclopropyl alkenes,' the organometallic and other chemistry of multiple metal-metal bonded compounds,m and catalytic aspects of pentamethylcyclopentadienyl-rhodiumand -iridium complexes." a G.J. Leigh Inorg. Chem. 1978 17 2047. Pure Appl. Chem. 1978,50,1-64 and 677-742. Y.Ishii and M. Tsutsui Fundamental Research in Homogeneous Catalysis Vol. 2 Plenum Press 1978. J. K. Burdett Coord. Chem. Rev. 1978,27 1. ' H. Yamamoto and H. Nozaki Angew. Chem. Internat. Edn. 1978,17 169. M. D. Johnson Ace. Chem. Res. 1978,11 57. 'T. K. Marks Prog. Inorg. Chem. 1978,24 51. R. H. Grubbs Prog. Inorg. Chem. 1978,24 1. ' H. Vahrenkamp Angew. Chem. Internat. Edn. 1978 17 379; G. Schmid ibid. 1978 17 392. E. Band and E. L. Muetterties Chem. Rev. 1978,78,639. 'E. L. Muetterties Angew. Chem. Internat. Edn. 1978 17 545. ' S. Savel Ace. Chem. Res. 1978,11 204. F. A. Cotton Ace. Chem. Res. 1978,11,225;M. H. Chisholm and F. A. Cotton ibid. 1978,11,356,and M. H. Chisholm Trans. Met. Chem. 1978 3 321. P. M. Maitlis Ace. Chem. Res. 1978 11 301.311 A. J. Deeming and J. Evans Part I Alkyls Aryls Carbonyls Cyanides Carbenes Carbynes By J. Evans 1 Metal Carbonyls Mononuclear Carbonyls.-Calorimetric measurements on the carbonyl complexes M(C0)4L2 and M(CO)3L3 (M = Cr Mo or W; L = py or MeCN) have been used to estimate the M-L bond enthalpies.' The DMM-= values increase along the series NCMe < py < CO the total differences being of the order of 10-20 kJ mol-'. Calculation of the proton affinity of (MeC,H,)Mn(C0)3 (825f 8 kJ mol-I) was possible from ion cyclotron resonance equilibrium measurements.' Although Fe(CO)5 has no permanent dipole moment it appears to have one at microwave frequencies and this is thought to arise from a square pyramidal i~omer.~ Data obtained from this dielectric relaxation study indicate an 8 kJ mol-' activation energy to pseudorotation.There has been an extensive vibrational study of single and mixed crystals of metal carbonyl complexe~.~ Intermolecular coupling between vco vibrations was absent in W(CO)(PhCCPh)3 but was evident for at least some such modes in more complicated examples. Resonance Raman excitation profiles have been particularly useful in resolving and assigning MLCT electronic absorptions in Mo(CO) complexes of unsaturated bidentate nitrogen donor ligands e.g. diazabutadienes and pyridine-2- ~arbaldehydeimines.~Electronic properties have also been studied by u.v.~ and X-ray7 photoelectron spectroscopy. Deductions of CT donation and T acceptance abilities of PX3 ligands are in line with electronegativity arguments.The shape of the 01,peak of the X-ray p.e.s. spectrum of Fe(CO)5 vapour appears to consist of two overlapping curves with the axial and equatorial peaks being separated by 0.8 eV:7a the axial oxygens have the higher binding energy. Spectra of Group VI hexacar- bonyls and their derivatives have satellites due to electron shape the most prominent of which were assigned as MLCT transitions for the M(C0)6 species.7c ' F. A. Adedeji J. A. Connor C. P. Demain J. A. Martinho-Simoes H. A. Skinner and M. T. Z. Moattar J. Organomefallic Chem. 1978,149 333. ' J. Fernando G. Faigle A. M. Da Costa S. E. Galembeck and J. M. Riveras J.C.S.Chem. Comm. 1978 126. E.N.Di Carlo and E. P. Zurback J. Arner. Chem. Soc. 1978 100 3959.44D. N. Kariuki and S. F. A. Kettle Inorg. Chem. 1978 17,41. 4b D. N.Kariuki and S. F. A. Kettle Inorg. Chem. 1978 17 1018. 4c D. N.Kariuki and S. F. A. Kettle J.C.S. Dalton 1978,262. 4dM,Arif S. F. A. Kettle and C. C. Tso Inorg. Chim. Actu 1978,31 191. 4c S. L.Barker L. Harland and S. F. A. Kettle Inorg. Chim.Acra 1978 31 217. 4fS.L. Barker L. Harland S. F. A. Kettle andF. F. S. Stephens Znorg. Chim. Acfa 1978 31 223. '"R. W.Balk D. J. Stufkens and A. Oskam J.C.S. Chem. Comm. 1978 1016. 5bL.H.Stahl D. J. Stufkens and A. Oskam Znorg. Chim. Am 1978,26,255. ''R.W.Balk D. J. Stufkens and A. Oskam Inorg. Chim. Acfa 1978 28 133. ""H. Daamen and A. Oskam Inorg. Chim. Acfa 1978 26 81. 6bL.W.Yarbrough 111 and M. B. Hall Znorg. Chem. 1978 17 2269."M. A. Ukimer and M. Lattman Inorg. Chem. 1978 17 1084. "dH. Daamen G. Boxhoorn and A. Oskam Znorg. Chim. Acfa 1978,28,263. "'A. Flamini E. Semprini F. Stefani,G. Cardaci G. Bellachioma and M. Andreocci J.C.S. Dalton 1978 695. 7aS. C. Avanzino W. L. Jolly P.-A. Malmquist and K. Siegebahn Inorg. Chem. 1978 17,489. "H. Binder and D. Sellman 2.Nuturforsch. 1978,33b 173. 7c G. M.Bancroft B. D. Boyd and D. K. Crober Inorg. Chem. 1978,17 1008. Organometallic Chemistry 313 The first stable amine carbonyl complexes of Cu have been synthesized.* [Cu(dien)(CO)] BPh has a distorted tetrahedral co-ordination geometry (Cu-C = 177.6 pm) and in the ethylenediamine analogue [Cu(en)(CO)]BPh4 (Cu-C = 180.6 pm) the fourth co-ordination site is occupied by a weak interaction with two carbon atoms of one of the rings in the BPh4 moiety.Treatment of trans-M~(N,)~(dppe)~ with benzyl propionate givesrise to trans-Mo(N2)(CO)(dppe) which reversibly loses N2 to form the 16-electron species M~(CO)(dppe)~.~ This square pyramidal complex has an apical carbonyl and there is a secondary interaction with an ortho-hydrogen of one of the ligand phenyl groups. New synthetic routes to substituted carbonyl cations have been reported,loa some of which are shown in Scheme 1. Formation of the strong Lewis acids [(CsH5)M(C0)3]' (M =Mo or W) by hydride abstraction with CPh3+ is notewor- thy.lob This carbonium ion will also abstract alkyl groups from RMn(C0),PPh3 derivatives to give synthetically useful solvated cations."' (CSHS)M(C~)~C~ [(CSHS)M(CO),(N~H~)I+ lPR3 [(CsHs) M(CO)&I+ T" (CSHS)M(C0)3HCPh3+h [(C,Hs) M(C0)31+ L =PR3 C2H4 CHzClz (CsHs)M(CO),H; M =Mo W.Scheme 1 New quantitative syntheses of metal carbonylate anions have been reported by cleavage of dimers with KH"O and reaction of Fe(CO) with K[BU~~BH]."~ The latter synthesis affords pure K,Fe(CO) uia the formyl complex (HCO)Fe(CO),-. The highly reduced anions Na,M(CO) (M =Cr Mo or W) have been synthesized.'* These insoluble salts have two very low frequency vco i.r. absorptions at ca. 1680cm-' and 1470cm-' thought to be due to M-C-0-Na interactions. Such interactions have been identified for NaCo(CO) in the crystal of [C~(salen)]~NaCo(CO),thf'~~ Ion pair formation has been found and in ~ol~tion~.~~~ to catalyse 13C0 incorporation into HFe(CO),-; this reagent has been exchanged onto the Amberlite A-26 resin and this simplifies purification procedures when using it to synthesize aldehydes from alkyl halides.14' 8aM. Pasquali F. Marchetti. and C. Floriani Inorg. Chem. 1978,17 1684. "M. Pasquali C. Floriani and A. G. Manfredotti J.C.S. Chem. Comm. 1978,921. M. Sato T. Tatsurni T. Kodama M. Hidai T. Uchida and Y. Uchida J. Amer. Chem. Soc. 1978,100 4447. IoaM.J. Nolte and R. H. Reirnann J.C.S. Dalton 1978 932. lobW.Beck and K. Schloter 2.Naturforsch. 1978 33b 1214. lo' P. J. Harris S. A. R. Knox R. J. McKinney and F. G. A. Stone J.C.S. Dalton 1978 1009. 'la K.Inkrott R. Goetze and S. G. Shore J. Organometallic Chem. 1978,154,337.'Ib J. A.Gladysz and W. Tam J. Ore. Chem. 1978,43,2279. l2 J. E.Ellis C. P. Parnell and G. P. Hagern J. Amer. Chem. SOC.,1978,100,3605. 13"G. Fachinetti C. Floriani P. F. Zanazzi and A. R. Zanzari Znorg. Chem. 1978,17 3002. 136 W.F.Edgell S. Hegde. and A. Barbetta J. Amer. Chem. SOC.,1978,100 1406. 14aM.Y.Darensbourg D. J. Darensbourg and H. L. C. Barros Inorg. Chem. 1978,17,297. 14bG. Cianelli F.Monescalchi A. Urnani-Ronchi and M. Panunzio J. Org. Chem.. 1978 43 1598. 3 14 A. J. Deeming and J. Evans Substitution of the organic ligand in C9H10Mo(C0)3(13CO) by several ligands e.g. PPh3 SbPh3 occurs stereospecifically (Scheme 2)? This may be due to the basal site preference of L in the MO(CO)~L intermediate and accordingly if L=CO [or P(OMe)3] there is 13C0 scrambling.Fenske-Hall molecular orbital calculations have been used to follow CO dissociation from MXI(CO)~' and Mn(CO),X (X = H or Br).l6 cis-Labilization effects arise from stabilization of the unsaturated intermediate rather than any interactions in the reactant. l80incorporation into neutral metal carbonyls from aqueous Na"0H has been activated by phase-transfer catalysis using Bun4NI.l7 Scheme 2 The (C,H,)V(CO),' radical anion has been shown to be involved in reduction of alkyl halides by (C,H,)V(CO)3H-.'8 Rates of CO substitution of (C,H,)W(CO),H are non-reproducible and occur photochemically with a quantum yield of >30.19 Small amounts of (CSH5)2M2(C0)6increase the quantum yield and the (C,H,)W(CO); radical is thought to be the chain propagator.Mn(C0); has been generated by pulse radiolysis of Mn,(CO), and Mn(CO),X (X = Br or I)20aand the more stable Mn(C0),(PBu3)~ by extended U.V. irradiation of substituted dimers.206 A number of 17-electron complexes of Groups VI and VII substituted carbonyls have been synthesized by chemical and electrochemical oxidation.21 They are markedly more reactive than their 18-electron counterparts with respect to iso- merization and CO labilization. The effectiveness of CO factored force fields in studying isotopically enriched matrix-isolated metal carbonyls has been discussed,22 and full reports of the photo- chemistry of M(CO) in matrices have been pre~ented.~ Matrix adducts of M(CO) are formed. Polarized photolysis of Ar--MO(CO)~ in Ar-N2 matrices leaves it oriented because of dichroic photodepletion; this does not occur for N2Mo(C0)5.Reorientation to positions less favourable to absorption is thought to involve an Is D. J. Darensbourg and A. Salzer J. Amer. Chem. SOC.,1978. 100,4119. l6 D. L. Lichtenberger and T. L. Brown J. Amer. Chem. Soc. 1978,100,366. '' D. J. Darensbourg and J. A. Froelich J. Amer. Chem. SOC.,1978,100,338. R. J. Kinney W. D. Jones and R. G. Bergman J. Amer. Chem. SOC.,1978,100,635. l9 N. W. Hoffman and T. L. Brown Znorg. Chem. 1978,17,613. W.L. Watz 0.Hackelberg L. M. Dorfman. and A. Wojcicki J. Amer. Chem. SOC.,1978,100 7259. 'Ob D. R. Kidd C. P. Cheng and T. L. Brown J. Amer. Chem. Soc. 1978 100,4103. "OA. M. Bond B. S. Grabaric and J. J.Jackowski Znorg. Chem. 1978,17,2153. 21b A. M. Bond B. S. Grabaric and Z. Grabaric Znorg. Chem. 1978,17 1013. 'Ic A. M Bond R. Colton and M. E. McDonald Znorg. Chem. 1978,17,2842. 22 J. K. Burdett M. Poliakoff J. A. Timney and J. J. Turner Znorg. Chem. 1978,17,948. 23 J. K. Burdett J. M. Grzybowski,R. N. Perutz M. Poliakoff J. J. Turner and R. F. Turner Znorg. Chem. 1978,17,147; J. K. Burdett A. J. Downs G. P. Gaskill M. A. Graham J. J. Turner and R. F. Turner ibid. 1978 17 523. Organometallic Chemistry 315 internal rearrangement of the M(CO)5 frzgment via a trigonal bipyramidal isomer. Ab initio calculations on Cr(C0)5 predict a 'AI(C4")ground state with a 3A;(D3h) state 38 kJ mol-' higher in energy.24 The electronic absorption at -500 nm was attributed to a 'A1+'E transition and should be very sensitive to the matrix environment.The primary process in the photosubstitution of Cr(C0)6 has been assigned as a 1Ale+3T1gtransition (366 nm light) and loss of dissociation efficiency from 100% must be due to radiationless decay.25 Cr(CO),(NO) has been observed as an intermediate in the photochemical reactions sequences between Cr(C0)6 and Cr(N0)4.26 CO dissociation was considered to be the first step in the photo- substitution and -oxidation reactions of Mn(C0)5-;27" the quantum efficiency of the loss of W(CO),X- (X =Br NCO or N3) in CO saturated CHCl was found to vary by 300% with different co~nter-ions.~~~ 1.r. laser irradiation has been used to study change in 13C180 enriched Fe(CO) in a nitrogen matrix.28 A solution of Fe(CO)5 and metal hydroxides in alcohols catalyses the water-gas shift reaction.29a Fe(CO)5 and HFe(CO),- were identified under a high CO pressure at 60 "C and room temperature respectively; formyl complexes were not observed.The salt [HPt(CO)PPr',),]OH has been observed in the catalysis system involving Pt(PPri3) in HCo(CO) has been found to catalyse the H2 reduction of CO to methanol and methyl f~rrnate,~'" and some ruthenium systems which contain [RuI,(CO)~]- in solution catalyse the conversion of MeOAc and even Me20 into EtOAc in the presence of CO (150 atm);306 this last step requires a small pressure of H2 (3-5atm). Small amounts of CH and C2H6 have been detected from the reduction of a co-ordinated CO group in (C5H5)NbH(CO) with hydr~gen.~" Spectroscopic studies on the W(CO)5PR3 AlBr3 metathesis catalyst system indicate that a solvated W(C0),PR3 species is formed via Br3Alt OCW(C0)4PR3.31"O2oxidation then gives rise to W(C0)4Br2.This kind of catalyst system shows stereoselectivity unusual for rnetathesi~.~'~ Selectivity decreases with increasing size of R in cis-and trans-RCH=CHMe. Steric interactions in the formation of the olefin carbene complex must be important rather than those within the metallacyclobutane ring. Dinuclear Carbony1s.-Light induced calorimetry has been used to measure the normal reaction enthalpy for the cleavage of Re2(CO), by 12;32the Re-Re bond 24 P. J. Hay J. Amer. Chem. SOC.,1978 100 241 1. 25 J. Nasielski and A. Colas Inorg. Chem.1978,17 237. 26 S.K.Satika B. I. Swanson 0.Crichton and A. J. Rest Inorg. Chem. 1978 17 1737. 27aR. A. Faltynek and M. S. Wrighton J. Amer. Chem. Soc. 1978,100,2701. 27b R.M. Dahlgren and J. I. Zink J.C.S. Chem. Comm. 1978,863. 28 B. Davies A. McNeish M. Poliakoff M. Tranquille and J. J. Turner J.C.S. Chem. Comm. 1978,36. 29aR. B. King C. C. Frazier R. M. Hanes and A. D. King jun. J. Aqer. Chem. SOC.,1978,100,2985. 29b Y. Yoshida Y. Ueda and S. Otsuka J. Amer. Chem. Soc. 1978 100 3941. 30aJ. W.Rathke and H. M. Feder J. Amer. Chem. SOC..1978,100,3623. 30b G.Braca G. Sbrana G. Valentini G. Andrich and G. Gregorio J. Amer. Chem. Soc. 1978,100,6238. 30c J. A. Labinger K. S. Wong and W. R. Scheidt J. Amer. Chem. SOC.,1978,100,3254. 31aY. Ben Taarit J.L. Bilhou M. Lecomte and J. M. Basset J.C.S. Chem. Comm. 1978,38;J. L.Bilhou A. K.Smith and J. M. Basset J. Organometallic Chem. 1978,148 53. 31b M. Lecomte J. L. Bilhou W. Reimann and J. M. Bassett J.C.S. Chem. Comm. 1978 341. 32 A. W. Adamson A. Vogler. H. Kunkely and R. Wachtor. I. Amer. Chem. SOC..1978,100 1298. 316 A. J. Deeming and J. Evans strength is very much less (218 kJ mol-') than twice the Re-I one. Photodis-sociation of Re2(CO)lo with a 300 nm laser only involves Re-Re cleavage.33 It was estimated that 3 of the available energy (126 kJ mol-') was retained as internal energy in the photofragments. A comparison of the AH' values for homolytic fission of series of Mn2(CO)lo-nL and [CO(CO)~L]~ complexes has been made with the energy of the u+u+ electronic tran~ition.~~ values are substantially smaller AH' and reflect a steric weakening of the metal-metal bond especially for PCy complexes as well as substituent electronic effects.CO~(CO)~ has been found to exist as a mixture of the bridged and two non-bridged forms in solution and frozen The two non-bridged forms have D3dand D2d symmetries with the latter being the high-temperature form. Bridging hydride ligands have been located in a number of crystallographic studies on dinuclear carbonyl~.~~ The different scattering properties of neutrons and X-rays can lead to an apparent discrepancy between the two methods. The electron density maximum of the bridging hydride in Mo~(C,H,)~(CO),(~-H)(~-PM~,) is 0.2 A closer to the Mo-Mo axis than !he centre of nuclear density leading to a shrinkage in the Mo-H distance (by 0.07 A) and a widening of the Mo-H-Mo angle (by 11") in the X-ray Electron deformation densities have been measured by combined X-ray and neutron diffraction measurements on tran~-[(C,H,)Fe(Co)~J~ at low temperatures.37a There are no significant residues along the Fe-Fe axis.Ab initio calculations reproduce the deformation density in this complex.37b A Mulliken overlap population of -0.05 was calculated for the Fe-Fe interaction and it is apparent that a delocalized multicentre picture is better than a simple metal-metal bond when there are bridging ligands present. There has been some discussion about the binding of the bridging carbonyl in Pd' and Pt' dimer~.~~ The CO stretching frequency in Pt2C12(p-CO)(p-dppm)2 is 1638 cm-' suggesting that the ligand may be acting as a four-electron donor as in (l).38a This proposal has been countered with the suggestion that the ligand acts as a a-I \ \ /Ph,P-/-PPh2 two-electron donor-bridging a long metal-metal distance !s the Pd dimers3" [Pd2C12(p-CO)(p-dpam)2 (2) has a Pd-Pd distance of 3.274 A38c1; CO stretching 33 A.Freedman and R. Bersohn J. Amer. Chem. SOC.,1978,100.4116. 34 R. A. Jackson and A. J. Pk Inorg. Chem. 1978,17,997,2330. 35 D. L. Lichtenberger and T. L. Brown Inorg. Chem. 1978,17 1381. 36aH.B. Chin and R. Bau Inorg. Chem. 1978,17,2314. 36b J. L. Peterson P. L. Johnson J. O'Conner L. F. Dahl and J. M. Williams ibid. 1978 17 3460. 36c J.L. Peterson and J. M. Williams ibid. 1978,17 1308. 37rA.Mitschler B. Rees and M. S. Lehman J. Amer. Chem. SOC.,1978,100,3390. 37bM.Bknard ibid. 1978,100,7740. 38aM. P. Brown R. J. Puddephatt M. Rashidi and K. R. Seddon J.C.S. Dalton 1978 1540. 3*bL.Benner and A. L. Balch J. Amer. Chem. SOC.,1978,100,6099. 38c R. Colton M. J. McCormick and C. D. Pannan Ausr. J. Chem. 1978,31 1425. 317 Organometallic Chemistry Ph2AsTAsPh2 I CI C1- Pd' 'Pd -C1 I I Ph As,,AsPh (2) frequencies of -1715 cm-' were reported for the Pd2X2(p-CO)(p-dppm)2 series. The bridging ligand in these dimers at which the Pd-C-Pd angle is 119",has been termed a dimetallated f~rmaldehyde.~~'' Rh' and Ir' dimers have been synthesi~ed.~~ The Rh-Rh distance in (3) is 2.841 8 and the complex participates in a rapid dynamic equilibrium with (4).+ Ph,P /\PP LC1\l-I P,I 'h2 L ,Rh-\ ,Rh,CO -OCIC I The synthesis of (C5H5)2M02(C0)4 has been by thermolysis of (C5H5)2M~Z(C0)6 shown to involve (C5H5)M~(C0)3 The Mo-Mo distance (2.448 8,)is larger than other triple bonded complexes and an interaction between the CO and Mo2 7r systems is This complex forms addition products with soft nucleophiles and electrophiles (I2 and HCl).40" It also reacts with PtL species to form air-sensitive trinuclear complexes (5); [(C5H5)Mo(CO),]2[p-Fe(C0)4]was also synthesized. Both heating and photolysing mixtures of (C5H5),M2(CO) (M = Mo or W) produces some mixed metal dimer~.~" The disappearance quantum yield at 350 nm of Mn2(CO)lo in the presence of PBu3 or P(OEt) is reduced by the presence of CO;41" caged radical pairs are formed by homolysis and these substitute rapidly on separating.Photolysis of the mixed metal and (C5H5)M(CO)3Fe(C5H,)(CO)2 complexes (C5H5)M(CO)3Co(C0)4 (M = Mo or W) also causes homolytic cleavage.416 Rate orders of C1 abstraction from CCl were established. D. Robinson Inorg. Chim. Acra 1978,27 L108. M. Cowie J. T. Mague and A. R. Sanger I. Amer. Chem. SOC.,1978,100,3628. 40rM.D.Curtis and R. J. Klinger J. Organometallic Chem. 1978,161 23. "*R. J. Klinger W. M. Butler and M. D. Curtis J. Amer. Chem. SOC.,1978,100 5034. *&M. H.Chisholm M. W. Extine R. L.Kelly W. C. Mills C. A. Murillo L.A. Rankel and W. W. Reichert Inorg. Chem. 1978 17 1673.41aD. R. Kidd and T. L.Brown J. Amer. Chem. SOC.,1978,100,4095. 41b H.B. Abrahamson and M. S. Wrighton J. Amer. Chem. Soc. 1978,100 1003. A. J. Deeming and J. Evans An efficient synthesis of NaHFe2(C0)8 has been rep~rted."~ This anion was demonstrated to be involved in the first step of the reduction of the olefinic bonds of LYPunsaturated systems viz. formation of Na[RCH2.CH(COR).Fe2(C0)8]. Polynuclear Carbony1s.-The bonding capabilities of transition metal clusters have been assessed by extended Hiickel calculations on ligand-free assemblies of rhodium atoms." An energy separation between the cluster valence orbitals (4d 5s and partly 5p) and high lying sets was considered to give a cut-off which governs the choice of stoicheiometry and structure of polynuclear carbonyls.New methods of treating thermochemical data of carbonyl clusters have been Metal-metal bond strengths were estimated from data on pure metals using a dependence on internuclear distance (adMM-".,) and their proportion of the total bonding energy considered to have been previously overestimated. A neutron diffraction study on H20s3(CO)lo has demonstrated that the two hydride ligands symmetrically bridge the short 0s-0s edge. (0s-H 1.850 A)."' is formed when this hydride reacts with CO~(C~)~~~~~ H3C~O~3(C0)12 and other mixed metal tetranuclear clusters found by treating it with nucleophilic metal cornplexe~."~~ [(C2H4)2PtPR3] [(C2H4)Ni(PPh3)3] MeAuPPh, and [(C2H4)2Rhacac] yielded [H2Os3Pt(C0),,(PR3)] [H20s3Ni(CO)10(PPh3)2] [HAuOs3(CO) 10(PPh3)] and [H20s3Rh(acac)(CO) respectively.Condensation of (C2H4),PtPPh3 with H20s(CO) allowed isolation of (6). Liberation of CO groups by R3N0 oxidation has been used to form substituted metal carbonyls of Mn Re and 0s."' OS~(CO)~,(NCM~)~, thus produced reacts with NEt to form equal amounts of H20s3(C0)10 and HOS,(CO)~~(~-CH-CH:NEt2).48" A similar dehydrogenated ligand has been implicated in the Rh,(CO), catalysed H-D exchange between NEt and D20.48b OS~(CO)~~(NCM~)~ also reacts with HW(CO),(C,H5) to yield the new clusters [HOS~W(CO)~~(C~H~)] 42 J. P. Collman R. G. Finke P. L. Matlock R. Wahren R. G.Komoto and J. I. Brauman J. Amer. Chem. SOC., 1978,100,1119. 43 J. W. Lauher J. Amer. Chem. SOC., 1978,100,5305.44 K. Wade Inurg. Nucl. Chem. Letters 1978,14,71; C. C. Housecroft K. Wade and B. C. Smith J.C.S. Chem. Comm. 1978,765. 45 A. G. Orpen A. V. Rivera E. G. Bryan D. Pippard G. M. Sheldrick and K. D. Rouse J.C.S. Chem. Comm. 1978,723. 46aS. Bhaduri,B.F. G.Johnson J. Lewis,P. R.Raithby,andD. J. Watson J.C.S. Chem. Comm. 1978,343. 46bL.J. Farrugia J. A. K. Howard P. Mitrprachachan J. L. Spencer F. G. A. Stone and P. Woodward ibid.; 1978 260. 47 U. Koelle J. Organornetallic Chem. 1978 155 53; B. F. G. Johnson J. Lewis and D. Pippard ibid. 1978 145 C4. 48aJ. R. Shapley M. Tachikawa M. R. Churchill and R. A. Lashewycz J. Organometallic Chem. 1978 162 C39. 48b R. M. Laine D. W. Thomas,L. W. Cary and S. E. Bottrill J. Amer. Chem. Suc. 1978 100,6527.Organometallic Chemistry 319 and [H30~3W(CO)ll(C5HS) Pyrolysis of OS~(CO)~~P(OM~) has yielded three pentanuclear products with fragmented phosphite ligands.” Two of these [HOs,C(CO)14{ OP(OMe)2}] and [HOs5C(CO)13{OP(OMe)OP(OMe)2}], have central carbides and a distorted trigonal bipyramidal Oss arrangement; the third Os5(CO)lSP(OMe) possesses a square pyramidal Oss geometry with a face bridging P(0Me) group. Extended Huckel calculations based on Fe4(C5H5)48-and Fe,(CO),;- have been used to probe hydride site preferences and the orientation of the M(CO) groups.s1 The M(CO)3 groups prefer to be staggered with respect to the Fe-Fe bonds in the second anion but there was little energy difference between possible arrangements of four added hydrogens bridging four edges in H4R~4(C0)12 (with DZdsym-rnetr~’~~); edge bridging arrangements of C3 (Ru) and C2 (Ru and 0s) were observed for the H3M4(C0)12- ions.526*c Up to three protons have been quan- titatively removed from H,RU,(CO)~~ was using KH.53” While HzR~3(C0)122- found to have three bridging carbonyl groups in solution (using 13C r~.m.r.),’~= the osmium analogue possesses terminal carbonyls only in the HOS~(CO)~S-can be alkylated on the sulphur atom to form a reactive cluster which readily forms adducts in which the thiolate ligand migrates from a p3to a p2site.’ Alkylation of HOS~(CO)~~-with MeS0,F occurs on the oxygen of the bridged carbonyl group;”” site exchange in the M(CO) group in HOS~(CO)~,(COE~) occurs in two stages suggesting a trigonal twist process.Low-temperature protonation of HFe3(C0)11- also occurs on the oxygen of the bridging CO group so H2Fe3(CO)ll has a very different structure from its osmium analogue.556 49 M. R. Churchill F. J. Hollander J. R. Shapley and D. S. Foose J.C.S. Chem. Comm. 1978 534. J. M. Fernandez B. F. G. Johnson J. Lewis P. R. Raithby and G. M. Sheldrick Acta Cryst. 1978 B34 1994;A. G.Orpen and G. M. Sheldrick ibid. 1978 B34,1992; J. M. Fernandez B. F. G. Johnson J. Lewis and P. R. Raithby J.C.S. Chem. Comm. 1978,1015. 51 R. Hoffmann B. E. R. Schilling R. Bau H. D. Kaesz and D. M. P. Mingos J. Amer. Chem. SOC.,1978 100,6088. ’*=R.D.Wilson S. M. Wu R. A. Lowe and R. Bau Znorg. Chem. 1978,17 1271. 52b B. F. G. Johnson J. Lewis P.R. Raithby and C. Zuccaro Acta Cryst. 1978 B34 3765. P. F. Jackson B. F. G. Johnson J. Lewis M. McPartlin and W. J. H. Nelson J.C.S. Chem. Comm. 1978 920. 53aK. E. Inkrott and S. G. Shore J. Amer. Chem. SOC.,1978,100 3954. 53bB. F. G. Johnson J. Lewis P. R. Raithby G. M. Sheldrick and G. Suss J. Organornetallic Chem. 1978 162 179. s4 B. F. G. Johnson J. Lewis D. Pippard and P. R. Raithby J.C.S. Chem. Comm. 1978,551, Acra Cryst. 1978 B34,3767 D. Gavens and M. J. Mays J. Organometallic Chem. 1978,162 389. 55bH. A. Hodali D. F. Schriver and C. A. Ammlung J. Amer. Chem. SOC.,1978,100,5739. A. J. Deeming and J. Evans OS~(CO)~~ reacts with ethylene and PhCCPh under forcing conditions to form OS6(C0),6(CR)2 (R = Me or Ph) derivatives (7).56 Continued reaction with C2H4 yielded OS6(C0)16(MeCCMe)C (8).One of the products of the reaction between OS~(CO)~~ and PhOH at 175-185 "C is H20~3(C0)9(OC6H4) (9; R=H) the structure of which was established by comparison with the benzyl deri~ative.~' This carbon bridged OC6H4 ligand is converted into an oxygen bridged OPh one {in HOs3(CO)l,(p2-OPh)} on treatment with CO at 140 "C. The dynamical properties of M4(CO)12(M = Co or Rh) derivatives in solution have been reported58 and an alternative approach to rationalizing these exchange proces- ses pre~ented.~~ These bridged structures possess an icosahedra of carbonyl groups and site exchange is thought to be via a cuboctahedral transition state as adopted by Ir4(CO)12.60 The symmetry restrictions outlined depend on the cuboctahedron being a transition state rather than an intermediate.The C,isomer of (C5H5)3Rh3(C0)3 undergoes a rapid intramolecular exchange process without isomerizing to the C3 structure probably involving one CO group migrating from a p2to a p3site.61 A reinvestigation of the reduction of (C5H5)2Rh(C0)2 by sodium amalgam has led to the isolation of [PPN][(C5H5)2Rh3(CO)4] (10) which possesses semi face bridging carbonyl groups.62 Extended Huckel calculations suggest that the organic ligand in CO~(CO)~CCH~+ would avoid a central position.63 CO~F~(CO)~S acts as a sulphur donor in its Cr(C0)5 It was observed that pyrolysis of ASM~~M(CO)~(C~H~) add~ct.~~ (M = Cr Mo or W) substituted tricobalt carbon clusters resulted in incorporation of the hetero transition metal centre 65a and this reaction has been used to synthesize the chiral clusters (1l).656 It is interesting in this regard that the carbide Rh12C2(C0)25 forms "T.R.Eady J. M. Fernandez B. F. G. Johnson J. Lewis P. R. Raithby and G. M. Sheldrick J.C.S. Chem. Comm. 1978,421. 56bJ. M. Fernandez B. F. G. Johnson J. Lewis and P. R. Raithby Acta Cryst. 1978 B34 3086. 57 K. A. Azam A. J. Deeming I. P. Rothwell M. B. Hursthouse and L. New J.C.S. Chem. Comm. 1978 1086. '* S. Aime L. Milone D. Osella and A. Poli Inorg. Chim. Acta 1978,30,45;J. Evans B. F. G.Johnson J. Lewis T. W. Matheson and J. R. Norton J.C.S. Dalton 1978 626. 59 B. F. G. Johnson and R. Benfield J.C.S. Dalton 1978 1554. 6o M.R. Churchill and J. P. Hutchinson Inorg. Chem. 1978,17,3528. R. J. Lawson and J. R. Shapley Inorg. Chem.. 1978,17,772. 62 W. D. Jones M. A. White and R. G. Bergman J. Amer. Chem. SOC.,1978,100,6770. 63 B. E. R. Schilling and R. Hoffmann J. Amer. Chem. SOC.,1978,100,6274. 64 F. Richter and H. Vahrenkamp Angew. Chem. Internat. Edn. 1978,17,444. 65"H. Beurich and H. Vahrenkamp Angew. Chem. Internat. Edn. 1978,17 863. 6sbF.Richter and H. Vahrenkamp ibid. 1978,17,864. Organometallic Chemistry 321 M = Cr Mo and W (11) enantiomorphous crystals.66 Treatment of tetraglyme solution of [Rh(CO),?acac] with a metal carbonylate and H2S (or SO,) under 300 atmospheres of H and CO yields a salt of [Rh17(S)2(C0)32]3-, which has an encapsulated S-Rh-S linkage within a D4d Rh16 envir~nment.~~ Two new centred polynuclear anions Rh15(C0)273-and Rh14(C0)254- have been isolated.68 While the former has a Rhls structure with hcp and bcc character the latter is a bcc fragment.Pt12(C0)242- undergoes a rapid metal exchange'with Rh12(CO)302- under CO to form the mixed metal PtRh,(CO),,- a derivative of Rh,(CO),, characterized by X-ray diffraction and 19'Pt Treatment of PtL2C12 complexes with metal carbonyl anions has yielded a number of new These include Pt2C02(CO)s(p2-CO)3(PEt3)2, Pt3C02(CO),(p2-CO),(PEt,) (trigonal bipyramidal Pt3C02 a~rangement),~~' Pt5(CO)(p2-CO)s(PR3) (edge bridged tetrahedron of Pt atom^)^" and Pd2M02(CsH5)2(p3-CO)2(p2-CO),(PEt,) (12)70d possessing a Pd-Pd bond (2.582 A).Carbonylation of P~(OAC)~ has yielded a rectangular cluster [Pd(CO)(OAc)] (13);71the CO bridged 0 66 V. G. Albano P. Chini S. Martinengo M. Sansoni and D. Strumolo J.C.S. Dalton 1978,459. 67 J. L. Vidal R. A. Fiato L. A. Cosby and R. L.Pruett Inorg. Chem. 1978,17 2574. "S.Martinengo G. Ciani A. Sironi and P. Chini J. Amer. Chem. Soc. 1978,100 7096. 69 A.Fumagilli S.Martinengo P. Chini A. Albinati S. Bruckner and B. T. Heaton J.C.S. Chem. Comm. 1978,195. 'OOJ. P. Barbier and P. Braunstein J. Chem. Research (S),1978,412. 70bJ. P. Barbier P. Braunstein J. Fischer and L. Ricard Inorg. Chim. Acra 1978 31 L361. 70c J. P. Barbier R. Bender P. Braunstein J. Fischer and L. Ricard J. Chem. Research (S),1978 230. 70d R. Bender P. Braunstein Y.Dusavoy and J. Protus Angew. Chem. Internat. Edn. 1978,17 596. 71 I. I. Moiseev T. A. Stromnova M. N. Vargaftig G. Ja. Mazo L.G. Kozima and Yu.T. Struchkov J.C.S. Chem. Comm. 1978,27. A. J. Deeming and J. Evans edges (2.663A) are substantially shorter than the acetate bridged ones (2.909A). The product of co-condensing nickel and pentane at -196 "C and subsequent warming in stages is a powder containing nickel carbon and hydrogen.72 ESCA measurements fit sp2 or sp3 carbon environments and treatment of the powder with H2or H20yields C1-C5 hydrocarbons. Pentane cleavage is thought to occur before warm up. Materials produced by pyrolysing supported Rh Ir and Pt carbonyl clusters catalyse H reduction of C0.73 Both initial cluster nuclearity and support basicity influence the product distributions with more basic supports favouring alcohols rather than hydrocarbons.Hydrocarbons are also produced on 7-A1203in the absence of hydrogen due to involvement of surface hydroxy-gro~ps.~~ Total cluster decomposition was generally observed above 250 "C;Os3(CO)1z and OS~(CO)~~ were exceptions. Water is cleaved by Ru3(CO) 12-Si02pyrolysed systems liberating H2.75 Subsequent exposure with methane liberates CO and more H,; addition of N2to the gas mixture yields NH3. The interactions between Rh6(CO), and Si02,76a functionalized silicas766 and functionalized polymers76c have been studied. Substi- tuted clusters are formed at first and subsequent aggregation of the rhodium particles was observed in the polymer system.Triosmium clusters have been anchored to silica by phosphine and bridging ethynyl ligands and characterized by i.r. comparisons with isolable analogues,77u a technique also used to establish the binding of phosphine substituted Ir4(CO)12 derivatives to -PPh2 functionalized The bridging ligand may hinder metal aggregation or breakdown. An alternative method using the terdentate M~S~(PBU~)~ ligand has been [RU~(CO)~(M~S~(PBU~)~}] was synthesized and found to have three semi-bridging carbonyl groups. 72 S. C. Davis and K. J. Klabunde J. Amer. Chem. SOC. 1978 100 5974. 73 M.Ichikawa Bull. Chem. SOC.Japan 1978,51 2268 2273; J.C.S. Chem. Comm. 1978 566. 74 A. K. Smith A. Theolier J. M. Basset R. Ugo D. Commereuc and Y. Chavin J. Amer.Chem. SOC. 1978,100,2590. 75 S. Naito and K. Tamaru J.C.S. Chem. Comm. 1978 1105. 76nJ. L.Bilhou V. Bilhou-Bougnol W. F. Graydon J. M. Basset A. K. Smith G. M. Zanderighi and R. Ugo J. Organometallic Chem. 1978 153 78. 76bH. Knozinger and E. Rumpf Inorg. Chim. Acta 1978,30 51. 76c M.S.Jarell B. C. Gates and E. D. Nicholson J. Amer. Chem. SOC. 1978 100 5727. 77aS. C.Brown and J. Evans J.C.S. Chem. Comm. 1978,1063. 77b J. J. Rafalko J. Leito B. C. Gates and G. L. Schrader jun. J.C.S. Chem. Comm. 1978 540. 77rJ. J. De Boer J. A. van Doorn and C. Masters J.C.S. Chem. Comm. 1978 1005. 323 Organometallic Chemistry 2 Carbonyl Analogues and CO Complexes The reported anions Re(CN)64- and Re(CN)s3- have been reformulated as Re(CN)74-.78a Some chalcogenide bridged polynuclear cyanides of the types [Re4(CN),,(p3-E)I4-(E = S and Se) and [Rez(CN)8(p2-S)]2- were chara~terized.'~' Fe(bip~)~(CN)~ The reduces Br03- and S2Og2-by an outer-sphere mechanis~n.'~~ rate of the second reaction in aqueous methanol decreases with increasing propor- tions of methanol and this appears to be due to a destabilization of the transition Change transfer excitation of tran~-[Pt(CN)~X~]'-(X = C1 Br or N3) promotes reductive elimination of two X radicals.80 The unstable N; radicals liberate Nz rapidly and do not recombine with the Pt atoms.The mechanisms of luminescence quenching of Cr(bi~y),~' and M(bipy),'+ (M = Ru or 0s) by cyano complexes include energy transfer e.g. CI-(CN)~~- reductive electron transfer (e.g.Fe(CN),"-) and oxidative electron transfer e.g. Fe(CN)63-.81a Solutions and salts of [RU(NH~)~~~]~+ with Fe(CN);- exhibit an outer-sphere intervalence charge transfer absorption in the near i.r.81b An extended Hiickel tight-binding scheme has been used to study the band structure in Pt(CN),'-chains.82 Partial oxidation of 0.3 electrons per Pt was found to give an energy minimum when the Pt-Pt separation was less than 3 A. This separation has a marked effect on the conductivity of these materials and depends upon the counter ions.83a Pt-Pt distances of 2.910 and 2.930 A were observed for (NH4)2[Pt(CN)4]Clo,3, 3H20 whereas in the potassium and some anhydrous separations of -2.85 A were apparent. The thiocarbonyl complexes Fe(C0)4CS84a and Fe(TPP)CSg4' have_ been synthesized using C12CS.Interaction of (CsHS)Fe(CO)z- with (PhO),CS has yielded (CSHS)zFez(CO)3(CS).8s S-alkylation of the bridging CS group occurs with OsHX( CO) ( Cs)(PPh3)25Os(CO)2X(PPh,)2(CHS) NaBH4 OS(CO)~(PP~~)Z(V 2-CHzS) OSC~~(CO)~(PP~~)~ + MeSH aOSC~(CO)~(PP~~)~(SM~) Scheme 3 78aW. P. Griffith P. M. Kiernan and J. M. Bregeault J.C.S. Dalton 1978 1411. 78bM. Laing J. M. Bregeault and W. J. Griffith Znorg. Chim. Acra 1978 26 L27. 79aJ. P. Birk and S. G. Kozub Znorg. Chem. 1978 17 1186. 79bM. J. Blandamer J. Burgess and R. J. Haines J.C.S. Chem. Comm. 1978 963. A. Vogler A. Kern B. Fusseder and J. Huttermann Z. Nafurforsch 1978 33b 1352; A. Vogler A. Kern and J. Huttermann Angew. Chem. Internat. Edn.1978 17 524. 'laA. Juris M. F. Manfrin M. Maestri and N. Serpone Znorg. Chem. 1978 17 2258. 'lbJ. C. Curtis and T. J. Meyer J. Amer. Chem. Soc. 1978,100,6284. '* M.-H. Whangbo and R. Hoffrnann J. Amer. Chem. SOC. 1978,100,6093. 83aP. L. Johnson A. J. Schulz A. E. Underhill D. M. Watkins D. J. Wood and J. M. Williams Inorg. Chem. 1978,17,839. 83b G. Hegor H. .I.Dieseroth and H. Schulz Acta. Cryst. 1978 B34 725. 83c R. K. Brown and J. M. Williams Znorg. Chem. 1978,17 2607; A. J. Schultz D. P. Gerrity and J. M. Williams Actu Cryst. 1978 B34 1673. 84aW. Preetz J. Organomelallic Chem. 1978 146 C23. 84bH. D. Mansuy J. P. Battioni and J. C. Chottard J. Amer. Chem. SOC. 1978 100,4311. R. E. Wagner R. A. Jacobson R. J. Angelici and M. H. Quick J. Organometallic Chem.1978,148 C35; M. H. Quick and R. J. Angelici ibid. 1978 160 C31. A. J. Deeming and J. Evans Meerwein reagents. A thiocarbonyl group bound to 0s has been reduced in a stepwise manner ultimately to MeSH as in Scheme 3.86 Isocyanide analogues of iron and cobalt dinuclear carbonyls have been reported. Fe2(qNEt)9 produced by photolysis of Fe(CNEt), has three bridging ligands with a CNC mean of 123°.87" Co2(CNAr) derivatives have two isocyanide bridges."' The dimers of [Rh(CNR)4]' and [Rh2{CN(CH2),NC}4]2' have been studied." A Rh-Rh distance of 3.193 A was observed in a crystal of [Rh(CNPh)4]2(BPh4)2.88c Oxidation of the p-tolyl derivative with I resulted in isolation of Rh2(CN-p-tolyl)812 the Rh-Rh separation being 2.785 Dissociation of [Ir(CNMe)4]22' in solution has been photoindu~ed.~~ While pyrolysis of OS~(CO)~ ICNBu' yielded a disubstituted derivative of OS~(CO)~~, direct interaction of the hexamer with CN-p-tolyl gave an addition compound (14) in which one isocyanide ligand is a four-electron donor.91 An alternative four electron arrangement has been observed for Mn2(dppm)2(C0)4(p2- CN-p-tolyl) in which one Mn atom bonds to the carbon atom and the other to both C and N atoms.92 Co(Pr-sa1en)K reversibly binds CO in thf solution to give the red adduct Co(Pr- ~alen)KCO~(thf).~~ The C02 ligand is carbon-bonded to the cobalt atom and the oxygen atoms interact with two K' ions.An 7' bonding mode has been observed for AgC02 prepared in an Ar-C02 matrix at -10-25 K.94 T.J. Collins and W. R. Roper J. Organometallic Chem. 1978,159 73. 870J.M. Bassett M. Green J. A. K. Howard and F. G. A. Stone J.C.S. Chem. Comm. 1978 1000. 'l6Y. Yamamoto and H. Yamazaki Inorg. Chem. 1978,17 3111. 88aV.M. Miskowski G. L. Nobinger D. S. Kliger G. S. Hammond N. S. Lewis K. R. Mann and H. B. Gray J. Amer. Chem. Soc. 1978,100,485. 886K. Kawakami M. Okajima and T. Tanaka Bull. Chem. SOC.Japan 1978,51,2327. 88c K. R. Mann N. S. Lewis H. B. Gray and J. G. Gordon 11 Znorg. Chem. 1978,17 829. 89 M.M. Olmstead and A. L. Balch J. Organometallic Chem. 1978,148 C15. 90 G. L. Geoffroy M. G. Bradley and M. E. Keeney Znorg. Chem. 1978,17,777. " C. R. Eady P. D. Gavens B. F. G. Johnson J. Lewis M. C. Malatesta M. J. Mays A. G. Orpen A. V. Rivera G. M. Sheldrick and M.B.Hursthouse J. Organometallic Chem. 1978,149 C43; A. V. Rivera G. M. Sheldrick and M. B. Hursthouse Acra Cryst. 1978 B34 1984; A. G. Orpen and G. M. Sheldrick ibid. 1978 B34 1989. 92 L. S. Benner M. M. Olmstead and A. L. Balch J. Organometallic Chem. 1978 159,289. 93 G. Fachinetti C. Floriani and C. F. Zanuzzi J. Amer. Chem. SOC., 1978,100,7405. 94 G. A. Ozin H. Huber and D. McIntosh Znorg. Chem. 1978 17 1472. Organometallic Chemistry 325 3 Alkyls Aryls and Acyls Photolysis of Li2C2 at -45°C produced a species which gave a mass spectrum attributable to Li4C4.95 Ab initio calculations indicate face-bridging sites for the Li atoms. Hydrolysis liberated acetylene rather than tetrahedrane. Inversion proces- ses of alkyl-lithiums have also been studied by ab initio calculations and it was concluded that the planar intermediate was best stabilized by an Li-Li edge.96 Inversion of silyl- and germyl-lithiums is slow having an activation energy of at least 100 kJ m01-l.~' Co-condensation of alkyl iodides with Ca Sr or Ba has yielded RMI derivative^.^^ I The reaction between Me3& C(SiMe3)SiMe2 and DMSO to give (SiMe,)C:C(SiMe3)SiMe20SiMe2 is considered to involve Me2Si0.99 The reactivity -of Me2CCMe2SiMe2 (a source of SiMe2) is modified by the presence of PPh3 suggesting the involvement of the ylide Ph3P'-SiMe2.loo Elimination of Me,SiCl from (SiMe3)2SiMeC1 at 700 "C leaves the Me,Si-SiMe moiety which dimerizes to Me2SiCH2SiH2kH2 and MeHSiCH2SiHMeCH2. lo' This fragment appears to be responsible for reactions involving Me2% SiMe2.Flash vacuum pyrolysis (-7 10 "C) of diallylsilanes provided a simple route to silacyclobutanes. lo* STO-3G ab initio calculations indicate that the resonance energy of the unstable silabenzene is 3 that of benzene;103a pyrolysis of C5H5Si(Me)(CH2CHCH2) in the presence of CF3CCCF3 yields the adduct of silatoluene (C,H,SiMe). lo3' Chloride abstraction from Me2SiC12 with Li has yielded a mixture of medium ring cyclosilanes (Me2Si) (n= 5-9);104 the penta- and hexa-silanes have large plastic crystal temperature ranges. Reduction of A1Bui3 by potassium produced a compound formulated as K2(B~i3AIAlB~i3).105 The A1Cl3 0-complexes of cyclobutadienes e.g. Me4C4AlC13 are dynamic and exchange predominantly by 1,2 AlCl shifts.lo6 Two Ar6Sn2 dimers (Ar = 2,4,6-Me&& and 2,4,6-Et3C,H2) reversibly cleave having Sn-Sn dissociation energies of 190 and 125 kJ mol-I respe~tively.'~' TCNE inserts into an Sn-R bond in R4Sn derivatives both thermally or photochemic- ally.lo' These processes follow a common electron transfer mechanism involving the charge transfer complexes (R,Sn'TCNE-).Oxidative addition reactions of PhBr to Sn[CH(SiMe3),12 or Sn[N(SiMe3),12 are catalysed by a more reactive halide e.g. 95 G. Rauscher T. Clark D. Poppinger and P. von R. Schleyer Angew. Chem. Internat. Edn. 1978,17 276. 9d T. Clark P. v. R. Schleyer and J. A. Pople J.C.S. Chem. Comm. 1978 137. 97 J. B. Lambert and M. Urdaneta-Perez J. Amer. Chem. SOC., 1978,100 157.98 B. G. Gowenlock W. E. Lindsell and B. Singh J.C.S. Dalton 1978,657. 99 D. Seyferth T. F. 0.Lim and D. P. Duncan J. Amer. Chem. SOC.,1978,100 1626. lo" D. Seyferth and T. F. 0.Lim J. Amer. Chem. SOC.,1978 100 7074. '01 W. D. Wulff W. F. Goure andT. J. Barton J. Amer. Chem. Soc. 1978 100,6236. Io2 F. Block and K. Revelle J. Amer. Chem. SOC., 1978 100 1630. '03..H. B. Schegel B. Coleman and M. Jones jun. J. Amer. Chem. SOC.,1978,100 6499. "I3*T. J. Barton and G. T. Burns J. Amer. Chem. SOC.,1978 100 5246. 104 K. Matsumura L. Brough and R. West J.C.S. Chem. Comm. 1978,1092; D. W. Larsen B. A. Soltz F. E. Stary and R. West J.C.S. Chem. Comm. 1978 1093. '(" H. Homberg and S. Krause Angew. Chem. Znternat. Edn. 1978 17 949. P. B. J. Driessen and H.Hogeveen J. Amer. Chem. SOC.,1978 100 1193. lo' H. U. Buchlaus and W. P.Neumann Angew.Chem. Znternat. Edn. 1978 17 59. lo' K. Mochida J. K. Kochi K. S. Chen and J. K. S. Wan J. Amer. Chem. SOC.,1978,100,2927. A. J. Deeming and J. Evans EtBr.'" The reaction products are solvent dependent and are thought to involve first Et' and the Ph' radicals; the latter are intercepted in THF. The first stable aryl complex of Iv has been synthesized (15) and in fact is stable indefinitely when crystalline.' lo AH;values have been measured for the M(C5H5)2Me2 complexes and the M-Me bond strengths estimated to be 149.5 and 197.8 kJ mol-' for Mo and W respec-tively.11' Preferred binding modes in C5H5X complexes have been investigated by exten- ded Huckel calculations."2 The critical factor is the energy of the e acceptor set on X.This is low for Mn(CO), favouring q5 co-ordinations but high for Me q1 co-ordination being adopted. The decreasing barrier to rotation on changing Me through SiH3 and GeH3 to SnH3was correlated to the stabilization of an acceptor e set of orbitals. There have been a number of examples of restricted rotation in metal alkyls. Barriers of over 18kJ mol-' were measured for rotation about metal-methyl bonds e.g. (C5H5)2ZrMe2,'13a and these were raised to 49-64 kJ mol-' in the more hindered (C5H5)2Zr(R)CH(SiMe3)2 derivative^."^^ A long Zr-C bond (2.329A) was observed for one of this series (R =Ph). A barrier of 36 kJ mol-' was found for rotation about the C-C bond in (CO)5WCHOMe-C6H3Me,.'13c The MMe63- anions of Er and Lu have been ~ynthesized;"~" although thermally stable they are very water sensitive.Seven- and eight-co-ordinate THF adducts of MBut4-(M = Sm Er or Yb) are similarly air- and rnoisture-sen~itive.'~~~ Thermo-lysis of the samarium complex at 40 "C yielded 3.25 mol of Me3CH and 0.5 mol of ethylene per mol of complex and there were no /3-hydride elimination products. While LiCH2SiMe3 forms MR3(THF)2 and M%- complexes with Y Er or Yb the more bulky LiCH(SiMe3)2 yields MClR3- found to have tetrahedral co-ordination for Yb."' No 89Y coupling was observed in the 13C n.m.r. spectrum of Y(CH,SiMe,),-at room temperature indicating a rapid intermolecular exchange of '09 M. J. S. Gynane M. F. Lappert S. J. Miles and P.P. Power J.C.S. Chem. Comm. 1978 192. R. L. hey and J. C. Martin J. Amer. Chem. SOC.,1978,100,300. 'I' J. C. G. Calado A. R. Dias J. A. Martinho Simoes and M. A. V. Ribeira Da Silva J.C.S. Chem. Comm. 1978,737. N. Trong Anh M. Elian and R. Hoffmann J. Amer. Chem. SOC.,1978,100 110. 113aR.F.Jordan E. Tsang and J. R. Norton J. OrganometallicChem. 1978 149 C53. '13' J. J. Jeffery M. F. Lappert N. T. Luong-Thi J. L. Atwood and W. E. Hunter J.C.S. Chem. Comm. 1978,1081. C. P.Casey S. W. Polichnowski H. W. Tuinstra L. D. Albin and J. C. Calabrese Znorg. Chem. 1978 17 3045. 'I4=H. Schumann and J. Miiller Angew. Chem. Znternar. Edn. 1978,17 276. 114bA.L. Wayda and W. J. Evans J. Amer. Chem. SOC.,1978 100,7119. J. L. Atwood W. E. Hunter R. D. Rogers J.Holton J. McMeeking R. Pearce and M. F. Lappert J.C.S. Chem. Comm. 1978,140. Organometallic Chemistry -CH2SiMe3 groups. MR3 (M=Cr V or Ti) and MR3Cl (M=V Zr or Hf) complexes of the CH(SiMe3)2 ligand have been reported.116a The CrR3 species is slightly non-planar (C-Cr-C angle 117.6'). Cr(CPhCMe2)4 has a tetrahedral geometry and there is little evidence of multiple Cr-C bond character.'l6' The Re-C bond lengths (-2.025 A) in trigonal bipyramidal RePh3(PEt2Ph) indicate some v-bonding effe~ts;"~ the phenyl rings are nearly in the equatorial plane. Several ortho-metallated Cr2 complexes e.g. (16) have been osynthesized and possess very short Cr-Cr formally quadruple bonds (-1.83 A).118The bond length in Cr2[(CH2)2PMe2]4is slightly longer (1.895 Other quadruply bonded alkyls identified have included the W2Mes4- anion and mixed acetate-alkyls of Re"'.12o Reaction of Cr2(OA~)4 with Mg(CH2SiMe3) in the presence of PMe3 has yielded (17).121 The Cr-Cr bond (2.1007 A)is asymmetrically bridged by two alkyl Me,P CH,SiMe, \/ /\ Me,SiH,C PMe (17) groups and one hydrogen of each methylene group is close (2.25 A) to a chromium atom.Bridging methyl groups have been identified in (MeCHCHCHMe),Ni,- (p-Me)2122n Lanthanide derivatives of this latter and (C5H5)2Y(p-Me)2AlMe2.'22' II6OG. K. Barker M. F. Lappert and J. A. K. Howard J.C.S. Dalton 1978 734. 116bC. J. Cardin D. J. Cardin and A. Roy J.C.S. Chem. Comm. 1978,899. 'I7 W.E.Carroll and R.Bau J.C.S. Chem. Comm. 1978,825. F. A. Cotton and S.Koch Inorg. Chem. 1978,17,2021;F.A. Cotton S. A. Koch and M. Millar ibid. 1978,17,2084,2087. 'I9 F. A. Cotton B. E. Hanson and G. W. Rice Angew. Chem. Internat. Edn. 1978,17,953. '''OD. M. Collins F. A. Cotton S. A. Koch M. Millar and C. A. Murillo Znorg. Chem. 1978,17,2017. IZobR.A. Jones and G. Wilkinson J.C.S. Dalton 1978 1063. R. A. Anderson R. A. Jones and G. Wilkinson J.C.S. Dalton 1978 446; M. B. Hursthouse K. M. Abdul Malik and K. D. Sales ibid. 1978 1314. 1220C. Kruger J. C. Sekutowski H. Berke and R. Hoffmann 2.Naturforsch. 1978,33b 1110. ""G. R. Scollary Aust. J. Chem. 1978 31,411. A. J. Deeming and J. Evans type and also [(CSH5)2MMe]2 complexes act as homogeneous ethylene poly- merization catalysts. 122c The dimers are in rapid equilibrium with monomers under polymerization conditions and are deactivated by elimination of alkanes involving hydrogen abstraction from the cyclopentadienyl rings.A large isotropic shift has been observed for the 'H resonance of partially deuteriated HOS~(CO)~~CH~.'~~" One hydrogen of the bridging group is thought to be interacting strongly with an osmium atom giving a rapid equilibrium between two inequivalent sites. This hydrogen is transferred to the metal triangle in the formation of H20s2(CO)loCH2 in rapid equilibrium with its methyl isomer.123b An unusual metal-carbon interaction has been identified in (18),formed by addition of Me1 to C6H3(CH2NMe2)2PtBF4.'24 The platinum is involved in an q' interaction to the arene ring (Pt-C 2.18 A) and this is suggested to be a model for a reductive elimination reaction co-ordinate.While oxidative addition of BzCl to Pd(PEt,) occurs with inversion of configura- tion at carbon (72% stereospecific) there is only 19% net inversion using BzB~;'~'" SN2and radical pathways may be competing. Isomerization of alkyl groups has been observed during the addition of acyl chlorides to IrC1(PPh3) (n =2 or 3)to give RIrC12(CO)(PPh,)2.'2sb This probably involves a P-hydride elimination-olefin insertion sequence. ci~-ptHMe(PPh~)~ eliminates methane at -25 "C by a first order process;'26 the rate determining step is CH elimination and PtL3 species are formed rapidly with added ligands. Two mechanisms have been identified for the cleavage of activated CH bonds by HM(Np)(dmpe) (M =Fe Ru,or 0s) to form HMR(drn~e)~.'~' One is rapid electrophilic attack (e.g.by HCN) and the other involves slow elimination of naphthalene followed by rapid oxidative addition of RH (e.g.MeCN).Elimination of methylcyclohexane from (CsHs)2Zr(H)CH2C6H1 is promoted by H2.1280 Deu- terium was incorporated into the alkyl group in the presence of D2so as well as a simple elimination procedure from a (C5H5),ZrHR-D2 addition complex the alkyl hydride is undergoing a 0-hydride elimination-olefin insertion side process. Eli- mination of isobutane from the related (CsMe5)2Zr(H)CH2CHMe2 has also been studied.128bA primary kinetic isotope effect was observed only when deuterium was 122c D. G. H. Ballard,A. Courtis,J. Holton J. McMeeking and R.Pearce,J.C.S. Chem. Comm. 1978,994. IzJaR.B. Calvert and J. R. Shapley J. Amer. Chem. SOC.,1978,100 7726. 1236 R. B. Calvert J. R.Shapley A. J. Schultz,J. M. Williams S. L. Suib and G. D. Stucky J. Amer. Chem. SOC.,1978 100 6241. G. van Koten K. Timmer J. G. Noltes and A. L. Spek J.C.S. Chem. Comm. 1978 250. It5OY. Becker and J. K. Stille J. Amer. Chem. Soc. 1978 100 838. lZJb M. A. Bennett R. Charles and T. R.B. Mitchell J. Amer. Chem. SOC.,1978 100 2737. L. Abis A. Sen and J. Halpern J. Amer. Chem. SOC.,1978 100,2915. C. A. Tolman S. D. Iltel A. D. English and J. P. Jesson J. Amer. Chem. SOC.,1978,100,4080,7577. IZsaK.I. Gel1 and J. Schwartz J. Amer. Chem. Soc. 1978,100 3246. 1Z8b D. R. McAlister D. K. Erwin and J. E. Bercaw J. Amer.Chem. Soc. 1978 100 5966. Organometallic Chemistry present in the ring methyl groups so the hydrogen is eliminated from one of these fragments. This process is also accelerated by H2 but in this case there was exclusive incorporation of H (D) from Hz(D2) gas in the isobutane. Oxidative addition to the intermediate (C5Me,)(C5MeSH)ZrR was proposed. Hydrogen addition to the cyclopentadienyl ring is also thought to be the initial step in the conversion of [(C,H,)CO(PM~~)~COM~]PF~ and CH using NaH.lZaC into (CSH5)Co(CO)(PMe3) Mo2Et2(NMe2) eliminates ethylene and ethane on treatment with C02,yielding MO~(O~CNM~~),.'~~ After initial loss of ethylene dinuclear elimination of ethane is proposed converting a formal metal-metal triple bond into a quadruple one.Reductive coupling from R,Fe(bi~y)~ and Ar2Ni(PEt3) has been induced by and in the latter case electr~chemical,'~~~ oxidation. Ni"' species were observed at -50°C and elimination occurs above that temperature. The stereo- chemistry of electrophilic M-C bond cleavage in cis-[(threo-PhCHDCHD)Mn(CO),PEt,] varies with the ele~trophile.'~' Inversion at carbon is dominant with Clz or Br in non-polar solvents but the degree of retention increases with solvent polarity and electrophile size (I2 or HgX2). SE2retention and inversion pathways are thought to compete. The extended Huckel method has been applied to the migration reaction pathway of MeMn(C0)5.'32 The five co-ordinate acetyl intermediate and transition state are close in energy and the major part of the activation is due to the destabilization energy of the uMn-Me orbital.A hydride shift was computed to have a lower energy barrier. Me(CO)Mn(CO)5 has been observed when MeMn(CO) is pressurized with CO (300atrn).', Subsequent exposure to H2 liberated acetaldehyde with the manganese as Mn,(CO),,; other systems were similarly studied but did not yield CH3CH0. The rate of alkyl migration in RFe(CO),- in the presence of PPh is highly dependent upon the counter ion.', Cation co-ordination to the carbonyl oxygen promotes alkyl migration to that group. Two diastereomers have been observed for (CSHS)2Zr(Ar)COAr (Scheme 4) and it is apparent that the initial CO attack on the diary1 is from outside the Ar groups to yield the first q2-aroyl complex.'35 Reaction of MoC1(CH2SiMe3),PMe3 with CO affords the q2-acyl > -6OT -78°C -Ar Ar Scheme 4 128c H.Werner and W. Hoffmann Angew. Chem. Internat. Edn. 1978,17,464. lZ9 M. H. Chisholm D. A. Haitko and C. A. Murillo J. Amer. Chem. Soc. 1978,100,6263. 130aT.T. Tsou and J. K. Kochi J. Amer. Chem. Soc. 1978,100 1634. 13'*M. Almemark and B. Akermark J.C.S. Chem. Comm.. 1978,66. 13' D. Dong,B. K. Hunter and M. C. Baird J.C.S. Chem. Comm. 1978.11. 13' H. Berke and R. Hoffmann J. Amer. Chem. Soc.,1978,100,7224. 133 R. B. King A. D. King jun. M. Z. Iqbal and C. C. Frazier J. Amer. Chem. Soc. 1978,100,1687. 134 J. P. Collman. R. G. Finke J. N. Cause,and J. I. Brauman J. Amer. Chem. Soc.. 1978,100,4766. 13' G. Erker and F. Rosenfeldt Angew.Chem. Znternar. Edn. 1978 17 605. 330 A. J. Deeming and J. Evans (p-C1)2[M~(q2-COCH2SiMe3)(C0)2PMe3]2. 136 CO is partially reduced by zirconium alkyls and hydrides. 13' For example insertion into (C5Me5)2ZrMe2 yields first (C5Me5),Zr(Me)COMe and then the metallocyclic complex (C,Me,),Zr-0-CMetCMe-0. The same ligand is produced by the ready CO incorporation into (C5Me5),MMe2 (M =Th or U).138 An X-ray diffraction study on the thorium complex indicated that the two metal atoms are bridged by two such ligands to form a ten-membered ring. A mononuclear complex analogous to the zirconium one is produced by the reaction of (C5Me5),M(CH2SiMe3) (M =Th or U) with CO. However an SiMe3 migration occurs on insertion into (C5Me5)M(Cl)- (CH2SiMe3)3 and (C,Mes)2M(C1)O(SiMe3)2:CH2 results.Alkyl complexes such as NiR,(bipy) and NiRX(bipy) react with CH,C12.'39 NiCl,(bipy) is the inorganic product and the organic ones indicate that CH has been inserted into a proportion of the Ni-C bonds prior to elimination. Diphenyl-acetylene is doubly methylated by (C5H5)CoMe2PPh3 (Scheme 5).14' Labelling studies demonstrate that the methyl transfers and hydrogen migration processes are all intramolecular. Q PhC:CPh* M + M + I Ph,P so Me Ph Ph Ph Ph Me 93Yo 7Yo Scheme 5 A number of tantallacyclopentane derivatives has been synthesized by the reac- tion of (C5H5)TaC12(CHBu') with olefins. For example propene moieties are coupled to yield (C5H5)TaC12(CH2CHMeCHMeCH2), and these complexes will catalyse olefin dimerization.14' The relationships between nickelacylopentanes and bis-olefin complexes have been examined in some detail. 142 While (PPh3)2Ni(CH,)4 eliminates mostly cyclobutane and no scrambling of CD groups was observed in a labelled complex (Scheme 6) the tris-phosphine complex which largely eliminates ethylene does scramble CD groups intramolecularly [(C5H5),fi(CD2CHZCH2CD2) behaves similarly]. PPh3 suppresses the iso-merization which is thought to occur uia an isomer of (PPh3)2Ni(CH2)4, which can uncouple to form a bis-olefin complex from which ethylene is slowly eliminated. 13' E. Carmona Guzman G. Wilkinson J. L. Atwood R. D. Rogers W. E. Hunter and M. J. Zaworotko J.C.S. Chem. Comm. 1978,465. 13' J. M. Manriquez D. R. McAlister R.D. Sanner and J. E. Bercaw J. Amer. Chem. SOC.,1978 100 2716. 13' J. M. Manriquez P. J. Fagan T. J. Marks C. S. Day and V. W. Day J. Amer. Chem. SOC., 1978,100 7112. 139 T.Yamamoto J.C.S. Chem. Comm. 1978 1003. 140 E. R. Evitt and R. G. Bergman J. Amer. Chem. SOC.,1978,100 3237. 14' S.J. McLain and R. R. Schrock J. Amer. Chem. SOC.,1978 100 1315. 142 R. H.Grubbs and A. Miyashita J. Orgattometallic Chem. 1978,161,371;J. Amer. Chem. SOC.,1978 100,1300,ibid. 1978 100 7416; R.H. Grubbs A. Miyashita M. Liu and P. Burk ibid. 1978 100 2418. Organometallic Chemistry D D D D x D D D D D D 11 D (Ph3P),Ni D etc. + (Ph,P)2Ni D -5 D * \AD Scheme 6 These metallacycles catalyse linear and cyclo-dimerizations of olefins. Thermolysis of (PPh3)3Ni(CH2)5 yields a mixture of CH4 C2H4 C5H12 C5H10 and (PPh3)2Ni(C2HJ and evidence for a transformation of the six-membered ring into a [H2C=Ni(CH2)4] moiety was I I Substituted platinacyclobutanes of the type PtC12L2(CHRCH2CH2) have been found to exist as a mixture of isomers in solution and these are in rapid equili- bri~m.~~~~ Pt(py),C12(CH2CMe2CHMe) has been found to isomerize to an olefin complex P~(PY)~C~~(~~~-CH~CM~P~~) in which there is an apparent 1,2 methyl shift;1446.a carbene-olefin complex could be a common intermediate for these processes.Thermolysis of L2Pt[CHR(CH2),] (n = 3 or 4) complexes in CH2C12 or CH2Br2 not only yields cycloalkanes and alkenes from the metallocycle but also homologous ones incorporating a solvent methylene group.145 Model experiments indicate an oxidative addition step to give a Pt1"(CH2X)(X) moiety.Platinacyclo- pentanes are also formed when butadienes and alkenes interact with Pto complexes.146 While 2,3-disubstituted butadienes yield platinacyclobutenes butadiene itself is dimerized. (Scheme 7) The ring system stereospecifically opens and closes when it reacts with one and two mols of PMe respectively. 143 R. H. Grubbs and A. Miyashita J. Amer. Chem. SOC.,1978,100 7418. 144aR. J. Al-Essa R.J. Puddephatt C. F. H. Tipper and P. J. Thompson J. Organometaffic Chem. 1978 157 C40. 144b B. M. Cushman and D. B. Brown J. Organornetallic Chem. 1978,152 C42; B. M. Cushman D. Brown S. E. Earnest and D. B. Brown ibid. 1978,159,431. 14' G.B. Young and G. M. Whitesides J. Amer. Chem. Soc. 1978,100,5808. G. L. Barker M. Green J. A. K. Howard and F. G. A. Stone J.C.S. Dalton 1978 1839. A. J. Deeming and J. Evans '5PMe %PMe Pt H Pt(cod) -5 (cod)Pt H Pt -Me3P,H$ /Me,P /Me3P ; \\ Scheme 7 Metallation of pyridines and quinolines by (CSHS),TiMe formed in situ occurs a to the nitrogen atom,'47a but palladation of 2-substituted 8-methylquinolines with Pd(OAc)* occurs at the 8-methyl group and only if the 2-substituent contains a sufficiently good ligand e.g. an imir~e.'~~' Model studies indicate that the ability of the quinoline to coincide with the co-ordination plane is important. Protonation of Ir[{P(o-OMeC,H3)(O-o-tolyl)2}{P(O-o-tolyl)~}(cod)]appears to occur simply on the metal but in fact initially electrophilic cleavage of the Ir-C bond occurs by proton addition at the metallated carbon to yield [(cod)Ir{P(OAr),}2]'.'48" Cyclometallation only follows a second protonation at the metal.This complex reacts with chlorine to yield a multiply chlorinated cyclo- metallated species. 14*' An X-ray crystal structure determination on a derivative revealed that chlorine substitution had occurred at the cyclometallated ring. Alkyl Rh"' porphyrin complexes have been synthesized using diazoalkanes. 149 For example treatment of Rh(0EP)I with N2CHC02Et in AcOH yields Rh(OEP)[CH(OAc)(CO,Et)] but N-alkylation occurs with Rh(0EP)Me under similar conditions. Nucleophilic cleavage of the Co-C bond in [1-methylheptyl C~'~(dmgH)~]' by C1- occurs with inversion of configuration consistent with this process being involved in halogen cleavage of carbon bonds to CO"'.'~~ Cyclic voltammetry has shown a single cathodic wave for methylcobinamide prior to loss of Me.''la Electrochemical cleavage of a Co-C bond in a BI2model complex has been found to proceed with retention of configuration at arbo on.'^'' The mechanism by which B12catalyses the 1,2 migration of a carbonyl group has been investigated by model Evidence was found for a carbanionic but a series of experiments on the rearrangements of butenyl- cobaloximes indicated a bimolecular process in which a Co"(dmgH) moiety binds to the w carbon of the CoTII bound butenyl This process was also proposed for butenyl-cyclopropylmethyl isomerizations.13C-labelling studies demonstrated that the a-butenyl carbon becomes bound in (C3HSCH2)Co(dmgH)2(py);'52' an intramolecular process was suggested in this case. Co-C homolysis occurs when I4'OB. Klei and J. H. Teuben J.C.S. Chem. Comm. 1978,659. A. J. Deeming and I. P. Rothwell J.C.S. Chem. Comm. 1978 334. 14'OD. J. A. De Waal E. Singleton and E. van der Stok J.C.S. Chem. Comm. 1978 1007. 148b M. J. Nolte E. Singleton and E. van der Stok J.C.S. Chem. Comm. 1978 973. H. J. Callot and E. Schaeffer J.C.S. Chem. Comm. 1978,937. Is" R. H. Magnuson J. Halpern 1. Ya. Levitin and M. E. Vol'pin J.C.S. Chem. Comm. 1978,44. lsloD. Lexa and J. M. SavCant J. Amer. Chem. Soc. 1978 100,3220. '"'L. Walder G. Rytz K. Meier and R. Scheffold Helv.Chim. Acta 1978,61 3013. 152aA.I. Scott J. Kang D. Dalton and S. K. Chung J. Amer. Chem. Soc. 1978 100 3603. A. Bury M. R. Ashcroft and M. D. Johnson J. Amer. Chem. SOC.,1978 100 3217. M. P. Atkins B. T. Golding and P. J. Sellars J.C.S. Chem. Comm. 1978 954. 14'' Organometallic Chemistry 333 Co"'-R moieties e.g.methylcobalamin are photoly~ed.'~~ Secondary reactions of the carbon radicals then occur. When formyl complexes are synthesized by reduction of a metal carbonyl with a trialkyl-borohydride e.g. Li(BEt,H) the corresponding boron alkyl is formed. Formyls appear to be strong hydride donors and whether donation is from the formyl itself or uia boron has been tested using a chiral borohydride and monitoring the optical activity induced in 1-phenylethanol produced by reducing aceto-~hen0ne.l~~~ Boron involvement was evident for [Mn2(CO),CHO]- but both [Mn(CO)4(COCHzOMe)(CHO)]- and [(C,H,)Fe(CO)(COPh)(CHO)]-act as hydr- ide donors.The hydride donating ability of [(PhO),PFe(CO),CHO]- has been inve~tigated.'~~' This formyl reduces ketones and alkyl iodides and also Re2(CO)lo to yield the dinuclear formyl Re,(CO),(CHO)- also formed by reduction of the carbonyl by alkyl-borohydrides. 154c In turn this dinuclear complex reduces Fe(CO),. 4 Carbenes and Carbynes The carbene F4SCH has been synthe~ized.'~~ The sulphur co-ordination geometry of this colourless gas is trigonal bipyramidal with the methylene group in an equatorial site. Silylene complexes of iron HFe(CO),(SiMe,R)(SiMe,) have been prepared by reaction of Fe2(C0)9 with HSiMe2SiMe,R (R=H or Me).156 Cyclo- rapidly addition of activated alkynes to (~2-CSz)Fe(C0)2(PMe3)2157" forms complexes of cyclic carbenes e.g.Fe(CO)2(PMe3)2CSC(C02Me)C(C02Me)S.'57b Full reports of the synthesis of complexes of aminocarbenes by cleavage of the olefinic bond in NRCH,CH,NRC :CNRCHZCH2NR158a or by three-fragment oxi- dative addition of [NMe2(CHCl)]Cl'58b have been presented. The preparation and reactivity of (C5H5),Ta(Me)(CH2) have also been fully Reactions like the bromide displacement from SiMe3Br to form [(C,H,)2Ta(Me)CH,SiMe3]Br reveal the nucleophilic character of the carbene carbon. Proton abstraction converts the silyl substituted carbon into a carbene The closely related complexes [(C5H,)2M(CH,SiMe3)2]X (M = Ta or Nb) afford carbene complexes (C5H5),M(CH2SiMe3)(CHSiMe3) on treatment with the base Li[N(SiMe,),].159c Crystallographic determinations on a number of tantalum carbene complexes have been reported. The preferred alignment of the methylene substituents perpendicular to the radial plane in the (C,H,),Ta(CHR)X derivatives is Is3 C. Y. Mok and J. F. Endicott J. Amer. Chem. SOC., 1978,100 123; A. J. Hartshorn A. W. Johnson S. M. Kennedy M. F. Lappert and J. J. MacQuitty J.C.S. Chem. Comm. 1978,643. 154aJ.A. Gladysz and J. H. Merrifield Znorg. Chim. Acta 1978 30 L317. 154b C. P. Casey and S. M. Neurnann J. Amer. Chem. SOC.,1978,100,2544. 154c J. A. Gladysz and W. Tam J. Amer. Chem. SOC..1978 100 2545. G. Kleeman and K.Seppelt Angew. Chem. Internat. Edn. 1978,17 516. 156 H. Sakurai Y. Kamiyarna and Y. Nakadaira Angew. Chem. Internat. Edn. 1978 17 674. 1s7aH.Le Bozec P. H. Dixneuf A. J. Carty and N. J. Taylor Znorg. Chem. 1978 17 2568. 1576 H. Le Bozec A. Gorgues,and P. H. Dixneuf J.C.S. Chem. Comm. 1978 573; J. Amer. Chem. SOC. 1978,100,3946. lSaaM.F. Lappert and P. L. Pye J.C.S. Dalton 1978,837;P. B. Hitchcock M. F. Lappert and P. L. Pye ibid. 1978 826. isnb A. J. Hartshorn M. F. Lappert and K. Turner ibid. 1978 348. IsqaR.R. Schrock and P. R. Sharp J. Amer. Chem. SOC., 1978,100 2389. R. R. Schrock L. W. Messerle C. D. Wood and L. J. Guggenberger J. Amer. Chem. SOC., 1978,100 3793. '59c M. F. Lappert and C. R. C. Milne J.C.S. Chem. Comm. 1978 925.A. J. Deeming and J. Evans increasingly distorted by the steric bulk of the R group (the angle of deviation is 0"for R = H 5.7" for R = Ph and 10.3"for R = Bu') e.g. (19).1596*159d This has the effect of lowering the energy barrier to rotation about the Ta=C bond but there are also two other structural effects in these complexes. The Ta-C-C angle becomes increas- ingly obtuse so that the geometry at carbon in one of the carbon moieties in (20) is almost T-shaped and as this angle widens so the Ta-C distance The carbene Ta(CH2Bu),(CHBu') is also nucleophilic reacting with acyl chlorides to form Ta(CH2B~')3(C1)(OCR:CHBu').'60" Although thermally stable it eliminates neopentane on treatment with phosphines the rate of which is highly dependent on the added ligand.l6Ob A phosphine adduct apparently can rapidly undergo a-elimination and the bis-carbene complexes T~(CHBU')~(CH~BU')L~ result.A variety of bis-neopentylidene complexes including (C5Me5)2Ta(CHBu')2PMe3 were synthesized starting from Ta(CHBu'),ClL. Treatment of (C5HS)TaC12(CHBu') with a base and PMe3 has yielded a carbyne complex (CsH5)TaCl(PMe3)2(CBu').'60' A crystallographic determination of the structure of (C5MeS)TaCl(PMe)2CPh found the Ta-C distance to be 1.849A. This type of chemistry has been extended to Mo and W.16' For example (Bu'CH~)~WCBU' has been isolated from the reaction of WC16 and LiCH2Bu'. This complex appears to be in equilibrium with its dimer. Neopentane is eliminated on heating with PMe3 forming a mixed alkyl-carbene- carbyne species W(PMe3)2(CHBu')(CH2Bu')(CBu').Dithiocarbene complexes have been synthesized using the reagent N~[TOSNNC(SE~)~].For example it reacts with W(CO),NCMe to form 162 W(CO),C(SEt),. A series of cycloheptatrienylidene complexes e.g. C7H6W(C0), have been synthesized and the ring appears to have substantial tropylium charac- ter.16 Fluorine abstraction by SbF from (C5H5)M~(C0)3CF2RF has allowed iso- lation of a series of perfluorocarbene complexes [(C,H,)MO(CO),CFR~IS~F~.'~~ Raman spectroscopy has been used to identify the vw= frequency in X(CO),WZCCR c~mplexes.'~~ For R =D and X = Br this is at 1315 cm-' but in 15"M. R. Churchill and F. J. Hollander Znorg. Chem. 1978,17,1957; M. R. Churchill F. J. Hollander and R.R. Schrock J. Amer. Chem. Soc. 1978,100,647. 159cM. R. Churchill and W. J. Youngs J.C.S. Chem. Comm. 1978 1048. R. R. Schrock and J. D. Fellman J. Amer. Chem. SOC.,1978 100,3359. J. D. Fellman G. A. Rupprecht C. D. Wood and R. R. Schrock J. Amer. Chem. Soc. 1978,100,5964. S. J. McLain C. D. Wood L. W. Messerle R. R. Schrock F. J. Hollander W. J. Youngs and M. R. Churchill ibid. 1978 100 5962. D..N. Clark and R. R. Schrock J. Amer. Chem. SOC.,1978,100.6774. 162 M. F. Lappert and D. B. Shaw J.C.S. Chem. Comm. 1978,146. N. T. Allison Y. Kawada and W. M. Jones J. Amer. Chem. SOC.,1978,100,5224. 164 D. L. Reger and M. D. Dukes J. Organometallic Chem. 1978,153,67. E. 0.Fischer N. Q. Dao and W. R. Wagner Angew. Chem. Znternat. Edn. 1978.17.50. Organometallic Chemistry the corresponding protio complex it mixes strongly with a symmetric methyl deformation.(C5H5)Fe(C0)2CH2+ has been identified in the gas phase using ion cyclotron resonance spectroscopy. Adding cyclohexane causes elimination of CH2 and bases form adducts. Attempts have been made to generate this ion by acidification of (CSH5)Fe(CO)2CH20Me.'666 At low temperatures the acidic solu- tions convert cyclohexane into bicyclo[4,1,0,]heptane consistent with the cation being present. Attempts to characterize the dppe substituted derivative however yielded the solvated salt [(CSHs)Fe(dppe)MeCN]BPh,. Protonation of (C,H,)Fe(CO)PPh,(C,Ph) has yielded the marginally stable vinylidene cation [(C,H5)Fe(CO)(PPh3)CCPhH)]'.'67aComplexes of the type [(C5HS)Fe(dppe)- CCR,]' (R=H or Me) are more as are [(CSH5)R~(PPh3)2-(CCHR)]' cations.167c The vinylidene group in (C,H,)MI~(CO)~-(CCHPh) can be transferred to a rhenium atom using (C5H5)Re(C0)2-(thf);'67d a bridged intermediate can be isolated.Fe(TPP) reacts with DDT in the presence of an excess of a reducing agent to form Fe(TPP)[CC( the related complex Fe(TPP)(CC12)(OH2) formed using CCL has been characterized crystallographically."" Pt2C12(dppm)2 reacts with CH2N2 to form a bridging methylene complex.'69 Photolysis of a mixture of (C,H,)CO(CO)~ and CH(C02R)N2 below -1 10"C affords (C5H5)2C02(p-CO)2{p-O-C(OR)-CH},isomerizes to {p-CH(COzR)}-which [CO(C,H,)(CO>]~ by an intramolecular rearrangement."' Dinuclear iron complexes with bridging carbyne ligands have been synthesized by two different routes.171 Li[ (C5HS)Fe(CO),] reacts with cyclopentene epoxide and subsequent acidification with HBF4 yields the salt [(p-CO)(p-C-CsH7){Fe(C5Hs)CO}2]BF4; the 13C n.m.r.signal due to the methine carbon was observed at 6448. Complexes of this type can be synthesized more readily by treating [(C,H,)Fe(CO),] first with RLi and then HBF,. [(C5H5)Re(C0),(CPh)]BCl4 is reduced by Et2AlH at -78 "C to (C5H5)Re(CO)2(CHPh).'72 Further reaction at -30 "C causes a second reduction to a benzyl complex (C5H5)Re(CO)2H(CH2Ph). Carbonylation of carbenes has also been reported. (C5H5)Mn(C0)2CPh2 incorporates CO under high pressure to yield (CSH5)Mn(CO)2(~2-Ph2CC0);173" the ketene ligand was hydrogenolysed to a mix- ture of Ph2CHCH0 and the corresponding alcohol.However (C5Hs)W(CO)- (PMe3)(C-p-tolyl) behaves differentl~.'~~' It readily absorbs two mols of CO to form 166aA.E. Stevens and J. L. Beauchamp J. Amer. Chem. SOC. 1978,100,2584. lasbP.E.Riley C. E. Capshew R. Pettit and R. E. Davis Inorg. Chem. 1978,17,408. 167aA. Davison and J. R. Solar J. Organometallic Chem. 1978 155 C8. 167bA. Davison and J. P. Selegue J. Amer. Chem. SOC. 1978,100 7763. 16" M.I. Bruce and R. C. Wallis J. Organometallic Chem. 1978 161 C1. 167d N.E. Kolobova A. B. Antonova and 0.M. Khitrova J. Organometalk Chem. 1978 146 C17. lasaD. Mansuy M.Lange and J. C. Chottard J. Amer. Chem. SOC. 1978 100,3213. l60b D. Mansuy M. Lange J. C. Chottard J. F. Bartoli B.Chevrier and R. Weiss. Angew. Chem. Internut. Edn. 1978 17 781. M.P. Brown J. R. Fischer S. J. Franklin R. J. Puddephatt and K. R. Seddon J.C.S. Chem. Comm. 1978,749. I7O W. A. Herrmann Chem. Ber. 1978 111 1077; W. A. Herrmann and I. Schweizer 2. Nuturforsch. 1978,33b 1128. l7I M.Nitay W. Priester and M. Rosenblum J. Amer. Chem. SOC. 1978,100,3620. E.0.Fischer and A. Frank Chem. Ber. 1978 111 3740. 173aW. A. Herrmann and J. Plank Angew. Chem. Internat. Edn. 1978. 17 525. 173b F. R. Kreissl W. Vedelhoven and K. Eberl Angew. Chem. Internat. Edn. 1978,17,859,860. 17' A. J. Deeming and J. Evans (C5H5)W(CO)2(PMe3)C(CO)( p-tolyl) C02is evolved when this complex is treated with CO under more forcing conditions and the initial carbyne ligand is converted into an ethynyl moiety in (C5H5)W(CO)2(PMe3)(CC-p-tolyl).Heating chromium carbonyl carbene complexes with acetylenes effectively adds a keten across the carbon-carbon bond. 174a For example Cr(C0)5(CPh2) and NEt2CCNEt2 yield (NEt,)C:C(NEt,)C(O)CPh,. Insertion of activated acetylenes readily occurs into a Cr-carbene bond and this reaction eventually can afford fused heterocyclic products as for example in Scheme 8.'746The bridging methylene Scheme 8 complex (C5H5)2Ti(p-Me)(p-CH2)AlMe2 has been synthesized by the reaction of (C5HJ2TiMe2 with AlMe3.175 (C5H5)2Ti(p-C1)(p-CH2)AlMe2, formed from (C5H5),TiCI2 and AlMe3 readily transfers CH2 to organic molecules. Cyclo-hexanone is converted into methylenecyclohexane; CH is added to ethylene to form propene.Olefin-carbene complexes have been proposed to be involved in olefin metathesis and an iron complex of these two ligand types has been ~ynthesized'~~ (Scheme 9). Q+ HBF+ EtzO 20°C -78°C ' ,r(-yoD 'ZH4* Me0 OC OMe Scheme 9 174aK.H. Dotz and R. Dietz J. Organometallic Chem. 1978 157 C55. 174bChem. Ber. 1978 111 2517; K.H.Dotz and I. Pruskil ibid. 1978 111 2059; K.H.Dotz and D. Neugebauer Angew. Chem. Internat. Edn. 1978,17,851. ''' F.N. Tebbe G. W. Parshall and G. S. Reddy J. Amer. Chem. Soc. 1978,100,3611. 176 W.Priester and M. Rosenblum J.C.S. Chem. Comm. 1978,26. Organometallic Chemistry The next step in the metathesis reaction is now accepted to be the formation of a metallacyclobutane complex.Carbon-carbon cleavage of the metallocycle effects metathesis. Alternative metal-carbon bond cleavage has been proposed as a mechanism of Ziegler-Natta olefin polymerization. *” a-Hydrogen elimination from the polymer chain will yield a hydrido-carbene complex. Following olefin co-ordination cyclization will yield a hydrido-metallacyclobutane complex. Steric control is exercised by the conformational preferences of the metallacycle.

ISSN:0308-6003    

DOI:10.1039/PR9787500311

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

Organometallic Chemistry PART 11 =-Bonded Organometallics By A. J. Deeming 1 q2-Alkene Compounds Preparation Structure and Fluxional Behaviow-Routine access to rapid methods of X-ray structural analysis allows many q2-alkene complexes to be studied struc- turally each year and while results taken individually are rarely exciting detailed comparisons are now possible. ,Several structures of complexes relating to [Rh(alkene)J [L = r)’-C5H5 or MeCOCHCOMe] have been determined. The complex [Rh(q’-C5Me5)(PPh3)(C2H4)] has shorter Rh-C(a1kene) bonds than for example [Rh( q5-C,H5)(C2H4)(C2F4)] [2.093 A (mean) compared with 2.1676) A] and a longer CH2-CH2 bond [1.408(16) compared with 1.358(9)A]. This is attributed to a greater r-component to the Rh-C2H4 bonding because of the greater u-basicity and lower w-acidity of PPh3 compared with CZF4.l The 20” twist of the two CH2 planes with respect to each other and the closely tetrahedral geometry of the C atoms are structural details of the PPh3 complex.Rh-C(a1kene) bonds in [Rh(CH3COCHCOCH3)( alkene) (CF3CrCCF3)] (a1 kene = C2& or cyclo-octene) prepared by alkyne addition to the corresponding bis (alkene) complexes are in the range 2.142-2.196 A,’ presumably because CF3C=CCF3 has similar ligating properties to CZF4. More complicated q2-alkene complexes in the same series to be studied structurally are [Rh( q 5-CsH5)(+)-(4S-carvone)]in which the co-ordinated C=C bonds of the diene ligand are far from parallel as in the bis(ethy1ene) complex but rotation about the Rh-alkene bond is not expected to be very energetically demanding.3 Other X-ray structures in this series are [Rh(MeCOCHCOMe)- (CH2:CHCMeOCH2CH:CHMe)I4 and [Rh(PhCOCHCOMe)( 1,6-dichlorocyclo- octa-1,5-diene)].’ Detailed vibrational thermochemical and n.m.r.studies on the effect of varying alkene diketone and metal (Ir or Rh) have shown that the substituent effects are comparable for both metals although the alkene-Ir bonding is 177 K. J. Irwin J. J. Rooney C. D. Stewart M. L. H. Green and R. Mahtab J.C.S. Chem. Comm. 1978,604. W. Porzio and M. Zocchi J. Amer. Chem. Soc. 1978,100,2048. ’J. H. Barlow G. R. Clark M. G. Curl M. E. Howden R. D. W. Kemmitt and D. R. Russell J. Organometallic Chem. 1978,144 C47. W. Winter B. Koppenhofer and V. Schurig.J. Organometallic Chem. 1978,150 145. R. Grigg B. Kongkathip and T. J. King J.C.S. Dalton 1978 333. J. JeEn9 and K. Hulm Acfa Crysf. 1978 B34,2966. A. J. Deeming and J. Evans stronger than for Rh.6 Other alkene complexes of &-metals to be structurally examined are [NEt4][PtC13(CH2:CHOEt)],'which shows a closer approach of the Pt atom to the terminal alkene carbon than to the OEt-substituted one (2.128 compared with 2.208 A) and [PdC12(1,2,5,6-q4-cyclo-octatetraene)].8 A kinetic study of the substitution by alkenes into [PtC1412- is reported' and a 'H and 2H n.m.r. study in liquid crystal solutions of [PtC12(C2H4)(NC5D5)] has established the relative positions of the hydrogen and platinum nuclei. Quadrupole splittings in the 2H spectra have been used to show that the pyridine ring is inclined at an angle to the co-ordination plane with rapid reorientations between symmetry related forms.lo The first reported X-ray structure of a six-co-ordinate ethylene complex [RuCI~(CO)(C~H~)(PM~,P~)~] (1)shows the q2-alkene to be aligned with the C-C bond parallel to the P-Ru-P axis which it could be argued is to prevent competition between the .rr-components of the Ru-C2H4 and Ru-CO bonds for the available metal d-orbitals." However the energy barrier to rotation about the Ru-C2H4 bond is low since rapid rotation occurs down to -40 "C; a single C2H4 'H n.m.r. resonance rather than an AA'BB' spectrum being observed. A similar series of octahedral q2-alkene complexes [W(C0)4L(alkene)] (L=PMe3 or AsMe3) (2) and [W(CO),(PMe,),(alkene)] (alkene =substituted monoene) have been examined spectroscopically.'* The preferred alkene alignment is parallel to the W-L bond as determined from the low-temperature 'frozen-out' n.m.r.spectra. This conformation relates to that for (1)and as with (l) ready rotation about the W-alkene bond occurs and activation parameters are given. Ab initio LCAO-MO-SCF calculations on tr~ns-[MoL~(alkene)~] (L =PH3)(3) have shown that the most stable cQnformation has mutually perpendicular alkene ligands each eclipsing the L-M-L axes.13" The computed alkene rotation barrier of 67kJ mol-' compares with the experimental oc I !.co L I '. value of 64kJ mol-'. The barriers for zerovalent Mo and W complexes (2) and (3) appear to be higher than for the divalent Ru complex (1);this could be explained in terms of differing w-contributions to the alkene-metal bonds lower for Ru" than Moo or Wo.A similar effect probably accounts for the higher barriers for [Ru(arene) (C2H4)2] than for [Rh(C,H,) (C2H4)2]. '3b A. C. Jesse. M. A. M. Meester D. J. Stufkens and K. Vrieze Znorg. Chim. Actu 1978,26 129; A.C. Jesse H. P. Gijben D. J. Stufkens and K. Vrieze ibid. 1978 31 203. 'R. C. Elder and F. Pesa Actu Cryst. 1978 B34 268. N. C.Baenziger C.V. Goebel T. Berg and J. R. Doyle Acta Cryst. 1978 B34 1340. M. Green and C. J. Wilson J. Chem. Res. (S) 1978 175. lo J. W. Emsley and J. Evans J.C.S. Dalfon,1978 1355. L.D. Brown C.F. J. Barnard J. A. Daniels R. J. Mawby and J. A.Ibers Znorg. Chem. 1978,17,2932. U.Koemm C.G. Kreiter and H. Strack J. Orgunometullic Chem. 1978,148 179. l3 (a) C.Bachmann J. Demuynck and A. Veillard 1Amer. Chem. Soc. 1978,100 2366; (6)M. A. Bennett and T. W. Matheson J. Organometallic Chem. 1978 153. C25. Organometallic Chemistry Treatment of [Pt(cod),] with a range of tertiary phosphines or AsPh (L) in ethylene saturated solutions leads to complexes [Pt(C2H4),L] for which alkene rotation has been studied by d.n.m.r.14 The X-ray structure (4) of the mixed C2H4,C2F4 complex has a trigonal planar co-ordination with alkene carbon atoms in the plane. Rotation about the Pt-alkene rather than about the C-C axis is established; in fact this latter process is unknown and Pt-H coupling observed at high temperatures rules out a reversible alkene-displacement mechanism.Replace- ment of one C2H4 in [Pt(C2H,),(PCy3)] by C2F4 lowers the rotation barrier for the remaining C2H4 by 12.6 kJ mol-' and reduced barriers as a result of reduced .rr-back-bonding from platinum are a rationalisation of this. Also as expected for a system where electronic rather than steric effects dominate higher barriers are found with the more basic ligands L. Photochemical displacement of CO by c2H4 leads to complex (3,which gives a C2& 'H n.m.r. singlet at 301 K but an AA'BB' spectrum at 230 K.' Rotational barriers for the W-C2H4 bond are very similar for the corresponding q5-CsH4 and q5-indenyl complexes. Different isomers were observed for the ethylene complex (6) as indicated by two v(C0) absorptions of similar intensity.16 The effect though is probably due to there being different conformations about the Fe-carbene rather than the Fe-ethylene bond.Mixed carbene-alkene complexes are important in alkene metathesis since these are believed to lead reversibly to metallocyclobutane intermediates thus (6) provides a model for this type of compound. Isomers with different alkene conformations (7a) and (7b) are observed for a propene-tantalum complex.l7 Complex (7) relates to the known complex [Ta(C,H,),(H)(C,H,)] and was prepared by treatment of [(Ta(C,H5),Cl2] with PrMgC1. An intermediate propyl complex undergoes &elimination to give propene and otber 2-alkene complexes may be formed similarly. Isomers (7a) and (7b) are interconvertible by alkene rotation but here the barrier is high.The complexes [Ta(C5H5),L(CH,)] (L = CH2 or C2H4) are related in that there is no ready rotation about the Ta-CH2 or Ta-C2H4 bonds.'* The C-C axis in the C2H4 complex is perpendicular to the CH plane of the other compound sothat equivalent metal orbitals are used for ?r-bonding in each case and since there is no suitable metal orbital at 90"no facile ligand rotation occurs. The complex with L = CH converts thermally (50% conversion) to that with L = C2H4 but this is better achieved by treatment with Me3P=CH2. + N.C.Harrison M.Murray J. L. Spencer and F. G. A. Stone J.C.S. Dalton 1978 1337. IS H.G.Ah J. A. Schwkzle and C.G. Kreiter J. Organometallic Chem. 1978,153 C7. l6 W.Priester and M. Rosenblum J.C.S. Chem. Comm. 1978,26. l7 A.H. Klazinga and J. H. Teuben J. Organometallic Chem. 1978,157,413. R. R. Schrock and P. R. Sharp J. Amer. Chem. Soc. 1978,100,2389. A. J. Deeming and J. Evans Treatment of [Nb(C5H5)2C12] with Pr’MgC1 in the presence of cyclo-octatetraene gives [Nb(q’-C,H,)(q2-C8H8)] obtained as a red-brown air-sensitive and paramag- netic solid.” An alternative synthesis of the same compound is to treat NbC15 with K2[C8H8] to give [NbC12(CsH8)](THF) which can then be treated with Na[C,H,]. The evidence for q 2-co-ordination of the cyclo-octatetraene is mainly based on reactivity; it liberates isomers of cyclo-octatriene with HCl (other q2-alkenes behave similarly) and with NaBH gives the diamagnetic q3-allyl complex [Nb(q5- C5H5)2(q3-C8H9)].Nobium(II1) alkene and alkyne complexes are also prepared by direct substitution of CO by C2H4 (80atm) to give [Nb(~s-C,H,)2C1(C2H4)] or by reduction of [Nb(CSH5)2C12] with Na/Hg followed by alkyne addition to give [Nb(C5H5)2Cl(alkyne)] (alkyne =propyne or perfl~orobut-2-yne).~~ The lack of rapid rotation about the Nb-C2H4 bond is shown by the non-equivalence of the ends of the alkene in the ‘H n.m.r. spectrum. The complex previously reported as [R~(styrene)(PPh~)~] formed by treating [RuH,(PPh,),] with styrene has been reformulated as [R~(styrene),(PPh~)~] and appears to be the first fully authentic 16e-ruthenium(0) complex.21 The two styrene ligands in this highly distorted tetrahedral complex (8a; P=PPh3) are quite different one having a normal q2-styrene co-ordination with the a-C further from the metal atom than the B-C.The abnormal styrene has a short phenyl-ruthenium interaction making the a-closer than the p-C to the metal. It may be that the 18e-form (8b) contributes to the ground state structure. Two 31P n.m.r. doublets are consistent with the asymmetric structure being retained in solution but (8) is only stable in styrene solution and even then only in equilibrium with [R~(styrene)~(PPh~)]. Complex (8) reacts with PPh3 to regenerate [RuH2(PPh3)41 (hydrides from PPh3) and is a ready source of other alkene-Ruo complexes.22 Dehydrogenation of tricyclohexylphosphine (PCy3) on reaction with [MCl(cyclo- ~ctene)~] (M=Rh or Ir) leads to complexes [MClL(PCy3)] which contain the isomeric chelating ligands L shown in (9a) and (9b).23 The lost H2is presumably used to form five-co-ordinate metal(II1) dihydrides which are by-products.P H; l9 C. P. Verkade A. Westerhof and H. J. de Leifde Meijer J. Organornetallic Chem. 1978,154,317. 2o S. Fredericks and J. L. Thomas J. Amer. Chem. SOC. 1978,100,350. 21 M. A. A. F. de C. T. Corrondo,B. N. Chaudret D. J. Cole-Hamilton A. C. Skapski and G. Wilkinson J.C.S. Chem. Comm. 1978,463. 22 B. N. Chaudret D. J. Cole-Hamilton and G. Wilkinson J.C.S. Dalton 1978 1739. ” S. Hietkamp D. J. Stufkens and K. Vrieze J. Organometallic Chem. 1978,152,347. 341 Organometallic Chemistry Substituted q2-fulvene complexes are formed replacing one CO ligand in [Mn(r15- C,H,)(CO),] by the fulvene to give [Mn(q5-C,H5)(q2-dimethylfulvene)]and [{Mn( q’-C,Hs)(C0)2}2(p-dime t hylfulvene)].Co-or dination in both cases is through C=C bonds in the five-membered ring.24 A q2-squaric acid complex (10)is derived by displacing ethylene from [Pt(C21&)(PPh3)2] and C-C cleavage in (10) can occur thermally to give the tautomeric product mixture (11) which is isomeric with the original q2-complex.25 The diphenylketen complex [Ni( q2-Ph2C:C:O)(PPh3)2] is formed on treatment of the corresponding C21& complex with the keten and on dissolving this breaks down to [Ni(CO)(PPh3)3];26 a similar reaction occurs on treating [Mn(C,H,)(CO),(THF)] with Ph2C:C:0 except that it is the CO group that is lost giving [Ni(C,H,)(CO),(Ph,C)].Interestingly in this case the keten to carbene conversion may be reversed on treatment with a pressure of CO to give [Ni(C5H5)- (C0),(q2-Ph,C:C:O)] and subsequent hydrogenation gives Ph2CHCH0 and Ph2CHCH20H.27 Metal Atom Derivatives of A1kenes.-The matrix-isolated (C2H4/Ar at 15-25 K) complexes of ethylene [Nin(CzH4),] (n = 1 m = 1 2 or 3; n = 2 rn = 1 2 and possibly species with n > 2)28and [Co,(C2H4),] (n = 1 2 or 4 with rn ~ariable)~’ have been described and their vibrational and electronic spectra discussed. For nickel species such as [Ni(C2HJ] and [Ni2(C21&)] calculations of binding energies and energies of transformation from q2-to di-cr-bonding have been carried OU~.~**~’ In the related reaction between Ni atoms and alkyl- fluoro- and chloro-substituted alkenes similar complexes of type [Ni(alkene),] (n = 1,2 or 3) are formed even for ally1 chloride.Warming the q2-ally1 chloride complexes does not lead by oxidative addition to the q3-allyl nickel complexes reported to be formed by similar treatment of nickel atoms and it was suggested that high-temperature work-up or the prior formation of nickel clusters are required for oxidative addition.,l ’* F. Edelmann K.-J. Jens and U. Behrens Chem. Ber. 1978 111 2895. 2J W.Beck F. Goetzfried and M. W. Chen Chem. Ber. 1978,111,3719. 26 H. Hoberg and J. Korff J. Organometallic Chem. 1978,152,255. 27 W.A.Hermann and J. Plank Angew. Chem. Internat. Edn. 1978,17,525. G. A. Ozin W. J. Power T. H. Upton and W. H. Goddard J. Amer.Chem. Soc. 1978,100,4750. 29 A. J. Lee Hanlan G. A. Ozin and W. J. Power Inorg. Chem. 1978,17 3648. 30 T.H. Upton and W. A. Goddard J. Amer. Chem. SOC.,1978,100,321. 31 G.A.Ozin and W. J. Power Inorg. Chem. 1978,17,2836. A. J..Deeming and J. Evans Reaction of r)*-Alkene Complexes.-Nucleophilic addition at 2-alkenes is an important reaction occurring in the palladium-induced oxidation of ethylene. The idea of co-ordinated OH- migrating to a cis-co-ordinated C2H4 originated from a kinetic analysis of the reaction of [PdCI4l2- with ethylene but must now be discarded on present evidence since a second report confirming trans-addition to C2H has appeared.32 The conclusion depends upon the assumption of CO insertion with retention of configuration at carbon in reaction (1).Nucleophilic addition of Me2NH at [PtC12(PPh3)(C2H4)] leads to a zwitterionic intermediate [&C12(PPh3)-+ (CH2CH2NHMe2)] which readily dehydrochlorinates to give the complex [Pt(CH2CH2NMe2)CI(PPh3)], which appears to be the first chelate of its kind for platinum.33 Nucleophilic addition at q2-allenes may be at the central carbon to give q3-allyl systems but also at a terminal carbon as in reaction (2),the product of which has been fully established by X-ray diffra~tion.~~ Cis- and trans-[PtCI2(amine)- Et NH cis-[PtC12(PPh3)(77 2-CH2:C:CMe2)] [PtC12(PPh3){C(CH2hHEt2): CMe2}] (2) (C2H4)] behave differently with amines (e.g.py).The trans-isomer simply undergoes nucleophilic attack at C2H to give the zwitterionic product (12),but where C1-is trans to C2H4 as in the cis-isomer this is substituted to incorporate two amines giving the product (13).35 CI O C H ,CH I -Pt -py I CI PY (12) (13) Although oxygen- and nitrogen-based nucleophiles do seem to attack q2-alkenes without prior co-ordination the transfer of hydride or alkyl to alkenes may occur intramolecularly and calculations on various possible mechanisms for the insertion of C2€&into Pt-H bonds have been made.36 No facile pathway for hydride migration to C2H4 was found for a five-co-ordinate complex nor for a direct route for a four-co-ordinate complex with trans C2H4 and H.The seemingly most favourable mechanism involves these ligands mutually cis in a four-co-ordinate complex indeed the mechanism with some experimental support.A planar arrangement of the four reacting atoms (M C=C H) seems a requirement and experimental evidence for 32 J. K. Stille and D. Divakaruni J. Amer. Chem. SOC.,1978,100,1303. 33 A.De Renzi A. Panunzi and A. Vitagliano. Gazzetta 1978,108,45. 34 A.De Renzi B. Di Blasio A. Panunzi C. Pedone and A. Vitagliano. J.C.S. Dalton 1978,1392. ” G. Natile J.C.S. Chem. Comm. 1978 654. 36 D.L.Thorn and R. Hoffmann J. Amer. Chem. SOC.,1978,100,2079. Organometallic Chemistry this has come from a study of the hydrogenation of cyclo-octa-1,5-diene (cod) catalysed by [1r(~od)(PPh~)~][PF~].~~ A formation of cyclo-octene (coe) when isomer (14) is in solution is fast but the rate is reduced as this isomerizes to (15) and it has been pointed out that only isomer (14) allows a planar Ir C=C H arrangement.Hydride migration to give a cyclo-octenyl intermediate must be 40 times faster for (14) than (15). Reversible equilibria between metallocyclopentane and bis(ethy1ene) complexes have been reported for complexes [ki(CH2CH2CH2CH2)(PPh3)2] and [h(CH2CH2CH2CH2)(CsHs)2].38 Evidence for this came from an analysis of the mixtures derived by reaction (3) which occurs faster than decomposition with loss of ethylene. No other deuteriated metallocyclopentane rings were observed to be formed. Activation of C-H bonds in ethylene occurs on reaction of but-2-yne with [Rh(qs-indenyl)(C2H4)2]to give complex (16) (X-ray structure; R =Me) as well as a Me (16) (R=H or Me) metallocyclopentadiene complex derived by but-2-yne It seems that an intermedate hydrido(viny1) complex must be formed which can then insert the alkyne into the Rh-H bond.Similar activation of ethylene has only previously been observed in clusters and here the combined involvement of two Rh atoms seems necessary. Displacement of acetate from vinyl acetate occurs when this is reacted with [Ni(PR3),(ethyl methacrylate)] to give [Ni(AcO),(PR,),] (n= 1 where R = cyclohexyl but n = 2 for smaller phosphine substituents) the vinyl group being liberated as eth~lene.~’ 37 R. H. Crabtree H. Felkin. T. Khan and G. E. Morris J. Orgunomefullic Chem. 1978,144 C15. R. H. Grubbs and A. Miyashita J. Amer. Chem. SOC.,1978,100 1300. 39 P. Caddy M. Green L. E. Smart and N.White J.C.S. Chem. Comm. 1978. 839. J. Ishizu T. Yamamoto and A. Yamamoto. Bull. Chem. SOC.Japan 1978,51,2646. 344 A. J. Deeming and J. Evans The high trans-labilising effect of ethylene operates in the aquation of [PtCl4I2- catalysed by [PtC13(C2H4)]- and a kinetic analysis has shown that truns-[PtC12(C2H4)(H20)] is the actual catalyst the rate of the catalysed reaction being proportional to its concentration. Reactions (4) and (5) are the key steps in the proposed mechanism replacement of C1- in the complex [PtC1,(C2H4)] formed in (5) +[PtC14I2-Ft [(C2H,)C1zPt(p-Cl)PtC13]2-~IIZ~S-[P~C~~(C~H~)(H~O)] +H20 (4) [(C2H4)C1zPt(p-Cl)PtC13]2- +H2O * [PtC13(C2H4)]- +[PtCl,(H20)]- (5) being rapid.41 The successive migration of an alkyl group as a polymer chain terminus to a cis-co-ordinated alkene at titanium(II1) (and other metals) is the mechanism generally proposed for Ziegler-Natta polymerization.Noting that alkene metathesis and polymerization catalysts are chemically almost indistinguish- able a new mechanism has been proposed and illustrated for propene in reaction (6) P P Me P Me p. Me Me I I \/ +propene \/ P-CHT CHMe C ___) C -propcne 11. CH, I II Ti-CHMe Ti H-Ti H -TI -11 CHMe H (6) (P= Stereoselective formation of syndiotactic polymer would be controlled by the relative orientations of Me-groups as the metallocyclobutane ring is formed. This mechanism seems to fit the available evidence at least as well as the commonly discussed mechanism. 2 q2-Alkyne Compounds Preparation and Structure.-The X-ray structure of [Fe2(C0),(Ph2PC~CBu')] (17) the first established structure for a compound of type [Fe(CO)4(alkyne)] shows the alkyne to lie in the equatorial plane of a trigonal bipyramid as do alkenes in similar complexes.43 Surprisingly no X-ray structure of a q2-C2H2complex was available prior to (18) being studied although p 2-C2H2 structures have been determined.4 The C-C and C-0 bonds of (18)are approximately parallel.A C2H2 complex of Mo'" has been observed by n.m.r. in the equilibrium (7) and although this was not [MoO(S~CNE~~)~] +alkyne e[M~O(S~CNEt~)~(alkyne)l (7) isolated the related HC=CCO2Me complex was.45 An improved synthesis of [Mo(C5H5),(C2H2)]has been described and the related propyne and but-2-yne complexes also obtained.Acid treatment liberates corresponding alkenes cis- MeCH=CHMe being obtained from [MO(C~H,),(M~CGCM~)].~~ '' M. Green and M. G. Swanwick J.C.S. Dalton 1978 158. 42 K.J. Ivin J. J. Rooney C. D. Stewart M. L. H. Green and R. Mahtab J.C.S. Chem. Comm. 1978,604. 43 A. J. Carty W. F. Smith and N. J. Taylor J. Organometallic Chem. 1978,146 C1. 44 L. Ricard R. Weiss W. E. Newton G. J.-J. Chen and 1. W. McDonald J. Amer. Chem. SOC., 1978,100 1318. 45 E. A. Maatta R. A. D. Wentworth W. E. Newton J. W. McDonald and G. D. Watt I. Amer. Chem. SOC.,1978,100 1320. 46 J. L. Thomas Inorg. Chem. 1978 17 1507. Organometallic Chemistry The dialkynes RC_C-C=CR (R =Me or Ph) react with [Pt(C2H4)k] (L = PPh3 or PMe2Ph) by successive co-ordination through the two multiple C-C bonds to give with an excess of the platinum reagent the complexes [Pt2L4(diyne)] (19).Interestingly a complex of this stoicheiometry but with L = Bu'NC adopts quite a different structure (20) with a Pt-Pt bond.47 Side-on N2co-ordinationis recognized as the counterpart of q2-alkyne co-ordination but no simple isolable mononuclear complexes have been described prior to [Zr(~5-CsHs)2R(N2)] [R =CH(SiMe,),] which gives a 1 :2 :3 :2 :1 e.s.r. quintet (together with 91Zr satellites) showing equivalent coupling to two 14N nuclei and of sufficient magnitude to indicate fairly high spin density at N2. Structure (21) is proposed.48 Reactions.-The titanium(I1) alkyne complex [Ti(C,H,)2(CO)(PhC~CPh)] formed from the dicarbonyl by CO displacement has an alkyne C-C length of 1.285(10)A.Hydrogenation gives [Ti(C,H,),H(CPh=CHPh)] with CO being lost and with cis-addition across the alk~ne.~~ Similar cis-addition occurs in reaction (8) (L= PPh3).,' The oxidative addition product undergoes methyl transfer to the alkyne or (85 '/o ) (15%) the alkyne ligand is lost to give the two respective platinum(I1) products. Presumably oxidative addition of H2is followed by hydrogen atom transfer in the titanium case and in the isomerization of [Pt(PPh3),(Me02CC~CC02Me)] to (22) (X-ray struc- ture) a similar sequence can be envisaged that is oxidative cyclometallation with *'I J. B. B. Heyns and F. G. A. Stone J. Orgqnometallic Chem. 1978,160,337. 48 M. J. S. Gynane J.Jeffery and M. L. Lappert J.C.S. Chem. Comm. 1978,34. 49 G. Fachinetti C.Floriani. F. Marchetti. and M. Mellini J.C.S. Dalton 1978. 1398. T.G.Appleton M. A. Bennett A. Singh and T. Yoshida. J. Organometallic Chem. 1978,154,369. A. J. Deeming and J. Evans ortho-H transfer to platinum followed by its transfer to the alk~ne.~~ The kinetics and mechanism of the internal oxidative addition reaction (9)have been studied the cis-product isomerizing further to the trans-complex in benzene. An intramolecular mechanism is indi~ated.~~ Metal Atom Deivatives.-Copper atoms (0.1 molo/o) trapped in an Ar matrix containing acetylene (0.3 to 10 molo/o) give species with e.s.r. signals attributable to [Cu(C2H2)J (n= 1 or 2) and q2-bonding is proposed rather than u-bonding as in [Al-CH=CH’].53 Nickel or palladium atoms (M) react with CF3C~CCF3 to give compounds which react with CO giving [M(CO)2(alkyne)] which on warming to near room temperature convert to the clusters [M4(C0)4(alkyne)] (known for Ni).54 No CO is taken up by some metals and simple thermally stable alkyne complexes were made for Co Ni Pd Pt Cu and Au.3 q’-Ally1 Compounds Preparation and Structure.-The preparation of [Re2(C3H5)4] was reported earlier and its X-ray structure is now known.” There are four chemically equivalent v3-allyl ligands of normal type with the dimer held together by a triple Re-Re bond (23),whereas in the stoicheiometrically equivalent Cr and Mo compounds (24)which contain quadruple M-M bonds bridging and q3-allyl ligands are both present.The reasons for these differences have not been established. The dimeric complex (23) (24) (M = Cr or Mo) ’’ N. C. Rice and J. D. Oliver J. Organomefallic Chem. 1978 145 121. ’’ J. Burgess M. E. Howden R. D. W. Kemmitt and N. S. Sridhara,J.C.S. Dalton 1978 1577. 53 P. H. Kasai and D. McLeod J. Amer. Chem. SOC.,1978,100,625. K. J. Klabunde T. Groshens M. Brezinski and W. Kennelly J. Amer. Chem. SOC.,1978,100,4437. ” F. A. Cotton and M. W. Extine J. Amer. Chem. SOC.,1978 100 3788. Organometallic Chemistry 347 [Fe2(Co)6(q3-c&)z] also has normal allyl ligand~.'~ The reason for the long Fe-Fe bond [3.138(3) A] probably relates to that put forward for the long bond in [CrZ(co)6( q 5-c5H5)Z1. The very familiar complex [PdzC1z(q3-2-methylallyl)z] reacts with [PdCl,(PhCN),] to insert a PdCl unit between the original two Pd atoms.57 Chloro- bridges hold the three metal atoms together although from the asymmetry of these bridges there appears to be a significant contribution from [(7'-C,H,)Pd]'[PdCl,]'-[Pd( q 3-C4H7)]'.[Pt(q 3-C3H5)(PCy3)2][PF6] (toluene) has a normal structure except that the q3-allyl group adopts two discrete orientations in the crystal with the central allyl carbon above or below the co-ordination plane with occupancy factors of 0.4 and Oh.'* The X-ray structures of [PdzC12(l-3-q3-6-chlorocyclo-octatrienyl)2] derived from [PdC1z(PhCN)z] and cyclo-octatetraene" and of [RU(~~-C~H~)(NO)(PP~~)~]~' have been described. A detailed analysis of a standard synthetic route to q3-allyl palladium complexes as applied to a wide range of alkenes has been made and mechanisms including oxidative addition to give hydridopalladium(1v) intermediates discussed.61 There is of course precedence for oxidative addition of alkenes as in the addition of propene to [Ru(qZ-MeCN)(PPh3),] to give [RuH(PPh3)(q3-C3HS)(MeCN)], and tauto- merism involving a hydrido (q3-allyl) and a q2-propene complex was considered to account for some reaction products of the q3-C3H5 complex.62 Ally1 complexes are also generated from allylic halides and from a kinetic study of the oxidative addition of allyl bromide to [Mo(CO),(phen)] in 1,2-dichloroethane this seems to involve the rate-determining loss of CO (probably solvent-assisted) prior to oxidative addi- ti~n.~~ In tetrahydrofuran solution a small second order kinetic term is also observed.The phenalenium ion (X') displaces ethylene from [Pt(CZH4)(PPh3),] to give [Pt(X)(PPh3)z]' and both n.m.r. and diffraction methods have established the q3-allyl mode of bonding in (25).64 Another example has been reported of carbenium ion stabilization by metal atoms modifying their bonding to the ligand. The q2-to q3-ligand transformation in reaction (10) allows a ready loss of OH-56 C. F. Putnik J. J. Welter G. D. Stucky M. J. D'Aniello B. A. Sosinsky J. F. Kirner and E. L. Muetterties J. Amer. Chem. SOC. 1978,100,4107. 57 P. M. Bailey E. A. Kelley and P. M. Maitlis J. Organometallic Chem. 1978 144 C52. 58 J. D. Smith and J. D.Oliver Znorg. Chem. 1978,17 2585. s9 N. C. Baenziger C. V. Goebel B. A. Foster and J. R. Doyle Actu Cryst. 1978 B34 1681. " M. W. Schoonover C. P. Kubiak and R. Eisenberg Znorg. Chem. 1978,17,3050. 61 B. M. Trost P. E. Strege;L. Weber T. J. Fullerton andT. J. Dietsche J. Amer. Chem. SOC. 1978,100 3407. '' E. 0.Sherman and P. R. Schreiner J.C.S. Chem. Comm. 1978,223. 63 J.-C. Rousche and G. R. Dobson J. Organometallic Chem. 1978 150 239. 64 A. Keasey P. M. Bailey and P. M. Maitlis J.C.S. Chem. Comm. 1978 142. A. J. Deeming and J. Evans R = H or Me; M = Rh(C5H5)or Fe(C0)3 in solution with the ready formation of the stable cationic complex.65 Electrophilic attack of BF3 at the ketonic oxygen atom of [Fe(C0)4-(q2-PhCH:CHCOPh)] leads to [Fe(C0)4(PhCH:CH-kPh-OBF3)] which could be easily formulated as a q3-allyl complex.66 Reaction of this product with cyclo- hexylamine (RNH2) gives complex (26) (X-ray structure) the amine adding as a nucleophile both at the carbon atom of a metal carbonyl to give the carbamoyl group as well as formally displacing the group [OBF3I2-.Twoproducts from the reaction of [Co(CO),]- and CH,:C(CH,Cl) have been shown by X-ray diffraction to be the q3-allyl complexes (27) and (28);crystals of (27) but a P(OMe) derivative of (28) being chosen for st~dy.~' \ /NR (CO),Fe-C \O (26) .A, (CO),Co-, -Co( CO) (27) (28) q 3-Allyl complexes are formed from the metallocyclopentane complex f I (diphos = Ph2PCH2CH2PPh2) [Pt(CH2CH2CH2CH2)(diphos)] by the abstraction of hydride ion by [Ph3C]+ in dichloromethane.68 The intermediate [Pt(CH,CH,CH=CH,)(diphos)]* is proposed but the isomeric q3-~rotyl complex is isolated.Displacement of C1- from the cyclopropyl complex [PtCI(C3H5)L2] (L =PMe2Ph) allows a very specific C2-C3 bond cleavage with no hydrogen atom transfer as shown by deuteriation; reaction (1l).69q3-Allylic complexes are also " I. T. Chizhevsky and A. A. Koridze J. Organometallic Chem. 1978,153 C28. 66 A. N. Nesmeyanov M. I. Rybinskaya L. V. Rybin N. T. Gubenko N. G. Bokii A. S. Batsanov and Yu. T. Struchkov J. Organometallic Chem. 1978 149 177. 67 K. Cann P. E. Riley R. E. Davis and R. Pettit Znorg. Chem. 1978 17 1421. P. Diversi G. Ingrosso and A. Lucherini J.C.S. Chem. Comm. 1978 735. 69 R.L. Phillips and R. J. Puddephatt J.C.S. Dalton. 1978 1732. Organometallic Chemistry 349 formed by opening C rings in the reaction of [PtD(N03)L2] (L = PEt or PPh3) with methylenecyclopropane and when L = PEt3 the product contains D specifically in the 2-position that is [Pt(q3-MeCHCDCH2)L2]+ is formed as the exclusive product. Me 4+ D-Pt + Pt D When L = PPh3 both q3-1-methyl- and -2-methyl-ally1 complexes are formed. Pathway (12) is proposed although attempts of corroborating this by isolating cyclopropylmethyl complexes by other routes were U~SUCC~SS~U~.~~ Phenyl-cyclopropane reacts with [IrCl(N2)(PPh3)2] to give [IrHC1(v3- PhCH-CH.CH,)- (PPh3)2] which is apparently the first structurally characterised hydrido (q3-allyl) complex,” but unlike [MoH(~~-C~H,)(P~~PCH~CH~PP~~)~], there is no rapid transfer of hydrogen atoms between the q3-allyl and the metal atom.q3-Acryloyl ligands relating to simple q3-allyl are present in the 1 1 adduct (29) formed between [FeH(C0)4]- and MeO2CC-CCO2Mp. Bond lengths in this molecule indicate a greater contribution of (29a) than (29b).72 Protonation with C0,Me 1-CF3C02H gives [Fe(CO),( q2-trans-Me02CCH=CHC02Me)]whereas Me’ addi- tion (using [Me30]’) gives what could be described as a prop-2-en-1-ylidene complex and its X-ray structure has been illustrated as in (30).73 Another q3-ligand is derived from an alkyne by treating [Mo(C,H,)(CO),Me)] with but-2-yne. The intermediate [Mo(C,H,)(CO),(CMe=CMeCOMe)] reacts with various ligands L(Bu‘NC CO or PPh,) to give [Mo(C,H,)(C0)(L)(q3-CMeCMeCO2)]; CO is incorporated into a lactone ring which acts as a q3-allyl.The X-ray structure is known where L = Bu‘NC.’~ The dynamic behaviour of pseudo-octahedral Mo and W complexes can be interpreted in terms of interchange between configurations such as (31a) and (31 b). Complexes such as [MO(~’-C~H,)(CO)~(P~~PCH,CH~PP~~)]+~~ 70 R. L. Phillips and R. J. Puddephatt J.C.S. Dalton 1978 1736. 71 T. H. Tulip and J. A. Ibers J. Amer. Chem. SOC. 1978,100 3252. 72 K. Nakatsu Y. Inai T. Mitsudo Y. Watanabe H. Nakanishi. and Y. Takegami J. Organometallic Chem. 1978,159. 11 1. 73 T. Mitsudo Y. Watanabe H. Nakanishi I. Morishima T. Inubushi and Y. Takegarni J.C.S. Dalton 1978 1298. 74 M. Green J. Z.Nyathi C. Scott F. G. A. Stone A. J. Welch and P. Woodward J.C.S. Dalton 1978 1067. ’’ J. W. Faller and D. A. Haitko J. Organometallic Chem. 1978 149 C19. A. J. Deeming and J. Evans and [M~(q~-C~H~)(CO)~(acac)(py)]'" have been studied. No evidence for dynamic behaviour was obtained from the 13C n.m.r. spectra of [Mn(q3-C3H,)(CO)4].77 Considerable twisting of the C ring brings HA (endo) close to the metal atom [Fe-H = 1.879(9)A; neutron diffraction] in the 16e-q3-allyl complex [Fe(q3-cyclo- octenyl)L3]' [L = P(OMe)3](32),which was formed by protonating the correspond- ing q4-diene comple~.~~*~~ Thus there is a bonding C-H-Fe interaction. 31P n.m.r. signals in ratio 1 :2 are obtained even down to -140 "C (AB spectrum) so that very + rapid site exchange between HA and HB must occur in solution.However cyclo- hexenyl and cycloheptenyl analogues give ABC 31P n.m.r. spectra at low tempera- tures consistent with an asymmetric structure. Sodium amalgam reduction of this cation gives the corresponding 17e-complex which gives a variable temperature e.s.r. spectrum with 31Pnuclei in ratio 1 1 :1at -140 "C. A fast process (10" s-'; 25 "C) leads to exchange of two 31P nuclei while a slower process (-2 X lo's-'; 25 "C) exchanges all 31P nuclei." The X-ray structure of a norbornene copper(1) complex contains a short Cu-HC distance of 2.01(15)8 but the true nature of this inter- action is unknown." q '-q 1nterconversions.-Thermal decarbonylation of [Mn(CO)5( q '-cis or fruns-crotyl)] gives only [Mn(C0)4( q 3-syn-crotyl)] but using [Ir(Ph2PCH2CH2PPh2)2]C1 as a CO-acceptor under mild conditions there is complete retention of configuration; reactions (13a) and (13b).** Slow q1-q3 interconversions are found for complexes [PtCltq '-allyl)(PPh3)(RNC)] (R = Me or Ar)83*84 which give q3-allyl complexes by 76 B.J. Brisdon and A. A. Woolf J.C.S.Dalton 1978,291,and G.Doyle J. Organometallic Chem. 1978 150,67. 77 A. Oudeman and T. S. Sorensen J. Organometallic Chem. 1978 156 259. " S.D. Ittel F. A. Van-Catledge C. A. Tolman and J. P. Jesson J. Amer. Chem. Soc. 1978,100 1317. 79 J. M.Williams R. K. Brown A. J. Schultz G. D. Stucky and S. D. Ittel J. Amer. Chem. Soc. 1978,100 7407. S. D. Ittel P. J. Krusic and P. Meakin J. Amer. Chem. Soc. 1978,100 3264.M. Pasquali C. Floriani A. Gaetani-Manfredotti and A. Chiesi-Villa J. Amer. Chem. SOC., 1978,100 4918. " N. N. Druz V. I. Klepikova M. I. Lobach and V. A. Kormer J. Organometallic Chem. 1978,162,343. 83 G.Carturan A. Scrivanti U. Belluco and F. Morandini Znorg. Chim. Acta 1978,27 37. '* G.Carturan A. Scrivanti U. Belluco and F. Morandini Znorg. Chim. Acta 1978 26 1. Organometallic Chemistry 351 -co ( trans *Mn(CO)5 + :,-Mn(CO) syn loss of C1- PPh3 or RNC and where R =2,6-Me2C6H3a CHZClz solution contains five different species containing q or q3-allyl ligands. A study has been made of the more dynamic system [PdCl(q 1-CH2Ph)(PEt3)z]+; and for the optically active 77 CHDPh complex no loss of activity occurs in these inter conversion^.^^ Exchange between ql-and q3-benzyl complexes in nitrile solutions is rapid enough at elevated temperatures to give n.m.r.line broadening. Reactions.-Reversible ring opening of q3-cyclobutenyl complexes [reaction (14)]86-88 occurs and with certain substituents and for L = acac both species may be RR R R=Ar; X=Ar' or OMe present in The ring-opening is stereospecific and conrotatory for L = acac but isomeric products are obtained when L = dithiocarbamate. The q3-allyl complex [Mn(C0)4( 1-3-q3-cyclo-octenyl)] is formed by isomerization of the 1,2,6-q3-isomer on standing in hexane solution but reverts to the 1,2,6-q3-mode of bonding in the PPh3 substituted form.89 Only a few of the many examples of the use or intermediacy of q3-allyls in organic synthesis will be given.COz-insertion into [Ni( q3-2-methylallyl)z] in the presence of PMe for example gives complex (33)and several more complex examples are given 0 It I PMe (33) 13' Y. Becker and J. K.Stille J. Amer. Chem. SOC.,1978,100,845. 86 S.H.Taylor and P. M.'Maitlis J. Amer. Chem. SOC.,1978,100 4700. 87 J. R.Jack C. J. May and J. Powell J. Amer. Chem. SOC.,1978,100 5057. 88 P. M.Bailey S. H. Taylor and P. M. Maitlis J. Amer. Chem. SOC.,1978 100,4711. 89 P.J. Harris S. A. R. Knox,and F. G. A. Stone J. Organometallic Chem. 1978,148 327. A. J. Deeming and J. Evans for C0,-insertion into q3-allyl bonds in the intermediate Ni complexes in butadiene oligomerization and in all cases organic carboxylato-complexes are formed.” Organic products of nucleophilic addition of [MeCOCHCOMeI-or [MeS02CHC02Me]- at (q3-allyl) palladium complexes have been studied all involving the nucleophile adding at a terminal allylic It is claimed that the electrophilicity of the ally1 ligand increases on incorporating tertiary phosphines or phosphites into the complex.q3-Allyls of Mn93 and C094 have been studied as hydrogenation catalysts for alkenes or arenes with emphasis on the range of applicability of these catalysts. 4 q4-Cyclobutadiene Compounds Preparation and Structure.-The nickel(0) cyclobutadiene complex [Ni( 7‘-C4Me4)(bipy)]was prepared by Na reduction of the long known nickel(I1) complex [NiC12(q4-C4Me4)],in the presence of bipy and isolated as very stable copper- coloured platelets giving intense blue The state of oligomerization in these phases is not known.The complex [Ni(q4-C4Ph4),] is the first simple bis (cyclobutadiene) metal and the electronic structure of the parent C4H4 complex based on INDO SCF MO calculations has been de~cribed.~’ The complex synthesized by the photochemical reactions (15) as bright orange moderately air-sensitive crystals is apparently the first unsubstituted C4H4early transition metal complex,98 and the X-ray structure of the closely related complex [M0(q4- C4Ph4),(C0),] is reported.99 The annellation of cyclobutadiene has been achieved by the double Wittig reaction (16; X=CH2 or CO) and where X=CO the X-ray structure is established. loo 72-Cyclobutadiene has been recognized in the complex 90 P.W. Jolly S. Stobbe G. Wilke R. Goddard C. Kriiger J. C. Sekutowski and Y.-H. Tsay Angew. Chem. Internat. Edn. 1978,17 124. 91 W. R. Jackson and J. U. Strauss Aust. J. Chem. 1978,31,1073. 92 B. M. Trost L. Weber P. E. Strege T. J. Fullerton andT. J. Dietsche J. Amer. Chem. SOC. 1978,100. 3416. 93 L. S. Stuhl and E. L. Muetterties Znorg. Chem. 1978 17 2148. 94 L. S. Stuhl M. Rakowski DuBois F. J. Hirsekorn J. R. Bleeke A. E. Stevens and E. L. Muetterties J. Amer. Chem. SOC.,1978,100,2405. ” U. Griebsch and H. Hoberg Angew. Chem. Internat. Edn. 1978,17,950. 96 H. Hoberg R. Krause-Going and R. Mynott Angew. Chem. Internat. Edn. 1978.17 123. 97 D. W. Clack and K. D. Warren J. Organometallic Chem. 1978 161 C55. 98 M. D. Rausch and A.V. Grossi J.C.S. Chem. Comm. 1978,401. 99 A. Efraty J. A. Potenza L. Zyontz J. Daily M. H. A. Huang and B. Toby I.Organometallic Chem. 1978,145,315. Organometallic Chemistry 353 (34)which has a localized C=C bond (bond lengths a 1.51; b 1.52; c 1.34 A) and interestingly this has an isomeric form in which the seven-membered ring is folded so that the P atom does not approach the metal; as a consequence q4-co-ordination is then required."' + PhP-RhL Reactions.-Cyclodimerization of alkynes is a general route to q4-cyclobutadiene complexes and conjugated diynes can give complexes such as (35a). Vacuum sublimation (lop4torr) through a hot tube (525 "C) converts (35a) into a 1:1mixture with (35b) but it was established that (35c) was not formed.This is evidence against a mechanism involving reversible cyclodimerizations with diyne intermediates and for one with a transient intermediate such as (35d).'02 5 q4-Diene Compounds Preparation Structure and Dynamic Behaviour.-The displacement of q4-enones (e.g. benzylideneacetone) from [Fe(q4-enone)(C0)2L] (L =tertiary phosphine phosphite or CO) by dienes etc. is a useful route to q4-diene complexes and the synthetic ~sefulness'~~ and the kinetics of displacementlo4 have been examined. Competing associative and dissociative pathways have been identified. A novel synthesis of q4-diene complexes is the treatment of [Co(CsH5)(PPh3)(q2-PhC-CPh)] with N2CHR (R=COzMe etc.) which at room temperature gives [Co(C,H5)(q4-RCH:CPhCPh:CHR)] (isomers) as well as products with coupled alkynes that have been studied by X-ray diffracti~n."~ The X-ray structures of (36) formed from MeCGC-CECMe and [Fe(C0)5],'06 of [RuH(q4-butadiene)-loo M.B. Stringer and D. Wege Aust. J. Chem. 1978,31,1607. lo' W. Winter and J. Strahle Angew. Chem. Internat. Edn. 1978,17 128. lo' J. R.Fritch and K. P. C. Vollhardt J. Amer. Chem. Soc. 1978,100,3643. lo' B.F. G. Johnson J. Lewis,G.R. Stephenson and E. J. S. Vichi J.C.S. Dalton 1978,369. J. A. S. Howell and P. M. Burkinshaw J. Organometallic Chem. 1978,152,C5. lo' P. Hong K. Aoki and H. Yamazaki J. Organometallic Chem. 1978,150,279. '06 G. G.Cash and R. C. Pettersen Znorg. Chem. 1978,17,650. 354 A. J. Deeming and J. Evans (PMe2Ph),][PF6],lo' and of the fluxional molecule [Fe(q4-cyc1ohexadiene)-(CO)z(EtNC)]'08 have been reported.One cyclo-octatetraene is readily displaced from [Fe(q4-C8H8)(q6-C8H8)] by monodentate phosphines or phosphites (L) to give [Fe( q4-C8H8)L3] but by Ph2PCH2CH2PPhz under N2to give [Fe(q4-C8H8)(diphOS)- (N2)][v(N2) = 2105 ~m-'].'~~ Interestingly,N2 co-ordination rather than a q4to q6 conversion of the C8H8 ligand takes place but as expected the Nzis readily displaced by CO. Lanthanide metal atoms react at -196°C with buta-1,3-diene to give after work-up brown solids of type [M(C4H6),] (M = Er Nb or Sm).'" These may contain bonding as in (37b) with an unco-ordinated double bond rather than the q4-bonding as in (37a). Clear evidence for (37b) type bonding was obtained for [Pt(q4-cod)(1,4-q2-CH2CR=CRCH2)] (R = Me or Ph) which was formed by treat- ing [Pt(cod),] with the appropriate diene."' This is of course an oxidative addition of 1,3-diene.Three separate X-ray structures have been determined for q4-complexes of type (38) prepared by reaction of [Fe2(CO),] with substituted cyclopropenes or by reaction of a complex of type (30)with PPh3 or CO. The q4-vinylketen description (38a) has been preferred by some"2 but the q3-allyl/acyl description (38b) by others,' 13*'14 partly on the basis of the CAC bond lengths as found in the appropriate molecules. R3 R4 R3 R4 R' R2 R3 R4 C"C/A Ref. \/ \/ CTC Rz \ 1 \* H Ph Ph Ph 1.494 114 C C \ C=O H H COzMe OMe 1.48 112 *O R< Fe' Me Me H H 1.442 113 (COh The dynamic behaviour of q4-diene complexes of iron continues to be of interest.[Fe(C0)3(q4-cycloheptatriene)] shows no n.m.r. line broadening up to about 100"C but by spin saturation transfer techniques the transfer of spin between ring positions lo' T. V. Ashworth E. Singleton M. Laing and L. Pope J.C.S. Dalton 1978 1032. H. Behrens G. Thiele A. Piirzer P. Wiirstl and M. Moll J. Organometallic Chem. 1978 160 255. H. Felkin P. W. Lednor J.-M. Normant and R. A. J. Smith J. Organometallic Chem. 1978,157.C64. 'lo W. J. Evans S. C. Engerer. and A. C. Neville J. Amer. Chem. Soc. 1978,100,331. '11 G.K.Barker. M. Green J. A. K. Howard J. L. Spencer andF. G. A. Stone J.C.S. Dalton 1978,1839. T. Mitsudo. T. Sasaki Y. Watanabe Y. Takegami S. Nishigaki and K. Nakatsu J.C.S.Chem. Comm. 1978,252. '13 P. Binger B. Cetinkaya and C. Kriiger J. Organometallic Chem. 1978,159,63. 11' G.Dettlaf U. Behrens and E. Weiss Chem. Ber. 1978 111 3019. 355 Organometallic Chemistry 1and 6 was detected for X =CH2 consistent with process (17)."' Where X =CO process (16) must be slow since by selectively destroying one of the two enantiomers illustrated using circularly polarised light (380-500 nm) a specific rotation of 0.012 f0.002"was measured.'16 Since this only corresponded to about 3% destruc- tion the estimated rotation for the pure enantiomer is about 700". The method of spin saturation transfer has been applied to a study of [Fe(q"-c~H~)(rl"-c~H~)l (CsH8 = cyclo-octatetraene)."' Whizzing of the q4-ring could not be frozen out (AGs< 23 kJ mol-') while there is no evidence for shifts in the other ring.The transition state for the exchange of the two rings as deduced from spin saturation transfer must have the four types of CH in the q6-rhg distinguishable. Dynamic 'H and 13Cn.m.r. studies on (Cr(CO),(q"-butadiene)] and [M~(CO),(q~-butadiene)~] have shown these to undergo polytopal rearrangements possibly via trigonal pris- matic transition states.'18 The complexes [CoL3(q4-diene)]' (L =tertiary phos- phine; diene =butadiene or isoprene) are square pyramidal from limiting low- temperature 'H and 31Pn.m.r. spectra but are fluxional at higher temperatures.'" Reactions.-q"-Diene complexes may be protonated to give q 3-allyl complexes. [RuH(q6-C6Me6)( q4-cyclohexa-1,3-diene)]+ was obtained by protonation and although the q3-allyl complex is not formed it is involved in a rapid equilibrium with the hydrido(q4-diene) complex.This is necessary to account for the three-proton n.m.r. signal (8 -2.90 p.p.m.) which is the average for RuH and two endo ring hydrogen atoms. 13' Another example of electrophilic addition is the formation of [Fe(CO)3(CsHsCOMe)]+ by treatment of the cyclo-octatetraene complex [Fe(CO)3(CsHs)] with the Friedel-Crafts acylating reagent (MeCOCl and AlC13). A [5,l,O]bicyclic system had been proposed for this as for the protonated q4-CsHs complex but the X-ray structure establishes a [3,2,1]-bicyclic ligand containing q 3-allyl and q2-monoene groups.'2o Oxidation of [Fe(CO)3(CsHs)] with AgPF6 for example gives the coupled product [(C0)3Fe(~5-C8H8-C8H8-~ 5)Fe(CO)3]2+and while a C-C bovd is formed between the two Cs rings each forms a [5,1,0]-bicyclic system.12' A1Cl3 induces carbonylation of [Fe(C0)3(q4-C6HS)] (C6H8 = cyclohexa-1,3-diene) to give the ring-expanded q4-1,3,5-cycloheptadien-2-onecomplex [Fe(CO),(C,H80)] CO being incorporated into the c6 ring.Thermal treatment of this under CO pressure gives further (transannular) carbonylation to give bicyclo [3,2,l]oct-2-ene-4,8-dione(CSHs02).'22 K. J. Kavel and M. Brookhart J. Amer. Chem. SOC.,1978,100,1619. S. Litman A. Gedanken Z. Goldschmidt and Y.Bakal J.C.S. Chem. Comm. 1978,983. 11' B.E.Mann J.C.S. Dalton 1978 1761. 11* C.G. Kreiter and S. bkar J. Organometallic Chem. 1978,152 C13.M. Bressan R. Ettorre and P. Rigo J. Organometallic Chem. 1978 144 215. 120 A. V. Rivera and G. M. Sheldrick Acta Cryst. 1978,B34,1716. lZ1 N.G.Connelly,M. D. Kitchen R. F. D. Stansfield S. M. Whiting and P. Woodward J. Organometallic Chem. 1978,155 C34. lZ2 B.F. G. Johnson,K. D. Karlin and J. Lewis J. Orgartometallic Chem. 1978,145 C23. A. J. Deeming and J. Evans Important 1,3-diene coupling reactions occur with [Pt(cod),] or [Pt(C,H,),(PMe,>] although it is unlikely that q4-co-ordination is involved at any stage Scheme 18. These products of course relate to intermediates in butadiene oligomerizations at nickel. The trans- arrangement of the vinyl groups in the divinylmetallocyclopentane is significant in that cis-divinylcyclobutane is obtained as a nickel-catalysed product.Since divinyl-metallocyclobutane isomers should be interconvertable by q 1-73-allyl interconversions it is not clear whether the cis- organic product is formed because reductive elimination is favoured for this arrangement or whether for nickel the cis-metallocycle is the stable form."' -[Pt(C2H4),(PMe3)] Scheme 1 *X-ray structure 6 qs-Diene Compounds Preparation and Structure.-Treatment of [W(C5H5)(C0),Cl3] with sodium cyclo- pentadienyl in THF gave a product of apparent formula [W(C,H,),(CO),] the yields of which are increased by addition of NaBH,. The X-ray structure (39) shows that two C,H groups have been added to a C ring to generate the substituted q3-cyclopentenyl ligand.'23 Treatment with sodium and then FeCI; gives a ferrocene derivative by introducing a Fe atom between the two unco-ordinated C5 rings.', Complex (39)is an 18e-system as is [W(C5H5),(C0),] by virtue of one q3-and one q5-ligand.The X-ray structures of and the corresponding indenyl complex'26 prepared in low yield by the reaction of W(CO) with indene are reported. Rapid interchange between the q3-and q5-ligands occurs. An improved synthesis of [M2(C0)6(q5-CsH4R),] (M = Cr Mo or W) by a classical route using Na[C5H4R] has been described. 127 More specialized routes to cyclopentadienyl complexes are reported. Diazocyclopentadiene C5H4N2 reacts with various metal halo complexes to give q5-C51-L,X (X = halide) and this has been applied to Fe and Re.128 Fulvenes 123 J. L. Atwood R.D. Rogers W. E. Hunter I. Bernal H. Brunner R. Lukas and W. Schwarz J.C.S. Chem. Comm. 1978,451. 124 H. Brunner R.Lukas and A. Woditsch J. Organometallic Chem. 1978 161 C49. 125 G.Huttner H. H. Brintzinger L. G. Bell P. Friedrich V. Bejenke and D. Neugebauer J. Organo-metallic Chem. 1978,145 329. 126 A. N. Nesmeyanov N. A. Ustynyuk L. G. Makarova V. G. Andrianov Yu. T. Struchkov and S. Andrae J. Organometallic Chem. 1978,159 189. 127 R. Birdwhistell P.Hackett and A. R. Manning J. Organometallic Chem. 1978,157 239. 128 W. A. Hermann and M. Huber Chem. Ber. 1978,111,3124. Organometallic Chemistry 357 are reduced with LiAlH4 to give substituted cyclopentadienyl anions that may be used to make q5-C5H,R c~mplexes,'~~ and by reacting [(EtO)SiMe2(C5H5)] or [(EtO),Si(C5H5)] with silica gel cyclopentadiene groups may be attached to the surface and metal atoms co-ordinated to these.One such silica-bound complex (40) has been applied to alkene hydroformylation. There is no tendency in these complexes to form binuclear or polynuclear complexes as with unsupported spe- cies.130 The structure of [Fe2(C0)4(q 5-C,H5)2] has been accurately redetermined at 74 K by X-ray and neutron diffraction and calculated electron deformation maps do not reveal electron accumulation between the metal atoms.13' 3,5-Dimethyl-aceheptylene reacts with Mn2(CO)lo to give complex (41) containing two Mn(CO) units bonded either side of the ligand each to a C5 group.'32 Manganocene is high spin (6Alg ground state) and shows cyclopentadienide-type chemistry.The 1,l'-dimethyl substituted compound shows cross-over between high and low spin forms and now the electron diffraction structures of both forms have been measured. The Mn-C distances are greater in the 6Al than in the 2E2 ground state form [2.433(8) compared with 2.144(12) A]. The mol fraction of high spin form [0.62(4)] at 100 "C in the gas phase compares well with that in toluene at 98 0C.'33 Complete methyl-substitution favours low spin and for [Mn(C5Me5)2] there is no evidence for thermal population of the high spin state. This complex undergoes reversible reduction to the diamagnetic complex [Mn(C5Me5),]- iso- electronic with decamethylferrocene.. 34 The first 13C n.m.r. isotope shifts in paramagnetic compounds have been measured for the metallocenes [M(C,R,),] (R = H or D; M = Co Fe+ Cr or V).These are discussed using ferrocene and perdeuterioferrocene as references. '35 The 13C and 'H n.m.r. spectra of the paramagnetic compounds [V(C5H4R),X] (R = Me or Et; X = halide) are well resolved and electron spin delocalizations as determined from n.m.r. shifts have been discussed. These complexes show no tendency to dimerise as does [Ti(C5H5),Cl]. with EtLi or Me3SiCHzLi (RLi) 136 Treatment of [V(C5H5),ClZ] gives solutions of the complexes [V(C5H5),R2]; these were characterized by their e.s.r. spectra which were compared with that of the parent dichloride and treated theoretically. lZ9 P. Renaut G. Tainturier and B. Gautheron J. Organometallic Chem.1978,148,35. 130 F.R. W. P. Wild G. Gubitosa. and H. H. Brintzinger J. Organometallic Chem. 1978,148 73. 13' A. Mitschler B. Rees and M. S. Lehmann I.Amer. Chem. SOC. 1978,100,3390. 13' M.R. Churchill and S.A. Julius Inorg. Chem. 1978,17 2951. 133 A. Almenninger A. Haaland and S. Samdal J. Organometallic Chem. 1978,149. 219. 134 J. C. Smart and J. L. Robbins J. Amer. Chem. SOC.,1978,100,3936. 135 F.H.Kohler and W. Prossdorf J. Amer. Chem. SOC. 1978,100 5970. F. H. Kohler and W. Prossdorf Chem. Ber. 1978,111,3464. 137 A. G. Evans J. C. Evans D. J. C. Espley P. H. Morgan and J. Mortimer J.C.S. Dalton 1978,57. A. J. Deeming and J. Evans Interchange between q3-and q5-C5H5 rings has been menti~ned'~~"~~ and 77'-and q5-rings commonly interchange as in a recent example [Mo(q'-C,H,)(q '-CsHs)(NO)(S2CNR2)] which also undergoes 1,2-shifts of the q '-ring and rotation about the C-N bond as independent fluxional proce~ses.'~~ Energy changes have been calculated for the cyclopentadienyl compounds C5H5X [X =H Me SiH, Mn(CO), Li CUR efc.] as the group X slides across the face of the C5 ring passing from a q'-arrangement through q3,q5,and finally to q2.The relative contributions of the acceptor orbitals of X of a and e symmetry control the preferred geometries and the lowering of the energy of the e orbital going down the group (X = CH, SiH3 GeH, or SnH3) is responsible for the decreasing barrier to sigmatropic shifts.13' Various calculations on q-carbon ring complexes have been carried out relating the influence of ring size to the metal-ligand interactions 'H n.m.r.shifts et~.'~' Reactions.-CF,C~CCF reacts with [MO(C~H~)~I(NO)] adding in a Diels-Alder fashion to one of the cyclopentadienyl ligands to give a bicylo-ligand and this appears to characterize cyclopentadienyl ligands that are less than pentuhaptu or where a greater than 18e-configuration occurs as with nickelocene. 14' Nickelocene also undergoes a strange reaction with bis(dipheny1phosphino)maleic anhydride Ph2PC4O3PPh2,to give a 70% yield of the complex (42) with one C5H5 ligand having inserted into the bidentate ligand. (42) is diamagnetic and a formal localization of a positive charge on nickel and a negative charge on the chelating ligand would account for Unusual behaviour of q5-ligands is also found in the thermal decom- position of [Zr(C5Me5),(H)(CH2CHMe2)]to give 2-methylpropane.143 There is no kinetic isotope effect on deuteriation at the metal-hydride site but surprisingly only on replacing CH by CD3 at the q5-rings. The hydrogen atom transferred to CH2CHMe2 is derived from a CH group not from ZrH and it is proposed that the reductive elimination occurs for the intermediate (43)and not the original complex. H-H M. M. Hunt W. G. Kita B. E. Mann and J. A. McCleverty J.C.S. Dalton 1978,467. N. T. Anh M. Elian and R. Hoffmann J. Amer. Chem. SOC. 1978,100 110. 140 D. W. Clack and K. D. Warren Inorg. Chim. Acta 1978,30,251; J. Organometallic Chem. 1978,157 421 and 1978,162,83. 14' M. M. Hunt and J. A. McCleverty J.C.S.Dalton 1978,480. 14' W. Bensmann and D. Fenske Angew. Chem. Internat. Edn. 1978 17,462. 143 D. R. McAlister D. K. Erwin and J. E. Bercaw J. Amer. Chem. Soc. 1978 100 5966. 144 S. Dzierzgowski R. Giezynski M. Jarosz and S. Pasynkiewicz J. Organometallic Chem. 1978 152 281. 13' 359 Organometallic Chemistry 7 q6-Arene Compounds Preparation and Structure.-The black paramagnetic arene complex [TiC12(C6Me6)][A1C14] is formed by reducing [TiCl,] with Et2AlCl in the presence of he~amethylbenzene,'~~ and Nb atoms react with benzene to give [Nb(C6H6)2] as deep red-purple very air-sensitive crystals. The corresponding toluene and mesity- lene compounds have also been described and their e.s.r. spectra re~0rded.l~~ [W(arene)2] has been prepared previously in low yields by reduction methods or on a small scale using W atoms from a hot filament but now using W atoms formed with an electron gun 1.4 g is obtained in 2.5 h.The compound is much more basic than Moor Cr analogues being protonated in dilute aqueous HCl.146 The preparations of various Moo and Mo" arene compounds including [Mo( q6-arene)(PR,),] are described.147 X-Ray structure determinations of [Mo(q7- C7H7)(BPh4)] and [NEt,][Mo(CO),(BPh,)] have established q6-C6HsBPh3in both'48 and the structure of [Fe(qs-CsHs)(q6-C24H12)]+ has shown that Fe is co-ordinated to one of the outer coronene c6 rings as expected from calculations.149 Using the complexes [RuC12(arene)12 the hydrogenation catalyst [RUHCl(C&k6)(PPh,)] has been ~ynthesized,"~ and reduction with sodium naphthenide in the presence of ligands leads to [Ru(C6H6)LL'] (L and L'are different tertiary phosphines or pho~phites)."~ Complexes of type [Ru(q4-arene)( q6-arene)] have been synthesised by cyclo- trimerization of alkynes with [R~(C~H~)(diene)]l~~ or from Ru atoms and arenes.15 The benezene complex was prepared from Ru atoms and its limiting low-temperature n.m.r.spectrum is consistent with the formulation [~u(q"-C~~~)(q'-C~Hg)l. Simul-taneous broadening of the n.m.r. Me-signals (intensity ratio 2 6 2 :2) of the dynamic complex [Ru(q4-C6Me6)(q6-C6Me6)] occurs and the most likely process involves [R~(q~-c~Me~)~]. Addition of AlMe dramatically affects the d.n.m.r. spectra by accelerating preferentially a localized exchange in the q4-ligand this being too slow for the pure complex to affect the spectra n0ticeab1y.l~~ The metal atom method has been applied to the synthesis of [Ni(C6F5)2(q6-toluene)], which is isostructural with the Co analogue already re~0rted.l~~ Reactions.-There is a nearly quantitative formation of the complexes [Cr(C0)3(fulvene)] by photochemical substitution of arene by dimethyl- or diphenyl-fulvene at the complexes [Cr(CO),(arene)].156 An interesting loss of N2 and HPF6 occurs on heating crystals of [Mn(Co),(q6-c6H,N,)][PF6] to give ring contraction to [Mn(C0)3(q5-C5H4CN)].157 Both benzyl anions and cations may be stabilized by co-ordination. Complete exchange of toluene methyl hydrogen atoms 14' F. G. N. Cloke M.L. H. Green and D. H. Price J.C.S. Chem. Comm. 1978,431. F. G. N.Cloke M. L. H. Green and G. E. Morris J.C.S. Chem. Comm. 1978,72. 147 E. Carmona-Guzman and G. Wilkinson J.C.S. Dalton 1978 1139. M. B. Hossain and D. van der Helm Inorg. Chem. 1978,17,2893. 149 G. Schmitt W. Keim J. Fleischhauer and U. Walbergs J. Organometallic Chem. 1978 152 315. Is" M. A. Bennett T.-N. Huang A. K. Smith and T. W. Turney J.C.S. Chem. Comm. 1978,582. H. Werner and R. Werner Angew. Chem. Internat. Edn. 1978,17,683. A. Lucherini and L. Porri J. Organometallic Chem. 1978,155 C45. 153 P. L. Timms and R. B. King J.C.S. Chem. Comm. 1978 898. M. Y. Darensbourg and E. L. Muetterties J. Amer. Chem. SOC.,1978,100 7425. K. J. Klabunde B. B. Anderson M. Bader andL.J. Rabonovich J. Amer. Chem. SOC., 1978,100,1313. F. Edelmann D. Wormsbacher. and U. Behrens Chem. Ber. 1978,111,817. G. A. M. Munro and P. L. Pauson J. Organometallic Chem. 1978,160 177. A. J. Deeming and J. Evans occurs for solutions of [M~~(pSMe>~(toluene)~] in D20-Na,P04 buffer (pD = 11) presumably via the co-ordinated benzyl anion,'58 whereas many examples of benzyl cation stabilization are known as in a recent Calculations for benzyl cations free and co-ordinated to Cr(C0)3 show an increased .rr-electron density in the C-C bond to the exocyclic carbon and indicate that the bend of 40"of this bond out of the arene plane towards the metal atom gives a stabilization of about 150 kJ mol-' .16' The fluorene complex [Cr(CO)3(q6-C13Hlo)] deprotonates with KOBu' to give an intermediate q6-species with a negative charge formally on the C ring which isomerizes with ti of several minutes to the q5-species reaction (19).This product methylates at Cr with Me1 but the methyl migrates to the C ring and Cr from this to the c6 ring back to its original position.l6* An e.s.r. and 'H n.m.r. study has shown that electron transfer between [Cr(arene)2] and [Cr(arene)2]' approaches the diffusion-control limit (kexch-3 x 10' mol-' dm3 s-') the rate being only slightly affected by methyl substitution at the arene.I6* 8 Nucleophilic Addition at Co-ordinated Carbocycles exo-Nucleophilic addition at [Fe(C0)3(q5-cyclohexadienyl)]+ has been confirmed for F-addition which only occurs with 'bare' F-(KF/18-crown-6 ether/CH3CN),'63 and for CN- addition.'64 exo-Addition of Pr'S- at a q3-allyl group co-ordinated at Fe also occurs.'65 The reaction of [M(C5Me,)(q4-C7H8)]2' (M= Rh or Ir; C7H8 = cycloheptatriene) with acetone gives the exo-isomer of [M(C5Me5)(q'-C7H8CH2COMe)]'.'66 Nucleophiles do not always add at the carbocycle of course and transient intermediates in the reaction of [M(C0)3(q7-C7H7)]' (M =Mo or W) with I- have been studied by flow 'H n.m.r.and stopped-flow spectrophotometric methods.'67 An intermediate with a M-I bond is rapidly formed but this then isomerizes by I- transfer from M to C7H7 not necessarily intramolecularly to give [M(CO),(C,H,I)] and finally CO is lost to give [M(C0)21(C7H7)]. This is ample demonstration that isolated products do not necessarily indicate the initial site of attack.The nucleophilic addition of tertiary phosphines at q4-and q6-cyclic IS8 W. E. Silverthorn C. Couldwell and K. Prout J.C.S. Chem. Comm. 1978 1009. IS9 D. Seyferth J. C. Merola and C. S. Eschbach J. Amer. Chem. Soc. 1978,100 4124. 160 D. W. Clack and L. A. P. Kane-Maguire J. Organometallic Chem. 1978 145 201. 161 A. N. Nesmeyanov N. A. Ustynyuk L. G. Makarova S. Andre Yu. A. Ustynyuk L. N. Novikova and Yu. N. Luzikov J. Organometallic Chem. 1978,154,45. 162 Ch. Elschenbroich and U. Zenneck J. Organometallic Chem. 1978 160 125. 163 B. F. G. Johnson K. D. Karlin J. Lewis and D. G. Parker J. Organometallic Chem. 1978,157,C67. 164 B. F. G. Johnson J. Lewis D. G. Parker P.R. Raithby and G. M. Sheldrick J. Organometallic Chem. 1978,150,115. 165 A. V. Rivera and G. M. Sheldrick Acta Cryst. 1978 B34 3374. 166 C. White S. J. Thompson and P. M. Maitlis J.C.S. Dalton 1978 1305. 167 P. Powell L. J. Russell E. Styles A. J. Brown 0.W. Howarth and P. Moore J. Organometallic Chem. 1978,149 C1. Organometallic Chemistry polyenes has also been studied mechanistically.'68 A theoretical study of the problem has indicated that attack at metal or CO in the series [M(CO),L] (M = Ni L = C2H4;M =Co L = CJHs etc. through to Cr) should occur since calculated 'frontier electron density parameters' favour attack at one or other of these sites depending upon M but that attack at alkene carbon should not occur initially.'69 9 Dinuclear and Polynuclear Compounds The range of hydrocarbon bridges between metal atoms is enormous.For example several papers have appeared describing bridging cyclo-octatetraene as in Scheme 2. [Ti2(CgH&] was known previously to have a p-CsHs as in (A) but reduction Scheme 2 Some M2(C8H8) arrangements (0= CH) gives the green diamagnetic complex [Ti2(C8H8)3]2- believed to contain the bridge as in (B); only one 'H n.m.r. singlet is observed so accidental coincidence or exchange behaviour is necessa~y.'~~ contains p-C,H8 type (c)but the [CO~(C~H~)~(C~H~)] structure of the oxidation product [CO,(C~H,)~(C,H,)]~' is ~nknown.'~' In the salt [Nd(C8H8)(THF)2] [Nd(C,H&] the anion and cation are linked by a bridge of type (D),'72while [MO2(CgHg)3] contains two q4-CgHg rings and a p-C8Hs as in (E).173 [Cr(C,H,),] reacts with [C,H8]2- to give [Cr2(CsH,),(CsH8)] in which the C ring has opened as in (F).174 On treatment of this Cr compound with CO [Cr2(C,H,),(CO),] and cyclo-octatetraene are formed.The C8Hs bridge in (F) is rather like similar bridges formed by alkyne oligomerization with [M2(C5Hs),(CO),] (M = Cr or Mo); D. M. Birney A. M. Crane and D. A. Sweigart J. Organometallic Chem. 1978 152 187. D.A.Brown J. P. Chester and N. J. Fitzpatrick J. Orgunometallic Chem. 1978,155 C21. 170 S. P. Kolesnikov J. E. Dobson and P. S. Skell J. Amer. Chem. SOC. 1978 100,999. 17' J. Moraczewski and W. E. Geiger J. Amer. Chem. SOC. 1978,100,7429. 172 C. W.DeKock S. R. Ely T. E. Hopkins and M. A.Brault Inorg. Chem. 1978 17 625. F. A. Cotton S. A. Kock A. J. Schultz and J. M. Williams Inorg. Chem. 1978 17 2093. "* W. Geibel G. Wilke R. Goddard C. Kriiger and R. Mynott J. Organometallic Chem. 1978,160,139. 362 A. J. Deeming and J. Evans the X-ray structure of [MO(CSH~)~{CSH~(COZM~)~}] shows an open CS chain but with different attachment at the Mo atoms to that in (F).17’ [M Reactions of alkenes and alkynes with [M2(C5H5)2(CO)4] =Cr (X-ray structure rep~rted’~~) and a11ene’79 Mo or W] have been studied and the a~etylene’~~”~~ adducts examined and crystal structures determined. In the alkyne adducts the C-C axis is perpendicular to the M-M axis and such systems have been studied theoretically.180~181Terminal q2-co-ordination of alkenes and alkynes in clusters is rare because of the strong tendency towards oxidative addition (C-H cleavage) or oligomerization but two T2-C2H4 complexes are reported [OS~(CCJ),~(C~H~)]’~~ and [HOs3(SMe)(CO),(CzH4)].ls3 The X-ray structure of the latter has been deter- mined. These were available because readily displaceable groups were present in the clusters used to make them. Oxidative addition of alkenes can give vinyl complexes and these are obtained from the above compounds. Three structures of vinyl compounds of type [HOS,(CO)~,(CRCHR’)] are reported. Where R = R’ = H the U-T arrangement (44a) is present (full neutron and X-ray studyiB4) but a p3-arrangement is adopted when R = R’= CF3.18’ In contrast the zwitterionic form (44c) occurs when R=H and R‘=NEt2.186 In the iridium clusters It ’a,\ 1 CH=NEt2 05 [I~,(C~)~(C,H~Z)Z(CSH~~)]’~~ derived from and [I~~(CO)~Z(C~H~~)(CSH~~)(C~H~O)~~~~ [Ir4(CO)12] and cyclo-octa-1,5-diene (CsH12) both p-vinyl and p-alkyne ligands derived by oxidative addition are present.The p3-indyne ligand in [H20S3(C0)9(p3-CgH6)] also derived by oxidative .addition (of indene) has been shown to contain dynamic co-ordination; evidence for concerted rotation and 175 S. A. R. Knox R. F. D. Stansfield,F. G. A. Stone M. J. Winter and P. Woodward J.C.S. Chem. Comm. 1978 221. 176 M. D.Curtis and W. M. Butler J. Organometallic Chem. 1978,155 131. 177 D.S.Ginley C. R. Bock M. S. Wrighton B. Fischer D. L. Tipton and R. Bau J. Orgunometallic Chem. 1978,157,41.178 W. I. Bailey M. H. Chisholm F. A. Cotton and L. A. Rankel J. Amer. Chem. SOC.,1978,100 5764. 179 W. I. Bailey M. H.Chisholm F. A. Cotton C. A. Murillo and L. A. Rankel J. Amer. Chem. SOC.,1978 100,802. 180 A. B. Anderson J. Amer. Chem. SOC.,1978,100 1153. 181 D.L.Thorn and R. Hoffmann Inorg. Chem. 1978,17,126. 182 B. F.G.Johnson J. Lewis and D. Pippard J. Organometallic Chem. 1978,145 C4. 183 B. F.G.Johnson J. Lewis D. Pippard and P. R. Raithby J.C.S. Chem. Comm. 1978,551. 184 A. G. Orpen D. Pippard G. M. Sheldrick. and K.D. Rouse Acru Cryst. 1978 B34,2466. 185 M. Laing P. Sommerville Z. Dawoodi M. J. Mays and P. J. Wheatley J.C.S. Chem. Comm. 1978 1035. 186 J. R.Shapley M. Tachikawa M. R. Churchill and R. A. A. Lashewysz J.Orgunometallic Chem. 1978 162,C39. 187 G. F.Stuntz J. R. Shapley and C. G. Pierpont Znorg. Chem. 1978,17 2596. 188 C. G. Pierpont G. F. Stuntz and J. R. Shapley J. Amer. Chem. SOC.,1978 100 616. Organometallic Chemistry 363 flipping of the indyne ligand comes from d.n.m.r. The related ortho-phenylene (benzyne) complex [H,OS~(C~)~(C,H~)] originally prepared directly from benzene and [OS~(CO)~~] may also be prepared from benzaldehyde or benzyl Alkynes react with metal clusters in many ways. They may be bisected as in the reaction of PhCGCPh with [os6(co)18] to give [os,(c~),,(~~-cP~)(~~-cP~)].'~~ p3-Co-ordination of alkynes is common but MeO,CC~CCO,Me (L) reacts with [Ir4(co)12] to give [Ir4(Co)8(p2-L)2(p4-L)2] containing a rectangular Ir4 geometry and a new form of alkyne to cluster bonding.'92 Oligomerization is however the dominant behaviour as in the formation of compounds of apparent formulae [Fe3(C0)6(EtC~CH)4],193[R~3(C0)7(B~tC~CH)4],194and[Os3(CO),(EtC~CH)2] (x = 9 or Alkyne ligands are not present in these compounds because new ligands are formed by C-C cleavage or formation hydrogen atom transfer from C to M or from C to C and CO incorporation into the organic ligand.Three separate reports of the formation of p2-CR-CR-CR bridges between nickel,196 palladi~m'~' or platinum198 have appeared. In asymmetric bridged compounds u-bonds from the terminal carbons to one metal atom and a q3-allyl bond to the other can be envisaged but for symmetrical bridges this description is inappropriate.The complex [H30s3(C0)9(CCR2)]' has been shown to have a non-centred probably tilted arrangement of the CCR ligand (n.m.r. evidence) while the related complex [Co3(C0),(CCR2)]' has been discussed in terms of a centred vertical arrangement. A theoretical treatment favours an arrangement for cobalt as for osmium.199 In9 A. J. Deeming J. Organometallic Chem. 1978 150 123. 19' K. A. Azam C. Choo Yin and A. J. Deeming J.C.S. Dalton 1978 1201. 191 J. M. Fernandez B. F. G. Johnson J. Lewis and P. R. Raithby Acta Cryst. 1978 B34,3086. P. F. Heveldt B. F. G. Johnson J. Lewis P. R. Raithby and G. M. Sheldrick J.C.S. Chem. Comm. 1978 340. 193 E. Sappa A Tiripicchio and A. M. M. Lanfredi J.C.S. Dalton 1978 552. 194 S. Aime G.Gervasio L. Milone E. Sappa and M. Franchini-Angela Inorg. Chim. Acta 1978,27 145. 195 M. R. Churchill and R. A. Lashewycz Znorg. Chem. 1978,17 1291. 196 P. D. Frisch R. G. Posey and G. P. Khare Znorg. Chem. 1978 17,402. P. bL Bailey A. Keasey and P. M. Maitlis J.C.S.Dalton 1978 1825. 19' 19' W. E. Carroll M. Green J. A. K. Howard M. Pfeffer and F. G. A. Stone J.C.S. Dalton 1978 1472. 199 B. E. R. Schilling and R. Hoffmann J. Amer. Chem. SOC.,1978,100,6274.

ISSN:0308-6003    

DOI:10.1039/PR9787500337

出版商:RSC    

年代:1978

数据来源: RSC

摘要:

Abbott E. H. 284 Abdallah M. A,. 15 Abdul Malik K. M. 327 Aberg M. 267 Abis L. 328 Abrahamson H. B. 317 Abramov V. M. 11 Abu-Dari K. 266,296 Adam R. D. 244 Adamczyk A. 116 Adams C. J. 258 Adams D. M. 162,201 Adams T. D. Z.,83 Adamson A. W. 315 Addison A. W. 306 Addison C. C. 259 Adedeji F. A. 312 Adkins R. R. 237 Adman E. T. 303 Adolf P. K. 304 Adzima L. J. 242 Ahmad F. 5 Ahmed A. 202 Ahrland S. 162 Aime S. 320 363 Ainscough E. W. 306 Airoldi C. 162 263 Akermark B. 329 Akhtar M. 238 Akimoto H.,215 Alange G. G. 238 Albano V. G. 321 Albin L. D. 326 Albinati A. 321 Albritton D. L. 215 Alcock N. W. 163,266 Aldashin S. M. 175 Alekseev V. I.. 167 Al-Essa R.J. 331 Alexander C. 143 Alexander S. S. jun. 6 Alexandrov Yu. A. 223 Al-Karaghouli A. R. 263 Allen J. D. 157 Allen C. S. 125 Allison N. T. 334 Allman T. 162 Almemark M. 329 Almenninger A. 357 Al-Najjar I. M. 41 A1 Oraibi Z. 212 Alqasmi R. 256 Al’shinskaya L. I. 198 Alt H. G. 339 Altena D. 241 Author Index Al’tman A. B. 254 Altmann J. A. 103 Aly A. A. M. 310 Aly M. M. 125 Alyea E. C. 162 Amar D. 76 Ambartzumian R. V. 55 57 63,64,65,68,73 76 83,84 Amey R. L. 255,326 Amin N. 238 Ammlung C. A. 319 Amos R. D. 252 Amsler P. E. 41 Anastasi A. 8 Anchini A, 302 Anders U.,201 Andersen E. L. 168 Andersen R. A. 260 Anderson A. B. 362 Anderson B.42 Anderson B. B. 359 Anderson 0.P. 162 Anderson R. A. 285,327 Anderson S. P. 55 Andrae S. 356 Andre S. 360 Andrescci M. 312 Andrews. L. 159,254,257 Andrews S. P. 204 Andriamizaka J. D. 210 Andrianov V. G. 356 Andrich G. 315 Anfinsen C. B. 5,6,7 Angelici R. J. 28,46,300,323 Anh N. T. 358 Aniansson E. A. G. 234 Ansari N. A. 248 Antonenko N. S. 46 Antonova A. B.. 335 Aoki K.,353 Appel R. 228 245 Appleby R. 162 Appleton T. G. 345 Appu-Rao A. G. 11 Arif M. 312 Arima S. 18 Arkle. V. 165 Armentrout P. B. 257 Armitage D. A. 240 Armstrong F. A. 295 Arnoldi. D. 69 Aruga R. 249 Ashby E. C. 160 Ashcroft M. R. 332 Ashe A. J. 199 364 Ashworth T. V.354 Asprey L. B. 88,246,264 Astakhin A. V. 181 Atherton M. J. 277 Atkins M. P. 332 Atkins P. W. 150 Atkins R. M. 284 Atovmyan L. O. 175 Atwood J. L. 261 271 272 288,326,330,356 Ault B. S. 157 253 Ault H. K. 250 Avakian P. 113 Avanzino S. C. 312 Avdef A,. 295 309 Averill B. A. 306 Aviram 1 10 Awad S. B. 191 Ayala J. A. 9 Ayminono P. J. 272 ham K. A. 320,363 Azhir A. 5 Babcock G. T. 141 Babel D. 278 Babich M. W. 278 300 Bach R. D. 40 Bachmann C. 338 Back R.A.. 74,92 Backmann F. 93,94 Backmann H. R. 93,94 Badcock C. C. 70 Bader M. 359 Badger P. E. R. 204 Baenziger,N. C. 163,338,347 Baertshi P.,279 Balyens-Volant,D. 106 113 Bagdasar’yan A. K. 275 Bagnall K.W. 265,266 Baidina I. A. 167 Baig M. A. 18 Baikie A. R. E. 305 Bailey P. M.. 347 351 363 Bailey P. S. 233 Bailey R. T. 49,61,91 Bailey W. I. 362 Baillii R. 281 Baird M. C. 329 Bakal Y.,355 Baker J. G.. 254 Balahura R. J. 37 Balch A. L. 316 324 Baldwin A. C. 215 Baldwin P. L. 5 Baldwin R. L. 5 7 8 Author Index 365 Bale J. R. 306 Balk R. W. 312 Ballard D. G. H. 261,328 Ballardini R. 308 Bancroft G. M.. 257,312 Band E. 311 Bandekar J.. 5 Bandoli G.,267 Banister A. J. 238 Banks R. H. 172,264 Bannister J. V. 8 Bannister W. H. 8 Baran E. J. 243,249 Barber M. J. 142 Barbetta A. 313 Barbier J. P. 321 Barbier P. 201 Barbay N. 8 Bard A.J. 138 310 Barker G. K. 179 271 327 354 Barker G. L. 331 Barker J. R. 79 Barker S. L. 312 Barlow J. H. 337 Barnard C. F. J. 338 Barnes D. J. 27 Baron E. J. 272 Barraclough C. G. 299 Barrau J. 209 Barros H. L. C. 313 Barta I. 219 Bartell L. S. 246 Bartetzko R. 238 Bartholmes P. 9 Bartlett,N. 195,256,257,258 308 Bartoli J. F. 335 Barton T. J. 208 210,325 Bartsch R. A. 298 Basalgina T. A. 223 Basile L. J. 106 Basiler E. 257 Basolo F. 290 Basset J. M. 315 322 324 Bastian V. 227 Bates J. K. 200 Bats J. W. 241 Batsanov A. S. 348 Battioni J. P. 323 Bau R. 303 316 319 327 362 Baudler M. 227 Bauer J. 232 Bauer S. H. 56 92 Baumann J. A. 307 Baumanns J.256 Baumer D. 234 Beall H. 310 Beamish J. C. 204 Bear J. L. 299 Beattie I. R. 272 Beattie J. K. 291 292 Beattie W. H. 264 Beauchamp J. L. 199 257 335 Beavan S. W. 116 Bechara E. J. H. 24 Beck W. 313,341 Becker C. H. 257 Becker H. J. 191 Becker Y. 328,351 Beddard G. S. 103 Bedell S. A. 28 Begley M. J. 221 Begun G. M. 202 Behnke W. D. 11,14 Behrens H. 354 Behrens U. 341,354,359 Beinert H. 141 Bejenke V. 356 Belevantsev V. I. 39 Belevskii V. N. 138 Belew J. S. 233 Belin C. 255 Bell L. G. 356 Bellachioma G. 312 Bellard S. 241 Bello J. 6 Bellows J. C. 91 Belluco U. 350 Belokoneva E. L. 198 Belov N. V. 198 Ben-Aim R. I. 92 Benard M. 284,316 Bencini A.299 302 Bender C. F. 257 Bender M. L. 26 Bender R. 321 Benfield R. 320 Bengartz A. 226 Benmair R. M. J. 75 Benn R. 163 Benner L. S. 316 324 Bennett M. A. 328 338 345 359 Bennett R. 27 Bennetto H. P. 252 Bensmann W. 358 Benson S. W. 234 Ben Taarit Y. 315 Bercaw J. E. 272 328 330 358 Berendsen H. C. J. 141 Berg J. M. 282,295 Berg R. W. 245 Berg T. 162,338 Bergerhoff G. 212 Bergkamp M. 296 Bergman J. G. 256 Bergman R. G. 314 320 330 Berke H. 327 329 Berkowitz J. 257 Berley S. A. 174 Berlman I. 111 Berman D. W. 257 Berman H. A. 17 Bernal I. 356 Bernard W. A. 133 Berner V. G. 21 Bernheim R. A. 146 Berninger R. W. 44 Bernstein E.R. 257 Berry M. 289 Berry M. J. 89 Bersohn R. 316 Bertini I. 298 310 Best S. A. 278 Betcher-Lange S. L. 10 Bethune D. S. 89 Beurich H. 320 Beveridge D. L. 234 Bhaduri S. 309,318 Bhat V. S. 243 Bhattacharyya R. G. 280 Biagioni R. N. 195,257 Bialkowski S. E. 54 78 Bicerano J. 166. 234 Bichowski B. 199 Bielaski-Kitchell B. 9 Bignozzi C. A. 308 Bilhou J. L. 315 322 Bilhou-Bougnol V. 322 Billing G. D. 253 Billman K. W. 73 Binder H. 204,312 Binger P. 354 Binstead R. A. 291,292 Birdwhistell R. 356 Birk J. P. 323 Birnbaum E. R. 21 Birney D. M. 361 Biro A. 287 Bischel W. K. 257 Bishop M. M. 293 Bitsoev K. B. 202 Bittenson S. 74 Bjerrum N. J. 236 Bjork I.8 Black J. G. 56 Blackburn G. M. 39 Blackmer G. L. 298 Blauenstein P. 162 Blanchard M. 51 Blandamer M. J. 323 Blaton N. M. 35 Blatt Y. 14 Blecher A. 226 Bleeke J. R. 352 Block E. 217 244 Block F. 325 Block K. E. 195 Bloembergen N. 56 Blum A. D. 8 Boas J. F. 140 141 Boate A. R. 122 124 246 247,257 Bobrik M. A. 295 306 Bochin V. P. 249 Bochmann M. 193 Bock C. R. 362 366 Author Index Bock H. 133 Bogge H. 279,280,304 Bohle C. 194 Boehm H. P. 245 Boti Z. 207 Boggs J. M. 10 Boguslavskaya L. V. 40 Bohra R. 156 Boiret M. 165 Bojes J. 238 Bokii N. G. 181 348 Boland B. J. 151 Bombieri G. 266 Bond A. M. 308,314 Bondarenko G. N.275 Bonner. F. T. 215 Bonny A. 213 Bonucci J. A. 215 Boormann P. M. 284 Booth R. J. 121 Borel M. M. 160 Borg D. C. 140 Borisov S. V. 167 Bornais J. 246 Bornmann L. 8 Bosio L. 204 Botto I. L. 243 272 Bottomley F. 306 Bottril S. E. 318 Boudhaut M. 209 Boucly P. 308 Bougon R. 255 Bour J. J. 304 Bouten P. C. P. 304 Bowden F. L. 270 Bowser J. R. 169,188 196 Box H. C. 128,133,136 Boxhoorn G. 312 Boyd B. D. 312 Boyd P. D. W. 297 Boyd P. M. 75 Braca G. 315 Brader A. H. 269 Bradley D. C. 156 305 Bradley M. G. 324 Bradlry E. B. 195 Brher W. 158 Braid M. 237 Braithwaite A. C. 38 Brand L. 9 Brandts J. F. 5 7 Brant P. 305,307 309 Brashears H. C.jun. 257 Brassington N. J. 249 257 Bratt S.W. 125 129 Brau C. A. 251 Brault M. A. 262 361 Brauman J. I. 79 292 293 298,318,329 Braun R. W. 246 Braun W. 74,80 91 Braunstein P. 321 Bravard D. L. 281 Bray R. C. 142 Breakell K. R. 205 Breedon N. 87 Bregadze V. I. 180 181 Bregante T. L. 295 BrCgeault J. M. 323 Bremner J. B. 300 Brennan M. 7 Brenner D. M. 79 Bresadola S.,183 Bressan M. 355 Brevard C. 257 Brewer R. G. 59 Brezinski M.; 346 Brier P. N. 254 Briggs T. S. 195 Brill W. J. 282 Brintzinger H. H. 356,357 Brisdon B. J. 350 Brisson D. H. 41 Brochon J. C. 22 Brockner W. 250 Brodhag C. 189 Brom J. M. 121 Bronger W. 290 Brookhart M. 355 Brough L.325 Brown A. J. 360 Brown C. 220 Brown D. A. 184,361 Brown D. B. 331 Brown D. H. 304 Brown D. R. 119,120,122 Brown H. C. 175 Brown I. D. 207,281 Brown J. M. 151 Brown L.D. 338 Brown M. P. 301,316,335 Brown R. K. 323,350 Brown R. M. 212 Brown S. C. 322 Brown S. D. 235 Brown T. G. 290 Brown T. L. 314,316 317 Brown T. M. 275 Brownlee R. T. C. 164 Brownstein M. 256 Brownstein S.,246 Bruce D. M. 258 Bruce M. I. 335 Bruckner S.,321 Bruice T. C. 30,294 Brune D. C. 140 Brunel D. 245 Brunner F. 63 Brunner H. 214,356 Brunvoll J. 189 243 Bryan E. G. 318 Brynestad J. 162 Buchlaus H. U. 325 Buchler J. W. 305 Buck H. M. 123 Buckingham D. A. 27,28,32 33,36,293 Buckland A.D. 229 Budding H. A. 213 Budzinski E. E. 136 Biinzli J-C. G. 262 Bugaenko L. T. 138 Bukowska-Strzyzewska,M. 263 Bukovec P. 205 Bullock J. I. 263,284 Bullock P. A. 12. Bulten E. J. 213 225 Bulychev B. M. 202 Bunker B. C. 126,307 Bunzey G. 281 Burak 1.,,251 Burdett J. K. 289 290 311 314 Burdett N. A. 214 Burgess J. 39 323 346 Burges A. 92 Burk P. 330 Burke J. M. 306 Burkhart R. D. 115 Burkinshaw P. M.,353 Burley J. W. 224 Burns G. T. 210,325 Burns R. C. 248,258 Burstein E. A. 14 17 Burton B. 122 Bury A.. 332 Busch D. H. 25,305 Busel E. P. 17 Bush C. A. 12 Bushueva; T. L. 17 Buss B. 241 Butcher R. J. 52 127 Butler G. 283 Butler J.N. 75 Butler W. M.,317 362 Buttershaw J. 151 Eyer R. L. 51 Byers D. M. 10 Bynum R. V. 271 Caballero J. 92 Cabral J. de O. 160 Cabral M. F. 160 Caddy P. 343 Cadman P. 216 Cady G. H. 255 Caira M. R. 266,284 Calabrese J. C. 169 173 326 Calado J. C. G. 288 326 Calas R. 204 219 Calderazzo F. 266 Callahan K. P. 183 184 Callaway B. W. 227 242 Callot H. J. 300 332 Calvert R. B. 328 Calvin M. 290 Calvo C. 236 Camassei F. D. 252 Caminate W. 199 Cammack R. 142 Campbell A. N. 206 Author Index Campbell D. 293 Campbell J. D. 82 Canivet P. 245 Cann J. R. 11 Cann K. 348 Cannon J. 293 Canti G. 298,310 Cantor C. R. 19 Canty A. J. 164 Capella L.205 Capote. M. A. 202 Capshew C. E. 335 Caranoni C. 205 Cardaci G. 312 Cardin C. J. 327 Cardin D. J. 288 327 Carlson B. 227 Carmona-Gmann E. 330,359 Carpentier C.-D. 207 Carrana C. J. 306 CarrC D. 163,206 Carre J. 250 Carrey E. A. 5 Carrington A. 118,151 Carroll W. E. 327 363 Carrondo M. A. A. F. de 199,309,340 Carsten K. 191 Carter J. C. 204 Carton P. M. 216 Carturan G. 350 Cartwright S. J. 39 Carty A. J. 333.344 Cary L. W. 318 Casablanca F. 222 Casas J. S. 204 Casavecchia P. 257 Casella L. 309 Casellato U.,264 Casey C. P. 326 333 Cash G. G. 353 Cassim J. Y. 13 Cassol A. 265 269 Castel A. 210 Castineiras A. 204 Castro C. A. 279 Catterall R.119 Catton G. A. 262 Cause J. N. 329 Caville C. 249 Cazes A. 204 210 Cecconi F. 307 Celon E. 266 Center R. E. 257 Cetinkaya B. 354 Chagas A. P. 162 Chaichit N. 164 Chaikin A. M. 251 Champarnaud-Mesjard Chan S. F. 39 Chan S. I. 272 Chan T. H. 245 Chandrasekaran E. S. 182 Chang C. H.F. 205 Chang J. C. 140 Chang M. 307 Chang T. Y. 50,51,53 Chanussot J. 254 Chanysheva I. R. 40 Charkin 0.P. 254,256 Charles R. 328 Charlier M. 16 Charpin P. 266 Chatt J. 282,283 Chaudret B. N. 340 Chavin Y. 322 Chedekel M. R. 147 Chegodaev P. P. 251 Chekalin N. V. 73,76,83 288 Chen C. H. 257 Chen G. J-J. 344 Chen H. 291 Chen J 41 Chen K. S. 144,325 Chen L. S.,308 Chen M.W. 341 Chen S. 290 Cheng C. 76 C. T. Cheng C. P. 314 Cheo P. K. 50 Chester J. P. 361 Chevalier R. 309 31D Chevrel R. 281 Chevrier B. 300 335 Chianelli R. R. 273 Chiang C. C. 242 Chiang C. K. 238 Chien. K. R. 92 Chien S. H. 146 Chiesi-Villa A. 350 Chiggino K. P. 107 Chignell D. A. 5 Chin H. B. 316 Chini P. 321 Chipman D. M. 234 Chisari A. 263 Chisholm M. H. 274 284 285. 286 311 317 329 362 Chisnell J. R. 282 Chiusano M. A, 176,177 Chivers T. 238 Chizhevsky I. T. 348 Chobert G. 214 Chock P. B. 21 Chodash D. F. 244 Chong K. S. 205 Choo Yin C. 363 Choppin G. R.,264 Chottard J. C. 323,335 Chow M. 146 J-C. Christe K. O. 216 235 252 255 Christensen R.L. 146 Christie B. 200 Christou G. 283 295 Chu G. Y.H. 301 Chung S.K. 332 Churchill M. R. 276,282,318 319,320,334,357,362,363 Ciampolini M. 262 Cianelli G. 313 Ciani G. 321 Cilento G. 24 Ciriano M.,301 Clack D. W. 352 358,360 Clardy J. C. 273 Clark G. R. 29,32,45,46 Clark D. N. 288,334 Clark C. R. 305,337 Clark J. H. 251 Clark M. D. 92 Clark R. J. H. 236 246 278 301,308 Clark T. 325 Clarke M. J. 307 Claude R. 297 Claudy P. 250 Claxton T. A. 122,131 Clay R. M. 302 Clemente D. A. 267 Clementi E. 128 Clifford A. F. 247 Cliffk B. E. 150 Cloke F. G. N. 276,289,359 Close D. M. 133 Clyne M. A. A.. 254 Coates H. 220 Cobbold D. G. 236 Cock P.37 Cockle S. A. 10 Coffey C. C. 301 Coggiola N. J. 60 Cohen S.A. 171 Cohen T. 44 Colas A. 315 Cole-Hamilton D. J. 271,340 Coleman B. 325 Coles B. R. 32 Colles M. 51 Collins D. M. 285,327 Collins M. P. S.,216,237 Collins T. J. 324 Collister J. L. 253 Collman J. P. 292 293 298 306,318,329 Colman P. M. 303 Colonna G. 6 Colquhoun H. M. 167 180 185,187 Colton R. 314 316 Combourieu J. 215 Commereuc D. 322 Commeyras A. 245 Compton R. N. 246 Condorelli G. 265 269 Connelly N. G. 355 Connolly J. W.,213 Connor J. A. 312 Cook D. H. 161 368 Cooksey B. G. 172 Coombe R. D. 254 Cooper C. D. 246 Cooper J. N. 251 Cooper J. W.. 122,123 Cooper S.R. 290,295,296 Cooperman B. S. 41,42 Coppens P. 237,238 Corbett J. D. 259,268 Corbridge D. E. C. 156 Corfman D. 11 Corigliano F. 272 Corkum R. 92 Cormier M. J. 22 Corrie J. E. J. 215 Cosby L. A. 321 Costa G. 308 Costes J-P. 197 Costes R-M. 266 cot L. 212 Cotter T. P. 63,67 Cotton F. A. 222 274 281 284,285,286,287,305,311 327,346,361,362 Cotton J. D. 213 214 Coucouvais D. 163 Coudanne H. 126,297,302 Couldwell C. 360 Couret C. 210 Cournoyer M. E. 253 Courtis A. 261,328 Covey W. D. 43 Cowie M. 317 Cowley A. H. 246 Cox A. 147 Cox B. G. 159 Coxon J. A. 254,257 Cozens R. F. 113 1’ Crabtree R. H. 343 Cradock S. 213 Cragel J. 282 Cramer R. E. 261,265,300 Cramer S.P. 282,306 Crampin J. 7 Crane A. M. 361 Crane G. C. 256 Crane W. S. 310 Crawford R. D. 251 Creaser I. I. 298 Crichton O. 315 Criegee R. 233 Cripps H. N. 113 Critchlow P. B. 305 Crober D. K. 312 Crocker C. 309 Crocombe R. A. 246 Cros G. 197 Cross S. N. W. 229 Cross V. R. 243 Cruickshank F. R. 49 61 91 Csanyi L. J. 207 Cubicciotti D. 268 Cueilleron J. 174 189 Cummings S. C. 308 Cumins W. J. 160 Cundy C. S. 218 Curic M. 21 1 Curl M. G. 337 Curran A. H. 254 Curry K. K. 196 Curtis E. C. 255 Curtis J. C. 296 323 Curtis M. D. 218 219 317 362 Curtis N. F. 309 Cushman B. M. 331 Cushner M. C. 246 Cygon M. 262 Cyrkier I. 195 Cyvin B.N. 250 Cyvin S. J. 171 250 Czarnecki J. J. 34 Czarnowski J. 235 Daake R. L. 259,268 Daamen H. 312 Da Costa A. M. 312 Dahl L. F. 316 Dahlgreen R. M. 315 Daily J. 352 Dale R. E. 19,102,116 D’Alessio G. 8 Dalle J. P. 111 Dalton D. 332 Dalton L. R. 139 Dan E. 112 Dance I. G. 310 Dance J-M. 251 DanEcEk J. 105 Daniel E. 15 Daniel F. 248 D’Aniello M. J. 347 Daniels J. A. 338 Danov S. M. 38 Dao N. Q. 288,334 Dapporto P. 262,274,307 Daren W-C. 80 Darensbourg D. J. 313,314 Darensbourg M. Y.,313,359 Darnall D. W. 21 Dartmann M. Das K. 299 Das M. 292 Das M. K,196 Das T. P. 140 Datton A. 247 Dauter Z. 250 David C. 106 107 112 113 David F. 264 Davidson D.W. 234,255 Davies A. G. 213 Davies B. 68 87,246,315 Davies J. E. 297 Davies S. G. 289 Davis A. R. 269,309 Davis F. A. 241 Davis M. S. 140 Author Index Davis R. E. 335,348 Davis S. C. 322 Davison A. 335 Dawoon J. H. 306 Dawoodi Z. 362 Dawson J. H. 303 Day C. S. 330 Day D. 234 Day R. O. 263 Day V. W. 330 Dazord J. 174 Deacon G. B. 262 De Boer J. J. 219 322 Declercq J. P. 219 De Corpo J. J. 240 Dederer B. 238 Dedieu A. 308 Deeming A. J. 320 332 363 de Giovani W. F. 262 De Graaf-Hess A. C. 23 Dehnicke K. 202,278 Deiseroth H-J. 158,237 de Jersey J. 304 Dekkers J. 28 de Kock C. W. 262,361 Dekok A. 23 de Leifde Meijer H. J. 340 dell’Amico G. 266 Delmotte F.17 Del Prl,A. 266 Delucia M. L. 237 Demain C. P. 312 de Maleissye J. T. 92 De Marco R. A. 246 Demarteau W. 107 112 de Meester P. 310 Demiray A. F. 250 de Moira P. P. 147 De More W. B. 214 Demuynck J. 338 Denney D. M. 248 Denney D. Z. 248 Dennis R. B. 52 Denniston M. L. 165,176 Dewar M. J. S. 166 de Oliveira W. 263 de Paoli G. 266 de Rango C. 266 De Ranter C. J. 35 De Renzi A. 342 Derrington C. E. 279 de S& G. F. 263 de Silva M. A. V. R. 288 de Shone R. 282 Desimore R. E. 282 Desio P. J. 162 Desmarteau D. D. 223 235 252,258 De Stefano A. J. 167 Dettlaf G. 354 Deutsch,,E. 213 308 Devaud M. 214 Dever D. F. 49,72,73 de Villardi G. C. 261,266 Author Index Devynck J.308 De Waal D. J. A. 332 Dewan J. C. 249,302 Dewar M. J. S. 166 de Wet J. F. 266 284 Dexter D. L.. 102 Dhillon D. S. 248 Diamantis A. A. 283 Dias A. R. 288 326 Dias F. S.,263 Dias S.A. 162 Di Blasio B. 342 Di Carlo E. N. 312 Dickinson R. 216 Diehl M. 238 241 Diehl R. 207 Diellmann J. F. 15 Dieman E. V. 273 Dienstbach F. 206 Dieseroth H. J. 323 Dietrich H. 166 Dietsche T. J. 347 352 Dietz R. 336 Dietzsch W. 128 Dillon K. B. 228,229 Dilworth J. R. 282 Dines M. B. 273 Dion M. 269 di Pasquala S. 272 Disalvo F. A. 235 Dismukes G. C. 290 Dittmar G. 248 Di Vaira M. 222 296 299 Divakaruni D. 342 Diversi P. 348 Dixneuf P.H. 333 Dixon D. A. 172,174 Dizikes L. J. 211 Dobbs A. J. 150 Dobkowski J. 146 Dobson G. R. 347 Dobson J. E. 361 Dockter M. E. 22 Dodd D. 41 Dotz K. H. 336 Dolgoplosk B. A. 275 288 Doljikov V. S. 73 83 Dolphin D. H. 300 306 307 Dong D. 270,329 Dong V. 309 Dooley D. M. 303 310 Dorfman L. M. 314 Dori Z. 287 Dorman W. C. 273 Dornfeld H. 163 279 280 310 Dorrity I. A. 267 289 Dose E. V. 291,292 Dotan I. 215 Douglade J. 231 Douglas D. J. 253 Douglass D. C. 254 Doun S. K.,246 Dousse G. 209 EberI K. 335 Dowd P. 146 Echols W. H. 114 Down M. G. 158 Edelblut A. W. 283 Downs A. J. 170 172 257 Edelhoch H. 6. 1423 314 Edelmann F. 341 359 Doxsee K. M. 298 Edelstein,N.M. 171,172,264 Doyle G. 350 265 Doyle J. R. 338 347 Eden J. G. 257 Drache M. 175 Edgell W. F. 313 Drager M. 220 226 Edmonds J. A. G. 46 Drago R. S. 126,307 Edwards A. J. 236,245,249 Dragulescu G. 46 Edwards H. G. M. 249,257 Drake J. E. 166 190 Edwards J. 265 Drew M. G. B. 160,163,267 Edwards J. D. 308 270,291 Edwards P. P. 119 Drickamer H. G. 5 Edwin J. 193 Driessen P. B. J. 325 Efraty A. 352 Drifford M. 254 Eftink M. R. 16 DroWynski J. 264 Egawa F. 301 Druckenbrodt W. G. 175 Egdell R. G. 172 206 Druz N. N. 350 Eggers D. F. 166 Duax W. L. 159 Eguchi G. 10 Duben J. 177 Eickman N. C. 303,310 Du Bois G. C. 304 Einarsson R. 15 Ducrew G. 309 Einstein F. W. B. 269 306 Dudarev V. Ya 249 309 Duesler E.N. 310 Eisele G. 192 Duffant N. 204 Eisenbarth R. 175 Duke B. J. 216,237 Eisenberg R. 347 Dukes G. R. 309 Eisenberger P. 269 Dukes M. D. 334 Eisenmann B. 247 Duncan D. P. 208,209,325 Eisinger J. 19 102 116 Duncan R. E. 301 Ekstrom A. 267 Duncan W. 213 Elder R. C. 213,308,338 Dunks G. B. 166,174 Elian M. 326 358 Dunn J. B. R. 292 Eller P. G. 256 264 Dunning F. B. 257 Ellerman J. 222 Dunogues J. 204,219 Ellinger Y. 270 Dupont T. J. 167 Ellinghaus J. 310 Dupre J. 62,67 Elliott C. M. 298 du Preez J. G. H. 266 Ellis J. E. 313 Dupre-Maquaire J. 62 67 Ellsworth D. L. 40 Duran N. 24 Elschenbroich Ch. 360 Durig J. R. 199 Ely S.R. 262 361 D’Urso N. R.. 246,278 Emmenegger F. 206 Dusavoy Y. 321 Emsley J. W. 338 Duyckaerts G.172 265 Endicott J. F. 333 D’yachenko 0.A. 175 Endres H. 309 Dye D. J. 176 177 Enemark J. H. 281 Dyke S. F. 298 Engberts J. B. F. N. 256 Dyrkacz G. R. 304 Engelke C. 191 Dyrkheev V. V. 234 Engerer S. C. 262 354 Dzelzkalns L. S.,215 Englehardt U. 252 Dzierzgowski S. 358 Englert A. 20 English A. D. 328 Eady C. R. 320,324 Enjalbert R. 204 Eaker D. W. 234 Epand R. M. 10 Earnest S. E. 331 Erb W. 204 Eastland G. W. 120 121 Eri T. 122 136 Eriksson B. 263 Eaton D. R. 275 300 Erker G. 329 Eaton G. R. 305 Erwin D. K. 278,328,358 Eaton S.S. 305 Eryshev B. Ya. 46 Eaton W. A. 292 Eschbach C. S.. 360 370 Author Index Escudie J. 210 Espenson J. H. 40 EsperHs S. 266 Espinola J. G. 263 Espley D.J. C. 277 357 Estes W. E. 302 Ettorre R. 355 Eujen R. 224 Eulenberger G. 208 Evans A. G. 277,357 Evans D. F. 261 Evans G. T. 150 Evans J. 166 320 322 338 Evans J. C. 277,357 Evans W. J. 261 262 326 Evdokimova E. I. 39 Evitt E. R. 330 Extine M. W. 274 284 285 286,317,346 Eyal M. 25 1 Eyring E. M. 214 Eysel H. H. 305 Ezhov V. K. 258 Fabbrizzi L. 302 Fachinetti G. 313 324 345 Fackler J. P. 309 Fagan P. J. 265 330 Faggiani R. 207 237 Faigle G. 312 Fairdough R. F. 19 Fajer J. 140 Falck L. 249 Falconer W. E. 235,236,251 256,260 Faller J. W. 349 Faltynek R. A. 315 Fanchiang Y.-T. 298 Fanning M. O. 184 Fanwick P. E. 281 285 Faria-Oliveira 0.M.M.,24 Farneth W. E. 81 Farrell J. 91 Farrell N. 307 Farrow M. M. 214 Farrugia L. J. 318 Favas M. C. 289 Favez C. M. P. 273 Fawcett V.,249 Fay R. C.. 269 Feder H. M.,315 Fedor L. R. 45 Fedotov V. G. 251 Fehlner T. P. 168 177 Fehrmann R. 236 Fehsenfeld F. C. 215 Feitelson J.. 8 Felicissimo A. M.P. 262 Felkin H. 343 354 Fellmann J. D. 276 334 Fellows R. L.. 264 Feltham R. D. 307 Felthouse J. R. 303 310 Felton R. H. 140 Fender B. E. F. 308 Fenske D. 358 Fenton D. E. 161,302 Ferguson D. 270 Ferguson E. E. 215 Ferguson G. 164 Fergusson J. E. 307 Fernandez J. M. 319 320 363 Fernando J. 312 Fernando Q. 309 Ferrante R. F. 121 Ferraro J. R. 127 300 Ferrel J.M. 233 Ferris N. S. 303 Ferroni R. T. 203 Fessenden R. W. 150,216 Feuerhahn M. 252 Fiato R. A, 321 Fielding L. 238 Fieselmann B. F. 271 Fife T. H. 32 35 Figgis B. N. 124 Filby A. G. 213 Filler R. 256 Filowitz M. 279 Findenegg G. H. 234 Fink D. 207 Finke R. G. 318 329 Firor R. L. 260 Fischer B. E. 303 Fischer D. 108 114 Fischer E. O. 288 334 335 Fischer H. 131 Fischer J. 321 Fischer J. R. 335 Fischer O. 281 Fisher B. 362 Fisher C. H. 257 Fisher E. R. 56 Fitch J. W. 281 Fitzpatrick N. J. 184 361 Flamini A. 271 312 Flannery M. R. 257 Fleischhauer J. 359 Fleming R. H. 284 Flengas S. N. 268 Flickiger R. 281 Floriani,C. 176,270,313,324 345,350 Hossmann W.136 Flynn G. 81 Flynn G. W. 63 74 Forster Th.,18 100 101 Folcher G. 266 Foner S. N. 251 Fong F. K. 91,232 Foong S. W. 39 Foose D. S. 319 Ford K. H. 298 Ford P. C. 37,296,298 Forman A. 140 Forsyth M. I. 187 Fortier S. 159 Fortin R. 51 Foster B. A. 347 Foster D. M. 27 Fouda S. A.. 307 Fourcroy P. H. 163 Fowles G. A. W. 284 Fox K. 246 Fox R. B. 113,114 Fox W. B. 246 Foxman B. M. 274 Fradin F. Y. 291 Fragala I. 265 269 Franchini-Angela M. 363 Frank A. 210,335 Frank C. W. 108 Frank P. 303 Frankel D. S. 62 Frankel R. B. 282 294 295 Franklin S. J. 335 Fraser G. W. 250 Frattali V. 14 Frazier C. C. 315,329 Fredericks S.,340 Freed J.H. 149 Freedman A. 316 Freeman H. C. 303 Freeman M. P. 91 Freeman W. A 309 Freidlin G. N. 46 Freisheim J. H. 14 Freund,S. M. 61,73,83,88,90 Frey P. A. 13 Frey R. 103 Freyberg D. P. 266 Friedman A. J. 241 Friedrich P. 356 Friesen G. D. 174,249 Frigon R. P. 11 Frisch P. D. 363 Frit B. 206 268 Fritch J. R. 353 Fritchie C. J. 281 Froelich J. A. 314 Fruge D. R. 232 Fuchikami T. 210 Fiillgrabe H.-J. 195 Fuess H. 241 Fukaya M. 135 Fukui K. 237 Full R. 193 Fuller C. C. 300 Fullerton T. J. 347 352 Fumagilli A. 321 Furukawa K. 213 Furzikov N. P. 55 57 63,68 Fuss W. 67,94 Fusseder B. 323 Fusstetter H. 198 Fykin L. E. 249 Gaetani-Manfredotti,A. 350 Gafni A.9 13 15 Gage L. D. 284 Author Index Gagne R. R. 292,306 Gaines D. F. 167 169 170 173 Gale R. J. 201 Galembeck S. E. 312 Gallagher P. K. 254 Galley W. C. 17 Galloway L. 232 Galy J. 126 204 250 302 Galyer L. 275 Gamsjager H. 279 Gamss L. A. 73 Gandini A. 74 Ganguli P. 292 Gantt E. 24 Garber A. R. 167,170 Garcia D. 77 Garcia-Blanco,S. 164 Gard G. L. 235,277 Garel J. R. 7 8 Garg S. K. 255 Garner C. D. 278 283 284 295 Gamier A. 310 Gamey J. F. 279 Gaskill G. P. 314 Gastinger R. G. 214 Gatehouse B. M. 164 296 Gates B. C. 322 Gatteschi D. 297 299 302 Gaudemer A. 308 Gaur D. P. 156 Gautheron B. 357 Gavens P. D. 319 Gavrilenko I.F. 288 Gavrilova L. A. 170 Gay R. R. 306 Gaze C. 133 Geanangel,R. A. 195 Geavens P. D. 324 Gebert E. 267 Gedanken A. 355 Geibel J. 293 Geibel W. 361 Geiger W. E. 361 Geiger W. E. jun. 126 Geldard J. F. 299 Gelius U. 257 Gell K. I. 328 Gellatly B. J. 266 284 Gemal A. L. 260 Gemmler A. 190 Gensmantel N. P. 34 Geofioyl G. L. 278,324 George G. A. 115 George T. A. 283 Gerchman L. L. 224 Gergragt Ph. J. 146 Gerloch M. 297 302 Germain A. 245 Germain G. 219 Gerrity D. D. 323 Gerschitz J. 8 Gervasio G. 363 Gervol J. 204 Gerwarth U. W. 192 194 Geustens G. 106 107 112 113 Ghelis C. 7 Gheorghiou C. 254 Ghilardi C. A. 222 297 299 Ghiron C. A. 16,23 Ghotra J.S. 260 Giannini I. 252 Gibian M. J. 233 Gibson J. F. 278 Gieren V. 238 Giese K. C. 272 Giezynski R. 358 Gijben H. P. 338 Gilbert B. 201 Gilbert B. C. 133 Gilbert B. P. 172 Gilbert J. 51 Giles J. R. M. 134 243 Gilje J. W. 196 265 Gill J. B. 242 Gillen K. T. 254 Gillespie R. J. 236 237 255 256 Gillies B. S. 306 Gillum W. O. 282 294 295 Gimarc B. M. 246 Gingerich K. A. 284 Ginley D. S. 362 Giunchi G. 128 Gitterman A. 39 Gladysz J. A. 236 313 333 Glass W.-K. 46 Glatt I. 77 Gleiter R. 238 Gleizes A. 250 Glemser O. 240,241 Glennon C. S. 308 Glick M. D. 282 Glicksmann H. D. 278 Glickson J. D. 205 Glidewell C. 226 Glover G. I. 24 Glowiak T.275 Go N. 6 Goddard W. A. 111 233 Goddard R. 352,361 Goddard W. A. 341 Godek W. S. 279 Godovikov N. N. 180,181 Goebel C. V. 338,347 Goedken V. L. 296 Goel A. B. 160,203 Goel R. G. 162,164 Goel S. 203 Gosele U. 103 Gotze. R. 194 313 Goetzfried F. 341 Goffart J. 172,265 Goggin P. L. 204 309 Golden D. M.. 79 215 37 1 Golden S. 118 Golding B. T. 332 Golding R. M. 124,292 Goldschmidt Z.. 355 Gombler W. 243 Goodall D. C. 242 Goodenough T. J. 288 Goodfellow R. J. 309 Goodgame D. M. L. 291,309 Goodgame M.. 290 Goodman M. F. 91 Goodwin H. A. 305 Gorbarov V. V. 223 Gordon G. 256 Gordon J. G. 11,324 Gordon R. J. 90 Gordon S. 264 Gordy W. 134 136 Gorelik V.M.. 275 Gorgues A. 333 Gorham J. D. 172 Gornostaev L. L. 254 Gorokhov V. S. 63 Gorokhov Y.A. 55 57 63 64 65 68 Gosselck J. 244 Goto M. 305 Gould E. S. 298 Goure W. F. 208 325 Gowenlock B. G. 160,325 Gower M. C. 63,73 Gowling E. W. 34 Grabaric B. S. 314 Grabaric Z. 314 Grabowski J. 24 Graceffa P. 118 Gratzel M. 208 232 Graham D. M. 196 Graham M. A. 314 Graham R. A. 215 Graham W. R. M. 121 Grande H. J. 23 Grandjean J. 159 Granger P. 248 257 Granier W. 212 Grant E. R. 54,59,60,71 Gratzer W. B. 5 Graves G. E. 228 Gravschenko A. I. 46 Gray,H. B. 278,284,299,303 310,324 Graydon W. F. 322 Graziani R. 266 Green J. C. 275 Green M. 41 179 301 324 331,338,343,344,349,354.363 Green M. L. H. 274,276,288 289,337,344,359 Green P. J. 277 Greenaway A. M. 307 Greene J. 218,219 Greenhough T. G. 180 185 187 372 Greenwood A. J. 259 Greenwood N. N. 166 169 173 174 Gregorio G. 315 Gregory D. 165 Gregson A. K. 275 Greiser T. 309 Griebsch U. 352 Grieser F. 234. Griffith W. J. 323 Griffith W. P. 307 323 Griffiths J. E. 236 254 Grigg R. 337 Griller D. 131 134 145 Grimes R. N. 165 169 178 188 Grobelny R. 275 Groff R. P. 113 Groshens T. 346 Gross R. W. F. 92 Grossi A. V. 352 Grubbs R. H. 311 330 331 343 Gruen D. M. 200 Grunwald E.,49,55,70,72,73 Gruznykh A. V. 128 Grzybowski J. M. 314 Gubenko N.T. 348 Gubitosa G. 357 Giinter J. R. 207 Guest M.-F. 284 Gutlich P. 291 Guggenberger L. J. 276,333 Guilard R. 270 Guillaumont R. 264 Guillet J.E. 99 110 112 113 Guillevic G.. 174 Guillory W. A. 54 77 78,88 Gundersen G. 250 Gunter M. J. 293 Gupta S. K. 284 Guru Row T. N. 238 Gusev A. I. 175 181 Guss J. M. 303 Gustavson T. K. 63 Guthrie D. H. 259 268 Gutierrez E. 249 Gutman D. 80 Gutsev G. L. 246 Guzman E. C. 288 Gwinn W. D. 195 Gynane,M. J. S.,214,271,326 345 Haaland A. 357 Haan S. W. 103 Haas A. 245 Haas E. 19,20 Haas Y. 81 Haase W. 309 Habeeb J. J. 290 Haber E. 7 Habib 0.M. O. 46 Hack W. 232 Hackelberg O. 314 Hackett P. 356 Haddad M.S.,302 Hadia M.283 Hadjiliadis N. 301 Hadley J. H. 134 136 Hagem G. P. 313 Hagen A. P. 227,242 Hagen K. 243 Hagenmuller P. 251 Hager L. P.. 306 Hagerman P. J. 5 Hahn E. 23 Hahn H. 205 Haines R. M. 323 Haitko D. A. 286 329 349 Halbert T. R. 298 Haley M. J. 158,259 Halfpenny J. 164 Halgren T. A. 172 Hall A.-J.,31 35 Hall D. O. 294 Hall J. H. 78 Hall M. B. 312 Hall R. J. 251 Halpern J. 25 328 332 Halpern J. B. 82 Halstead G. W. 264 Halstrdm J. 191 Haltiwanger R. C. 167 Halvorson H. R. 7 Ham D. O. 64 Hamilton G. A. 304 Hammaker R. M. 235 Hammes G. G. 23 Hammond G. S. 284,324 Hamshere S. J. 122 Hancock G. 82 Handel H. 159 Handwerk V. 232 Hanes R.M. 315 Hansen R. E. 141 Hanson B. E. 285 327 Hanson L. K. 292 Hanzlik R. P. 46 Harayama Y. 141 Harding J. H. 297 302 Harding L. B. 233 Hardy G. E. 183 Hare D. L. 11 Hargittai I. 243 Hargittai M. 189 Harland L. 312 Harlow R. L. 274 Harman M. E. 262 Harpp D. N. 245 Harrah L. A. 108 Harris J. M. 55 Harris P. J. 313 351 Harrison N. C. 339 Harrison P. G. 211 226 230 231 Harrison W. D. 242 Author Index Harrowfield J. MacB. 30 33 42 Hart F. A. 262 Hartford A. 81 Hartford J. W. 200 Hartman J. S. 189 Hartshorn A. J. 333 Hartsuiter J. G. 221 Hartzell C. R. 141 Hase H. 135 Hasegawa A. 129 130 HHsek J. 158 184 Haselbeck A. 10 Hasslberger G.227 Hastings J. 269 Hastings J. W. 21 Hatano K. 290 Hatano M. 12 Hatchard C. G. 113 Hatfield,W. E. 302 307 Hattori T. 230 Haubold W. 190 Hauge R. H. 119,210 Haugland R. P. 18 100 Haun M. 24 Hausen H.-D. 204 Hauser M. 103 Haushalter R. C. 181 Hawkes G. E. 262 Hawkins D. T. 256 Hawthorne M. F. 183 184 185,188 Hawthorne S. L. 269 Hay P. J. 257,315 Hay R. W. 27 28 29 32 36 43,45,46 Haycock D. E. 159,203,278 Hayes R. G. 282 Hayes S. E. 298 Hayes W. N. 264 Hayhurst A. N. 214 Haylett B. J. 291 Haymore. B. L. 283 Head R. A. 283,307 Heaton B. T. 321 Heberhold M. 305 Hedberg K. 243 250 Heeg M. J. 213,308 Heeger A. J. 238 Hegde S. 313 Hegor G. 323 Heh J.C.-K. 298 Heider I. 9 Heidner W. 241 Hein M. 238 Heinekey D. M. 163 Heintz A. 254 Helene C. 17 Helland B. J. 278 Heller G. 199 Hempel A. 250 Henderson R. A. 295 Henderson R. S. 211 Author Index Hendrickson D. N. 126 271 290,302,303,305,307,310 Henkel G. 280,310 Henkens R. W. 9 Herak R. 211 Herber R. H. 214 Herberich G. E. 191 Herbich J. 146 Herbot R. L. 51 Herlem M. 245 Hermanek S. 177 180,182 Hermann K. 229 Herrmann M. S. 11 Herrmann W. A. 335 341 356 Herron N. 163 Herskovits T. T. 18 Hertz R. K. 165 Hess B. 8 Hess H. 202 Hester R. E. 118 Heyns J. B. B. 345 Hibbert D. B. 151 Hicks P. R. 140 Hidai M. 3 13 Hietkamp S. 340 Hildebrandt G.F. 257 Hildebrandt,S. J. 173 Hildenbrand D. L. 268 Hildreth R. A. 24 Hill G. A. 70 Hill R. J. 266 Hill R. M. 257 Hillel R. 206 Hillenbrand D. F. 170 Hillier I. H. 278 284 Hills D. J. 201 Himmelspach J. 14 Himmelwright R. S. 303 Hipp C. J. 25 Hirota N. 144 Hirsekorn F. J. 352 Hitch B. F. 247 Hitchcock P. B. 333 Hitchman M. A. 300 Hlawata D. 158 Ho R. K. C. 279 Hoberg H. 341 352 Hochberg E. 284 Hodali H. A. 319 Hodgson D. J. 310 Hodgson K. O. 282,295,303 306 Hoefer R. 241 Hoekstra H. R. 267 Hoff C. D. 213 Hoffman,B. M. 290 Hoffman,N. W. 314 Hoffmann,E. G. 163 Hoffmann H. 234 Hoffmann R. 308 309 319 320,323,326,327,329,342 358,362,363 Hoffmann W.329 Hoge B. 241 Hogeveen H. 325 Hogg J. H. C. 206,247 Holah D. G. 171 308 Holbrook J. B. 157 Holland R. F. 264 Hollander F. J. 276 319 334 Hollis S.,163 Holloway J. H. 257 258 277 Holm R. H. 282 294 295 306 Holmquist B. 12 21 Holton J. 261 326 328 Holwerda. R. A. 298 Homberg H. 325 Honan G. J. 265 Hong P. 353 Hook J. W. 111 5 Hope H. 195 Hopgood D. 44 Hopkins T. E. 262,361 Hoppe R. 164,198,207,212 251,272 Horiike K. 15 Horn D. 245 Horne D. S. 91 Horne R. K. 254 Horrocks W. D. jun. 21 Horrocks W. de W. 261 Horsey B. E. 234 Horton H. R. 10 Horvath I. 207 Hossain M. B. 176 359 Housecroft C. C. 318 Houser T. J. 236 Houston P.L. 74 83 Hove E. G. 261 Howard J. A. K. 271 301 318,324,327,331,354,363 Howarth 0.W. 272,360 Howden M. E. 537,346 Howell J. A. S. 353 Howell J. L. 247 Howie R. A. 213 Howlander N. C. 284 Hoyle C. E. 110 HrdloviE P. 105 Hsien L. 23 HSU,C.-M. 42 Hsu Y. F. 248 Hu M. G. 195 Huang M. H. A. 352 Huang T.-N., 359 Hub H. H. 234 Hubbard J. L. 175 176 Hubberstey P. 158 Huber H. 304,324 Huber M. 356 Hubert-Pfalzgraf L. 273 Hudgens J. W. 54,72 Hudson R. F. 220 Hudson R. L. 122 137 251 Huestis D. L. 257 Hiittermann J. 130 133,323 Hiittermann J. 130 133 323 Huffman J. C. 182 Hugel R. P. 309 Hughes A. N. 171,308 Hughes D. L. 158 161 Hughes W. M. 257 Huglen R.202 Hui B. C. Y. 171,307,308 Huie B. T. 307 Hulet E. K.,264 Huml K. 158,337 Humphrey M. B. 273 Huneke J. T. 281,300 Hung L. K. 246 Hunt M. M. 289,358 Hunter B. K. 329 Hunter W. E. 261 288 326 330,356 Hurst N. W. 204 Hursthouse M. B. 260 262 285 305 309 320 324 327 Husebye S. 250 Hussain W. 283 Husson E. 272 Hutchinson J. P. 320 Hutchison C. A. jun. 125 Huttner G. 210 356 Hutton J. A. 270 Hutton R. E. 224 Hutton R. S. 146 Hwang T.-L. 208 Hwang W. C. 70 Hyde J. S. 139 142 Ibers J. A. 292,294,306,338 349 Ichikawa M. 322 I’Haya Y. J. 122 Iiyama J. T. 301 Ikawa T. 279 Ikeda R. 250 Ikeda S. 110 Ilbel S. D. 328 Ilyukhin V. V. 206 Inai Y. 349 Indelli M.T. 308 Inel Y. 216 Ingman F. 163 Ingold K. U. 131 134 138 Ingrosso G. 348 Inkrott K. E. 173,313,319 Innbushi T. 349 Inoue M.,290 Iqbal M. Z. 329 Irish D. E. 38 Irler W. 305 Inine E. A. 231 Irwin K. J. 337 Ishiguro M. 208 Ishii Y. 311 Ishikawa M. 208 210 Ishizu J. 343 374 Isobe M. 279 Johnson A. K. 38 Isuyama R. 263 Johnson A. W. 333 Ito T. 110 Johnson B. F. G. 318 319 Ittel S. D. 350 320,324,353,355,360,362, Ivanov M. A.. 260 363 Ivin K. J. 344 Johnson D. F. 306 Iwai S. 279 Johnson D. R. 245 Iwaki M. 306 Johnson E. C. 300, Iwasaki M. 133 135 Johnson H. D. 200 Iwatsubo M. 22 Johnson J. D. 11 Johnson J. F. 274 Jack J. R. 351 Johnson K. W.. 150 Jackowski J.J. 314 Johnson M. D. 41 311,332 Jackson G. 266 Johnson P. L. 171 301 316 Jackson G. E. 303 323 Jackson P. F. 319 Johnson P. R. 310 Jackson R. A. 316 Johnson R. W. 295 Jackson S. E. 145 Johnson W. L. 299 Jackson W. R. 352 Johnson W. M. 256 Jacob E. 255 Johnston H. S. 215 Jacob K. T. 205 Johnstone W. 61 Jacob P. 199 Jolly P. W. 352 Jacobsen H.-J. 226 Jolly W. L. 195 224 312 Jawbsen R. A. 278 300 Jones C. H. W. 250 323 Jones G. R. 249 Jaeger C. D. 138 Jones M. jun. 325 Jaenicke R. 8 9 10 Jones P. R. 162 Jain N. C. 203 Jones R. A. 327 Jakubetz W. 251 Jones R. H. 285 Jallon J. M. 22 Jones S. R. 254 James B. D. 171 Jones T. E. 303 James B. R. 306,307 Jones W. D. 314,320 Jameson G. B. 292 Jones W. M. 334 Janolino V.G. 10 Joppich-Kuhn R. 13 Janousek Z. 182 Jorbett C. D. 259 Jansen E. H. J. M. 123 Jordan R. F. 326 Jansen J. C. 297 Jorge R. A. 162 Jansen M. 231 Jorgensen W. L. 253 Jarchow O. 309 Jortner J. 64 Jarell M. S. 322 Joubert P. 255 Jarosz M. 358 Judeikis H. S.. 116 Jarrold M.,272 Judelbaum A. 244 Judish J. P. 257 Jastrzebski J. T. B. H. 225 Jawaid M. 163 Jugie G. 204 Jeannin Y. 277 Julius S. A. 357 J$cnL J. 337 Jun-ichi Aihara. 175 Jedrzejnak H. 250 Jurek R. 254 Jeffery J. 271 326 345 Juris A. 323 Jeffery J. W. 203 Jutzi P. 210 Jens K.-J. 341 Jensen L. H.. 303 Kabbani R. M. 191 Jensen R. J. 65 Kablau K.-D. 197 Jesse A. C. 338 Kadish K. M. 299 Jesson J. P. 328 350 Kadoshnikova N. V. 206 Jezowska-Trzeblatowska B.Kaesz H.D. 319 275 Kahn L. R. 257 Jia-Shen Wang. 167 Kahn O. 126,297,302 Jick B.-S. 236 Kairn W. 133 Jobert-Perol A. 245 Kaiser E. W. 260 Jorgensen C. K. 260 Kalasinsky V. F. 199 Johansson D. M. 248 Kaldor A. 9 Johansson G. 164 Kalinin V. N. 181 Johansson G. B. 249 Kalinina G. S. 223 Johns K.-W. 290 Kalsch J. F. 70 Author Index Kamboj I. K. 252 Kamiyama Y. 211,333 Kampel V. T. 180 181 Kan C. T. 171,308 Kane L. 172 Kanehisa M. I. 6 Kane-Maguire L. A. P. 360 Kanemoto S. 230 Kang J. 332 Kao H. I. 240 Kappenstein C. 309 Karban J. 233 Kariuki D. N. 312 Karl R. R. 246 Karlin K. D. 355 360 Karpovskaya M. I. 202 Kasai P. H. 120 346 Kasper J. S. 165 Kasrai M.159 Kastner M. E. 306 Katayama M. 74 Katchalski-Katzir E. 19 20 Kato H. 237 Katovic V. 278 284 Katz H. 254 Kaucic V. 205 Kaufmann K. 69 Kavel K. J. 355 Kawada Y. 334 Kawaguchi S. 301 Kawahara A. 301 Kawakami K. 324 Kawamura K. 301 Kawamura T. 132 Keasey A. 347,363 Keehn P. 70,76 Keehn P. M. 49 55,77 Keene F. R. 32,308 Keeney M. E. 324 Keiderling T. A. 294 Keim W. 359 Keller H. J. 309 Keller P. C. 194 Kellert F. G. 257 Kelley E. A. 347 Kelly R. L. 286 317 Kemmitt R. D. W. 337,346 Kemp J. J. 147 Kennedy J. D. 166 169 173 174 Kennedy S. M. 333 Kennelly W. 346 Kepert D. L. 258,279,289 Kern A. 323 Kessell S. L. 126 307 Kettle S. F. A. 312 Kevan L.119 Kevill D. N. 40 Khain V. S. 249 Khaled F. M. 157 Khan M. A. 243 Khan M. M. T. 41 Khan S. A. 246 Khan S. M. 21 Author Index Khan T. 343 Khare G. P. 363 Khitrova D. M.,335 Khomatov N. E. 46 Khoroshev S. S. 257,258 Kida S.. 297 Kidd D. R. 314,317 Kiernan P. M. 309,323 Kim Y. 310 Kimel S. 49 Kimura E. 214 Kinberger K. 193 Kincaid J. R. 306 King A. D. jun. 315,329 King I. J. 46 King R. B. 203,291,307,315 329,359 King S. E. 251 King T. J. 211,283,284,295 Kinney R. J. 314 Kinugawa K. 135 Kipling B. 39 Kipouros. C. J. 268 Kirakosyan G. A. 202 Kirby C. 185 Kirby G. W. 215 216 Kirchhoff W. H. 245 Kirmse R. 128 Kirner J. F. 347 Kirschner S.46 Kirste B. 140 Kirtman B. 234 Kiss J. 230 Kita W. G. 289 358 Kitamura F. 46 Kitaura K. 253 Kitazume T. 244,246,247 Kitchen M. D. 355 Kitigawa T. 306 Kittaka S. 230 Kiwi J. 232 Klabunde K. J. 322,346,359 Klaska K.-H. 309 Klazinga A. M. 277,339 Kleeman G. 246,333 Klei B. 332 Kleier D. A. 174 Klein M. L. 253 Klein M. P. 290 Klein R. 305 Klein U. K. A. 103 Kleinschmidt P. D. 268 Klemperer W. 260 Klemperer W. G. 279 Klepikova V. I. 350 Kleigel W. 192 Kliger D. S. 284 324 Kligler D. 257 Klimenko N. M. 254,256 Klimov V. D. 257 Klinger R. J. 317 Klippert E. 291 Klopffer,W. 105 108 114 Knapp G. S. 291 Knapp K. K. 194 Knauth H.-D. 256 Knetzer S.39 Kniep R. 203 Knobler C. B. 184 Knozinger H. 322 Knoke. G. 278 Knorr F. 10 Knox S. A. R. 289 313 351 362 Knudtson J. T. 63 Knutsen G. F. 201 Kobayashi A. 158 171 Kobayashi T. 217 Kobel'Kova N. I. 181 Kobrinsky P. C. 257 Koch D. 227 Koch. S. A. 285,286,287,327 361 Kochanski E. 252 Kochetov G. A. 8 Kochi J. K. 128 325 329 Kodama H. 230 Kodama M. 214 Kodama T. 283,313 Koehler M. E. 308 Koelle U. 318 Koemm U. 338 Konig E. 210 305 Konig H. 198 Koeniger F. 250 Koniger-Ahlborn E. 163 304 Koga T. 216 Kohler D. A. 166 Kohler F. H. 357 Kohn M. 246 Kokisch W. 305 Kokotailo G. T. 237 Kokovin G. A. 249 Kolari H. J. 299 Kolb J. R. 171 Kolesnikov S.P. 361 Kollmannsberger M. 250 Kolmakova E. I. 255 Kolobova N. E. 335 Kolodner P. 59 Kolthammer B. W. S. 288 Kolts H. E. 257 Kolts J. H. 257 Komoto R. G. 318 Kompa K. L. 63,83,93,94 Kondo H. 44 Kondo,K. 216 Kongkathip B. 337 Koniger-Ahlborn E. 279 280 Konwer D. 248 Koote J. A. 146 Kopelove A. B. 162 Koplick A. J. 262 Koppenhofer B. 337 Kopple I(. D. 12 Koren G. 64 Korff J. 341 Koridze A. A. 348 Kormer V. A, 350 Korp J. 233 Kotelevets E. S. 249 Kotov A. G. 128 Kovsman E. P. 46 Kozankiewicz B. 146 Kozima L. G. 321 Kozlova N. I. 202 Kozub S. G. 323 Kraatz U. 190 Kramer G. W. 176 Kramp D. C. 15 Krasnai J. P. 256 Krasnoperov L. N. 251 Krause R.A. 307 Krause S. 325 Krause-Going R. 352 Krautler B. 138 Krebs B. 163 226 236 238 240,279,280,310 Kreilick R. W. 127 Kreisel G. 275 Kreissl F. R. 335 Kreiter C. G. 338,339,355 Krishkown B. 73 Krishnamurthy S. 175 Krishnan V. 247 Krishnan V. G. 128 Kroll H. 27 Kroon J. 225 Krost D. A. 126 Kroto H. W. 165 211 Kriiger C. 194,327,352,354 361 Kriiger N. 202 Kruger R. L. 147 Kruse P. W. 53 Krusic R. J. 131,350 Kubas G. J. 256 Kubiak C. P. 347 Kubokawa Y. 231 Kuchen W. 253 Kunkowski R. L. 196 Kuhlmann W. 254 Kumada M. 208,210 Kume Y. 250 Kunkely H. 162 315 Kunze G. 249 Kuppers H. 287 Kurland R. J. 201 Kurreck H. 140 Kurtz D. M. 306 Kurylo M.J. 91 Kutner W. 240 Kuwajima K. 5,6 Kuyper J. 240 Kuzinin E. A. 206 Kuznesof P. M. 196 Kwan T. 41 Kwok H. S. 59 Kwvok M. A. 92 Kyle J. H. 279 376 Laane J. 214 Labes M. M. 240 Labinger J. A. 315 Lachambre J. L. 51 Lagow R. J. 224,237,246 Lagowski J. J. 310 Laguerre M. 219 Laine R. M. 318 Laing M. 323,354,362 Laird A. E. 215 La Mar G. N. 293 Lambert J. B. 325 Lambert S. L. 303 Landi A. 270 Landis P. S. 237 Landrum J. T. 290 Lanfredi A. M. M. 363 Lange M. 335 Lankard J. R. 89 Lappert M.-F. 214 218 261 271,276,326,327,333,334 345 Lappin A. G. 300 Larrabee J. A. 310 Larsen D. M. 63 Larsen D. W. 325 Larsson L. O. 263 Lashewycz R.A. 318 362 363 Laskowski E. J. 290,294,295 306 Lassigne C. R. 248 Laszlo P. 159 Latour J. M. 270 Latremouille G. 246 Lattman M. 312 Lam P. H. W. 243 Lauher J. W. 318 Launay J. P. 277 Laurence G. S. 283 Laurent J-P. 197 Laval J. P..268 Lavallee D. K. 162 Lavayssiere H. 209 Lavrik N. L. 251 Lawrance G. A. 299 Lawson R. J. 320 Lawton S. L. 237 Lay D. G. 285 Lay P. A. 299 Lazarini F. 231 Leach B. E. 44 Leach G. A. 309 Leary,K.,308 Leary K.M. 88,246 Leavis P. C. 14 Le Bihan M-T. 309 Le Bozec H. 333 Le Bras G. 215 Leclaire A. 160 Leclerc M. 20 Lecomte C. 270 Lecomte M. 315 Lederman D. M. 56 Ledlie D. B. 39 Lednor P. W. 354 Lee J.C. 11 Lee J.-H. 214 Lee J. Y. 133 Lee S. M. 67 Lee Y. T. 54 59 60 71 257 Lee Hanlan A. J. 341 Legasov Y. A. 236 251 257 Le Goaller R. 159 Legzdins D. 288 Legzdins P. 288 Lehmann E. 256 Lehmann M. S.,316,357 Lehmkuhl H. 163 Lehn J-M. 158 163 Lehrer S. S. 10 14 16 Leigh G. J. 283,3 11 Leito J. 322 Leligny H. 164 Lempereur F. 92 Lempereur M. 112 Lenkinski R. E. 205 Lentz D. 250,251,258 Leone S. R. 69 Leonyuk N. I. 198 Lerch K. 310 Lesiecki M. L. 77 78 88 Leslie J. P. 40 Letokhov V. S. 55,63,64,65 73.76.82 83 84 Leu Th. T. 214 Leusink A. J. 38 Leussing D. L. 43,44 Lever A. B. P. 299 Levin A. A. 246 Levitin I. Ya. 332 Levitzki A. 8 Levy,A.B. 200 Levy,H. A. 198,281 Levy J. H. 264 Lewis J. 293 308 318 319 320,324,353,355,360,362 363 Lewis N. S. 324 Lexa D. 332 Li K. K. 246 Li T. M. 5 Libby R. D. 304 Lichtenberger D. L. 314 316 Lichtenthaler R. N. 254 Liebman J-F. 246 256 Liem D. H. 163,164 Liesegang G. W. 214 Likforman A. 206 Likhite V. V. 40 Liles D. C. 226 Lilienthal H. R. 302 Lim M. C. 30 Lim T. F. O. 209,210,325 Lim Y. Y. 145 Lin M. C. 90 Author Index Lin S. T. 67 73 Lin T. 83 Lincoln S. F. 259 265 Lindner H. A. 222 Lindquist 0.. 248 249 Lindsell W. E. 160 325 Linek A. 184 Link R. 291 Lintvedt R. L. 302 Lippard S. J. 171 263 302 Lippoldt R. E. 14 Lipscomb W. N. 166 172 174,234 Lisensky G.C. 198 Lisle J. B. 131 Lister D. G. 199 Litman G. W. 16 Litman S. 355 Little J. L. 170 Litvinenko S. L. 40 Liu C. F. 309 Liu C-S. 208 Liu E. K. S. 224 Liu M. 330 Livage J. 277 Livingstone S. E. 292 Lloyd D. R. 275 Lloyd R. V. 130 Lo F. Y. 184 Lobach M. I. 350 Lock C. J. L. 237,305 Lockhart J. C. 159 Lmw L. M. 260 Loffredo R. E. 167 Logan N. 259 Loginov S. V. 307 Logvinenko V. A. 296 Lokhman V. N. 73 Long D. A. 249,257 Longato B. 183 Longworth J. W. 23 Lijpez-Castro. A. 163 Loran J. E. 42 Lorenz I-P. 244 Lory E. R. 92 Lotz T. J. 307 Louch W. J. 300 Lougheed R. W. 264 Love P. 240 Loveday S. R. 309 Lowe D. J. 142 Lowe R.A. 319 Lowenstein R. M. J. 76 Lowenstein-Benmair R. M. J. 76 Lowers R. H. 150 Lowson R. T. 200 Loy M. M. T. 89 Lubitz W. 140 Lucchese R. R. 236 Luche J-L. 260 Lucherini A. 348 359 Luchinat C. 298 310 Ludi A. 309 Author Index Luisi P. L. 13. 15 Lukac I. 105 Lukas R. 356 Lukehart C. M. 191 Lundgren J-O. 235 Luong-Thi N. T. 326 Luzikov Yu. N. 360 Lyman J. L. 59 61 65 88 246 Ma M. S. 300 Maatta E. A. 283 344 Mabbs F. E. 283,284,295 McAlister D. R. 272 328 330,358 McAlpine R. D. 92 McArdle J. V. 295 McAtee J. L. jun. 233 McBride J. M. 131 MacCallum J. R. 107 110 McCarley R. E. 272,273,278 284 McCleverty J. A. 289,358 McClusky F. K. 92 McCormick B.J. 305 McCormick J. P. 233 McCormick M. J. 316 McCowan J. D. 270 McCubbin T. K. 246 McCurry L. E. 201 McCusker L. B. 162 McDermid I. S. 254 McDiarmid A. G. 238 McDonald I. R. 253 McConald J. W. 281 283 344 McDonald M. E. 314 MacDonald R. G. 69 McDonald W. S.. 173 Macdougall J. J. 300 Macedo de Abren P. 113 McFall S. G. 163 McFarland J. T. 7 Machado A. A. S. C. 291 McIntosh. D. 324 McKay D. B. 125 Mackay. M. F. 164 McKee M. L. 166 McKess V. 291 Mackenzie R. D. 113 McKinley G. C. 304 McKinney R. J. 313 Mackinnon L. W. 215 Macklin J. W.. 256 McLain S. J. 276 330 334 McLauchlan K. A. 150 McLeod D. 120,346 Macleod I. D. 258 McMaster A. D. 213 McMeeking J.261 326 328 McNeese T. J. 274 McNeil D. A. C. 118 McNeil R. I. 129 McNeish. A. 87. 246 315 McPartlin M. 319 McPhail A. T. 196 284 McPherson G. L. 126 McPhie P. S.. 5 McQuate R. S. 44 Macquet J. P. 301 McQuillan B. W. 195 MacQuitty J. J. 333 Maestri M. 323 Maggers K. D. 305 Magnuson R. H. 332 Mague J. T. 317 Mahtab R. 337,344 Maier W. B. jun. 264 Mairesse G. 175 201 Maitlis P. M. 3 11 347 35 1 360,363 Makarov G. N. 55,57,63,64 65,68,84 Makarov V. A. 128 Makarova L. G. 356.360 Makeev G. N. 236,251 Makhija R. 250 Makotchenko V. G. 254 Malatesta M. C. 324 Malek J. 34,46 Malik K. M. A. 262 285 305 Malik N. A. 304 Mallinson P. R. 176 Malmquist P.A. 257 312 Mamantov G. 201 202 236 246,254 Mammi M. 247 Mander L. N. 293 Manfredotti A. G. 176 313 Manfrin M. F. 323 Mang H. 234 Mani F. 274 Mann B. E. 289,355,358 Man, K. R. 324 Manning A. R. 356 Manning R. G. 91 Manriquez J. M. 265 272 330 Mansuy D. 323,335 Mansy S. 301 Manuccia T. J. 62,92 Manzel K. 245 Manzer L. E. 271 Marangoni G. 266,267 Marassi R. 202 Marathe. V. R. 292 Marchetti F. 270 313 345 Marchon J. C. 270 Margerum D. W. 34 300 Margrave J. L. 119,210 Mariano P. S. 24 Maringgele W. 197 Marinova E. N. 249 Marisch N. 308 Mark H. B. jun. 240 Mark W. 249 Marker A. 164 Marks T. J. 171 252 265 266,330 Marks T. K. 3 11 Marov I. N.121 Marquez R. 163 Marsal C. 92 Marshall H. E. 122 Martell A. E. 44 Martin D. R. 176,177 Martin E. D. 176,177 Martin J. C. 242 243 255 326 Martin J. W. L. 309 Martin R. B. 30 Martin R. L. 291 Martinengo S. 321 Martinez-Camera S. 164 Martinho-Simoes J. A. 312 326 Marty W. 39 Marumo F. 279 Maruthamutha P. 216 Marynick D. S. 166,234 Masaguer J. R. 204 Mashiko T. 306 Maskiewin R. 294 Mason J. 240 Mason R. 289 Massaux M. 309 Massey A. G. 191 Masters C. 219,322 Matheson R. R. jun. 6 Matheson T. W. 320,338 Mathiasch B.; 220 Matlock P. L. 318 Matsubara T. 296 Matsumoto K. Y. 279 Matsumoto M. 308 Matsumura K. 325 Mattes R. 277 Mattia J. 272 Mattson B.M. 307 Matzuyama T. 147 Maugin M. 250 Maurin M. 248 Mausle H-J. 236 Mawby R. J. 338 Maxwell W. M. 178 May C. J. 351 May P. M. 303 Mayer S. W. 92 Mayerle J. J. 240 Maynard R. B. 261,265 Mays M. J. 319 324 362 Mazo G. Ja. 321 Meakin P. 131 350 Mealli C. 274 Medda P. K. 227 Medford G. 168 Meek D. W. 289 Meerbeck T. G. 38 Meester M. A. M. 338 Mehrotra P. K. 309 Mehrotra R. C. 156,203 378 Mehrotra S. K. 240 Meier K. 332 Meier P. F. 119 210 Meier P. 0.W. 278 Meikle K. D. 250 Meixner D. 254 Melhuish W. H. 233 Meller A. 195 197 Mellini M. 345 Menchetti S. 198 Meneghelli B. J. 167 Mennemann K. 277 Mentzen B. F. 167 Merbach A. E. 273 Mercier R.231 Merola J. S. 211. 360 Merrifield J. H. 333 Mertis K. 275 Merz L. 309 Messerle L. W. 276 333 334 Mews R. 240,247 Meyer C. 62,67 Meyer J. L. 272 Meyer P. 310 Meyer T. J. 296,307,323 Mezei M. 234 Michael J. V. 214 Michaely W. J. 46 Michaut J. P. 132 Michel G. 172 Middaugh C. R. 16 Midollini S. 222 296 299 307 Miernik D. 264 Miessler G. L. 307 Mihashi K. 21 Mikawa H. 109 Miki M. 21 Mikuriya M. 297 Milburn R. M. 42 Miles S. J. 214 326 Milicev S. 258 Milinchuk V. K. 128 Millar M. 285 286 287 327 Millard M. M. 301 Miller J. C. 159 Miller J. D. 38 Miller J. M. 189 Milligan W. O. 233 Milliken J. 238 Mills W. C. 317 Milne C.R. C. 276 333 Milne J. 249 Milone L. 320 363 Minami T. 230 Mines T. E. 125 Mingos,D.M. P. 187,305,319 Minihan A. R. 257 Minkwitz R. 245,252 Minshall P. C. 221 Mirti P. 159 Mishra S. P. 135 136 Miskowski V. M. 284 324 Misra B. B. 266 Mitchell K. A. R. 242 Mitchell T. R. B. 328 Mitcheson G. R. 278,284 Mitrprachachan P.,3 18 Mitschler A. 316 357 Mitsudo T. 349 354 Miyashita A. 330 331 343 Miyazaki T. 135 Mizobe. Y.,283 Moattar M. T. Z. 312 Mochida K. 325 Mobius D. 234 Morte W. 271 Moseler R. 305 Mohan M. S. 41 Mohan N. 279 Mohanty S. R. 266 Moiseev I. I. 321 Mok C. Y.,333 Molin Y.N. 93 251 Molinaro F. S.,292 Moll M. 354 Molloy K. C. 226 Monescalchi F.3 13 Mongeot H. 174 Monier J. C. 164 Monsigny. M.. 17 Montano P. A. 305 Montavon F. 163 Montenarh M. 245 Mooradian A. 51 63 Moore C. B. 69 70 92 253 Moore P. 163 360 Moore T. F. 167 Moorhouse S. 262 Mootz D. 203,253 Moraczewski J. 361 Morandini F. 183,350 Moraski R. V. 46 Moreland C. G. 196 Moret J. 248 249 Moreu J. J. E. 274 Morgan J. A. 214 Morgan P. H. 277,357 Mori M. 299 Morimoto T. 230 Morishima I. 349 Morokuma K. 253 Moro-Oka Y.,231 Morris G. A. 213 Morris G. E. 289 343 359 Morris J. H. 170 172 Moms P. 36 Morns P. J. 27 Morrison J. A. 224 Momson M. M. 233,290 Morrison T. I. 291 Morse S. D. 240 Morssink H. 256 Mortenson L. E. 282 Mortimer C.L. 158 161 Mortimer. J. 277 357 Author Index Morton J. R. 122 124 245 246,257 Moscarello M. A. 10 Moser W. 213 Moses P. J. 75 Moss G. P. 262 Motoichi M. 44 Moulton P. F. 63 Moyer B. A. 307 Mueller A. 250 Miiller A.. 136 163,273,279 280,304,310 Miiller D. 205 Miiller G. 177 Miiller J. 261 326 MiiIler K. D. 194 Muetterties E. L. 311 347 352,359 Mukaiyama T. 269 Mukamel S. 56 Mukerjee P.,234 Mukhametshin F. M. 254 Mukhtarova N. N. 206 Mulac W. A. 264 Mulks C. F. 140 Muller A. 236 Mullica D. F. 233 Mun S. K. 140 Munro G. A. M. 359 Munslow W. D. 80 Munson B. 242 Murabayashi S. 138 Muradyan L. A, 249 Murakami Y.,44,230 Murakata M. 42 Murata M.303 Mureinik R. J. 301 305 Murillo C. A, 285 286 317 327,329,362 Murmann R. K.. 272 Murphy W. F. 254 Murray C. K. 300 Murray K. S. 296,306 Murray M.. 339 Murti N. V. V. S. 266 Murty B. S. R. 45 Musumeci A. 263 Muto H. 135 Myakishev K. G. 174 Myakshin I. M. 254 Myer G. H. 240 Myer Y.P. 12 Myers C. E. 260 Mynott R. 352,361 Nadir U. K. 241 Nagai K. 74 Nagano O. 158 Nainan K. C. 203 Naito S. 308,322 Nakadaira Y. 211 217 333 Nakagawa K.-I. 208 Nakajima H. 7 Nakajima M. 171 Author Index Nakamura D. 250 Nakamura T. 213 Nakamura Y. 301 Nakanishi H.. 349 Nakanishi K. 253 Nakano. H. H. 257 Nakano T. 109 Nakatsu K. 308 349 354 Nakatsuji H.216 Nakon R. 28 Nall B. T. 7 Namging H. 212 Nanninga D. 192 Narayana P. A. 119 Nardelli M. 226 Nardi N. 262 Nash K. L. 264 Nasielski J. 315 Naslain R. 165 Nassimbeni L. R. 266 Natile G. 342 Naudod G. 114 Naumann D. 256 Naylor P. A. 42 Nazarov A. S. 254 Nebelin E. 191 Nehl H. 163 Neidle S. 304 Neilson L. 290 Neilson R. H. 196 Nel A. 277 Nelson A. C. 151 Nelson D. J. 123 131 133 150,243 Nelson J. H.. 300 Nelson S. M. 160 163 291 Nelson W. J. H. 319 Nesmeyanov A. N. 348 356 360 Nesterov D. Y. 175 Nesterova Ya. M. 296 Neta P. 216 Netti R. 266 Neugebauer D. 270,310,336 356 Neumann S. M. 333 Neumann W. P. 325 Neville A. C. 262 354 New D.B. 305 New L. 320 Newlin D. E. 28 Newman P. J. 296 306 Newton M. G. 307 Newton W. E. 281 282 283 344 Ng H. N. 236 Ng. Y. S. 160 Nguyen J. T. 50 Nguyen V.T. 53 Niacke E. 221 Nicholls C. J. 159 203 Nicholls L. J. 309 Nicholson B. H. 7 Nicholson E. D. 322 Niedenzu K. 195 Nielson A. J. 307 Niem T. 300 Nieto M. 9 Niki R. 18 Nikitina 2. K. 307 Nikonorov Yu. I. 254 Nisbet. M. P. 228 Nishigaki S.. 354 Nishina Y. 15 Niswander R. H. 285 Nitay M. 335 Nitta K. 6 Niwa M. 230 Nixon A. J. C. 275 Nixon J. F. 211 307 Nobinger G. L. 324 Noble M. E. 283 Nobuyuki Y. 44 Nolle D. 192 198 Noth,H. 93,94,165,188,192 194,196,197,198,210 Nolan K.B.. 28 32 36 Nolte M. J. 313 332 Nolte W-0. 236 280 Noltes J. G. 38,225 328 Noodleman L. 242 NordCn B. 301 Nordyke M. D. 298 Norman J. G. 299 Norman L. J. jun. 260 Norman P. R. 46 Normant. J-M. 354 Norris J. R. 257 Norris V. 30 Norris V. A. 303 North A. M. 91,108,110 Norton J. R. 320 326 Norton P. 53 Novak R. J. 240 Novara O. 128 Novikov G. I. 249 Novikova L. N. 360 Nowak A. V. 59,83 Nowell I. W. 161 Nozaka M. 6 Nozaki H. 311 Nozaki M. 306 Nozawa T. 12 Nozik Yu. Z. 249 Niinisto L. 263 Nugent W. A. 274 Nunome K.. 135 Nyathi J. Z. 349 Oakes V. 224 Oakley R. T. 219 Oberhammer H. 235 O’Brien C. R. 24 O’Brien P. J. 24 Ochrymowycz L. A. 303 O’Conner J.316 Oddon Y. 207 Oddy P. R. 170 Odom J. D. 167,199 O’Donnell T. A. 252,258 O’Donoghue T. D. 293 Ozkar S. 355 Ogden J. S. 272 Ogini W. O. 164 Ohi F. 208 Ohlsen J. R. 214 Ohno H. 213 Okada K. 279 Okahara M. 161 Okajima M. 324 Okawa H. 297 Okeya S. 301 Okinashima H. 208 209 Okon M. 64 Okorodudu A. 0.M. 237 Okuda M. 215 Olah G. A, 265 Oliver J. D. 175 346 347 Olmstead M. M. 324 Olovsson I. 235 Olszyna K. J. 55,73 Omer M. M. 243 Onak T. P. 179 Onan K. D. 196,284 Ono,T. 231 Oppenheim U. P. 64 Oppermann H. 249 Orama 0..177 310 Orchard A. F. 172,206 Ordonez K. P. 166 174 Orii Y. 12 Orlandini A. 297 Orme-Johnson W. H. 306 Oro L. A. 176 Orpen A.G. 318 319 324 362 Ors J. 89 Osella D. 320 O’Shea S.F. 253 Oskam A. 312 Osteryoung R. A. 201 Otero A. 227 Otsuka S. 306 308 315 Ott V. R. 281 Ottersen T. 297 Ou. C. C. 305 Oudeman A. 350 Overill R. E. 122 Owen J. D. 161 Owens F. J. 122 Oxley J. C. 293 Oye H. A. 202 O’Young C. L. 302 Ozaki A. 231 Ozin G. A. 304 324 341 Pacansky J. 229 Pace C. N. 5 Padma D. K. 243 Paetzold P. 175 Page M. L. 34 Pain R. H. 5 Palke W. E. 234 Palmer G. 12 141 Panfilov V. N. 93 Pannan C. D. 316 Pantell R. H. 59 Panunzi A. 342 Panunzio M. 313 Pao S. S. 170 Paoletti P.. 302 Paolucci G. 267 Papaefthymiou G. C. 294 Papatheodorou G. N.202 Papiernik R. 268 Papon P. 170 Parent C. R.. 151 Parkanyi L. 219 Parker C. A. 113 Parker D. G. 360 Parker F. 220 Parnell C. P. 313 Parrett F. W. 284 Parrott M. J. 123 Parshall G. W. 336 Pasch N. F. 107,113 114 Pasquali M. 176 266 270 313,350 Passmore J. 236,245 Pastan I. 6 Pasternack R. F. 306 Pastuszak R. 250 Pasynkiewicz S. 358 Patel C. K. N. 50 53 Paul I. C. 242 Paul R. C. 248 Paulat-Boschen I. 163,279 Pauson P. L. 359 Pavlucci G. 266 Payne D. R. 147 Payne M. D. 308 Payne M. G. 257 Payne N. C. 304 Payne W. A. 214 Peake B. M. 125 Pearce R. 261 326 328 Pearson R. G. 26 Pecht I. 14 16 Pedersen E. J. 191 Pedersen J. B. 149 Pedone C. 342 Pedregosa J.B. 272 Peer W. J. 310 Pelizzi C. 226 Pelizzi G. 226 Pellack M. A. 28 Pelter A. 176 Penn R. E. 244 Pennington B. T. 176 177 Peoppelmeier K. R. 268 Pepe G. 205,207 Pepperberg I. M. 172 Percival P. W. 150 Perkins M. J. 151 Perree-Fauver M. 308 Perry D. L. 210 Persson I. 162 164 Perutz R. N. 314 Pesa F. 338 Peshchevitskii B. I. 39 Pessine F. B.T. 83 Pestel B. C. 308 Peters 0.M. 35 Peters S. 306 Petersen O. 238 Petersen R. L. 133 140 142 243 Peterson E. J. 275 Peterson J. A. 264 Peterson J. L. 316 Peterson S. W. 267 Petrov Yu. I. 254 Pett V. B. 282 Pettersen R. C. 353 Pettit R. 335 348 Petty R. H. 306 Pfeffer M.,363 Philippot E. 248 249 Phillips D.107 116 Phillips R. L. 348 349 Phipps D. A. 46 Pickett C. J. 283 Pico C. 249 Pidgeon C. R. 51 Piens M. 106 Pierpont C. G. 362 Pierre J-L. 159 Piffard Y. 269 Pignolet L. H. 307 Pilbrow J. R. 140 Pilipovich D. 254 Pilon P. 162 Pinilla E. 176 Pinkerton A. A. 273 Pinson P. 62,67 Pipal J. R. 178 188 Piplani D. P. 27 Pippard D. 318 319 362 Pisaniello D. L. 259 Pisareva I. V. 181 Pitts J. N. 215 Plakhotnik V. N. 40 Plambeck J. A. 201 Plank J. 335 341 Platt E. 131 Platzner T. 208 Plesek J. 180 182 Ploog K. 165 Plotkin J. S. 177 Plurien P. 266 Pneumatikakis G. 301 Pocker Y.,40 Podberezskaya N. V. 167 Poe A. J. 316 Poeppelmeier K.R. 259 Pohl S. 221 280 Poli A. 320 Poliakoff M. 68,87 246,314 315 Author Index Polichnowski S.W. 326 Polo S. R. jun. 246 Polynova T. N. 296 Pontenagel W. M. G. F. 225 Pope L. 354 Pope M. T. 279 Popenko N. I. 260 Pople J. A. 325 Poppinger D. 325 Porai-Koshits M. A, 296 Porri L. 359 Porter G. 103 Porter R. F. 167 Porubcan R. S. 7 Porzio W. 337 Posey R. G. 363 Posselt H. S. 40 Post M. L. 284 Potenza J. A. 305,352 Potier J. 255 Potter J. D. 11 Poulet G. 215 Poulsen F. W. 202 236 245 Poulsen L. L. 253 Powell D. 300 Powell F. X.,245 Powell J. 351 Powell P. 360 Powell R. C. 109 Power P. P. 214 326 Power W. J. 341 Powers M. J. 307 Pozhidaev A.I. 296 Pratt J. M. 310 Preetz W. 323 Preiner G. 210 Prelesnik B. 211 Premilot S. 20 Preses J. M. 74 Prest D. W. 191 Preston K. F. 122 124 245 246,247,257 Preuss A. W. 232 Price D. D. 272 Price D. H. 276,359 Price T. R. 114 Priester W. 335,336,339 Prissette J. 252 Pritchard H. O. 89 253 Pritzkow H. 250 Privat J. P. 16 Proch D. 63 Prochaska E. S. 254 Proctor J. 238 Prossdorf W. 357 Pross E. 301 Protas J. 270 321 Proud J. 301 Prout K. 360 Pruett R. L.. 321 Pruskil I. 336 Pshezketskii S. Y. 128 254 Puaw J-P. 267 Author Index Puddephatt R. J. 156 301 316,331,335,348,349 Purzer A. 354 Puff H. 226 Pugh D. 61 Pulham R. J. 158 Pupp M.247 Purcell K. F. 305 Purcell W. L. 37 Purdie N. 214 Puretskii A. A. 55 57,63,64 68,84 Puri J. K. 248 Purkey R. M. 17 Puthoff H. E. 59 Putman N. 112 Putman-De Lavareille N. 107 Putnik C. F. 347 Puxeddu A. 308 Quack M. 56 Queirbs M. A. M. 307 Quel E. 92 Quick M. H. 323 Quigley G. P. 257 Rabek J. F. 99 134 Rabenau A. 252 Rabeneck H. 201 Rabenstein D. L. 162 Rabinovitch B. S. 61 Rabonovich L. J. 359 Rafalko J. J. 322 Raghavan N. V. 43 Rai A. K. 203 Raithby P. R. 293 309 318 320,360,362,363 Rakowski Du Bois M. 352 Ramachandran N. 23 Ramsden J. N. 293 Ramshaw J. A. M. 303 Ranby B. 99,134 Randall C. H. 267 Random L. 236 Rankel L. A. 317,362 Rao K.K. 294 Rao K.V. S. 136 Rapp B. 166 Rashidi M. 301 316 Rastsvetaeva R. K. 206 Rathke J. W. 315 Rathman D. 232 Rattray A. J. M. 204 Rausch M. D. 272,352 Rauscher G. 325 Rawlings J. 294 Raychaudhuri S. 266 Raymond K. N. 266,295,296 306 Razuvaev G. A. 223 Rechani P. R. 28 Reddy A. V. 14 Reddy G. S. 336 Reddy R. V. 89 Reed C. A. 290,292,306 Reed J. 12 269 Reed T. A. 12 Reeder K. A. 291 Reedijk J. 127 128,297 Rees B. 316,357 Reese H. R. 232 Reeve R. N. 228,229 Reger D. L. 334 Reichel C. L. 131 Reichert W. W. 286,317 Reid R. F. 106 107 Reimann R. H. 313 Reimann W. 315 Reinhardt P. W. 246 Reinhardt R. 236 Reis A. H. jun. 267 291 Reith H. 210 Rempel G.L. 307 Renaud J. 294 Renaut P. 357 Resler E. L. 56 Rest A. J. 315 Restivo R. J. 164 Rettig S. J. 192 205 Revelle L. K. 217 244 325 Reynolds J. G. 306 Rheault F. 51 Rhee S. G. 21 Rhodes G. K. 257 Ribeira Da Silva M. A. V. 326 Ricard L. 321 344 Rice C. E. 222 Rice D. A. 236,267 284 Rice G. W. 284,327 Rice N. C. 175,346 Richards R. L. 282 Richards W. G. 216 Richardson C. E. 11 Richardson E. K.,245 Richardson J. F. 304 Richardson M. C. 51 Richardson P. F. 127 Richman R. M. 126,307 Richter A. 175 Richter F. 320 Rickard C. E. F. 38 266 Riddle C. 166 Rideout D. C. 286 Ridge B. 295 Ridley W. P. 211 Riederer H. 130 Riess J. G. 222 273 Riethmiller S.199 Reitz R. R. 171 172 264 265 Rigny P.. 266 Rigo P. 355 Riley C. 165 335 348 Rimmelin P.,245 Rimsky A. 310 Rinik R. 93,94 Ring J. W.,253 Ringsdorf H. 234 Ripill D. 270 Ripmeester J. A. 234 255 Risbood P. A. 251 Ritter D. M. 166 Ritter G. 305 Ritter J. J. 73 83 Rivera A. V. 241 318 324 355,360 Riveras J. M. 312 Rivet J. 163 Riviere P. 204 210 Riviere-Baudet M. 210 Robbins J. L. 357 Roberts B. P. 122 123 134 243 Roberts J. L. jun. 233 Roberts P. J. 164 Roberts T. G. 74 Robertson A. J. B. 151 214 Robertson A. S. 195 Robertson G. B. 42 Robins G. V. 118 Robinson B. H. 125 Robinson C. P. 65 Robinson J. W. 75 Robinson S. D. 305 307 317 Robinson W.R. 290 Robinson W. T. 160 292 Robson A. C. 159 Robson B. 7 Rochester C. H. 229 Rockwood S. D. 52,61,65 Rodgers A. 160 Rodgers A. L. 266 Rodgers R. D. 272 Rodley G. A. 160,292 Rodriguez L. J. 214 Rodwell W. R. 236 Roder A. 271 Rosch L. 204 Roesky H. W. 237 238 240 24 1 Roettger J. 232 Rogers G. A. 30 Rogers R. D. 261 271 288 326,330,356 Roginskii V. A. 128 Rohlack D. 256 Rohrbasser C. 201,309 Rolison D. S. 281 Romanov G. V. 254 Roncin J. 132 Ronn A. M. 59,67,73 Rooney J. J. 337 334 ~oos, r. A. G. 291 Roper W. R. 324 Rorabacher D. B. 303 Rose E. 292 293 Rose F. 237 382 Rosenberg B. 111 Rosenberg E. 272 Rosenblum M. 335,336,339 Rosenfeld R.N. 79 Rosenfeldt F. 329 Rosolovskii V. Ya 170 175 251,255,307 Ross D. A. 110 Rosseinsky D. R. 267,289 Rossel C. 281 Rotella F. J. 282 Rothschild M. 64 Rothwell I. P. 320 332 Rousche J-C. 347 Rouse K. D. 318,362 Rousson R. 254 Rouvel J.. 273 Rowe K. 176 Roy A. 288,327 Royo P. 227 Rubbens A. 201 Ruben H. W. 172,265 Rubin B. 246 Ruby S. L. 252 Rudakov E. S.,40 Rudkin L. 107 110 Rudolph R.. 8.9 10 Rudolph R. W. 167,181,182 220 Ruik J. P. 65 Ruiz-Amil A. 164 Ruu-Vizcaya M. E. 128 Rumble N. W. 308 Rumpf E. 322 Rund J. V.. 194 Ruppert I. 227 Rupprecht G. A. 276,334 Russell D. R. 258,305,337 Russell L. J. 360 Russell P. 305 Rustuntseva A.E. 249 Ruthven D. M. 251 Rutt H. N. 65 Ryabov E. A. 76,82,83 Rybin L. V. 348 Rybinskaya M. I. 348 Rydon H. N. 295 Rynbrandt J. D. 61 Rytz G. 332 Ryutina N. M. 128 Saalfeld F. E. 240 Sabelli C. 198,203 Sacconi L. 222 296,297,299 307 Sackman E. 234 Sadler P. J. 304 Saeki Y. 306 Sarnstrand C. 231 Sagstuen E. 143 Saito M. 9 Saito N. 6 Saito T. 171 Sakai T. 305 Sakamoto M. 44 Sakurai H. 211,217,333 Salahub D. R. 168 Salahuddin A. 18 Salama S. B. 243 307 Salazar K.V. 264 Salentine C. C. 188 Sales K. D. 285 327 Salmon D. J. 305,307 Salzer A. 314 Samdal,S. 357 Samhoun K. 264 Sams J. R. 306 Sanchez A. 204 Sandford H. 199 Sandow T. 237 Sandstrom M.162. 164 Sanger A. R. 317 Sanner R. D. 330 Sansomi M. 321 Sappa E. 363 Saraev V. V. 128 Sargeson,A. M. 27,28,30,32 33,36,42,298 Sarkar S. K. 12 280 Sasaki T. 354 Sasaki Y.,158 171 Sasvari K. 219 Satchell D. P. N. 25 31 32 35,45 Satge J. 204 209 210 Satika S. K. 315 Sato M. 283 313 Sautereau H. 267 SavCant J. M. 332 Savel S. 311 Savory C. G. 169 Sawodny W. 255 Sawyer D. T. 233 290 305 Sbrana G. 315 Scandola,F. 308 Schack C. J. 216,235,252 Schafer H. 201 247 248 Schaefer H. F.,236,257 Schafer H.-G. 221 Schaeffer E. 332 $chaffer S. W. 8 Scharf W. 270 Schatz G. 22 Scheffold R. 332 Schegel H. B. 325 Scheidt W. R. 274 282 290 306,315 Schepers,G.14 Scheraga,H. A. 6 Scheringer,C.,166 Schiller P. W. 19 Schilling B. E. R. 319 320 363 Schilling F. C. 235 Schipper,P. 123 Schlapfer C. W. 201 309 Schlessinger J. 21 Author Index Schleussner G. 27 1 Schleyer P. von R. 325 Schlick S. 119 Schloter. K.,313 Schmehl R. H. 234 Schmid P. 138 Schmid W. E. 83 Schmidbauer H. 177 227 270,310 Schmitt,G. 359 Schneider,B. I. 251 Schneider,H. 159 Schnockel H. 229 Scholer H.-F. 228 Schoemaker R. L. 59 Scholes C. P. 140 Schoone J. C.. 225 Schoonover M. W. 347 Schoot Uiterkamp A. J. M. 141 Schrader G. L. jun. 322 Schreiber A. B. 16 Schreiner P. R. 347 Schriver D. F. 319 Schrobilgen G. J. 248,257 Schrock R.R. 276 288 330 333,334,339 Schroder M.. 307 Schroeder R. R. 302 Schroen R. 197 Schubert K. 140 Schubert U. 177 210 270 310 Schugar H. J. 305 Schultz A. J. 301 323 328 350,361 Schultz F. A. 281 Schulz H. 163,279,323 Schulz P. A. 54,59,60,71 Schumacher H. J. 235 Schumann H. 261,262,326 Schurig V. 337 Schuster F. 236 Schwarzle J. A. 339 Schwartz J. 328 Schwartz S. J. 200 245 Schwarz W. 202 204 228 356 Schweitzer G. K.,157 Schweizer I. 335 Schwier J. R. 190 Scollary,G. R. 261,327 Scott A. I. 332 Scott c. 349 Scott R. A. 310 Scouten,W. H. 23 Scozzafawa A. 298,310 Scrivanti,A. 350 Sealy R. C. 150 Searcy A. W. 201 Searle G. H. 308 Secemski I. I. 31 Seddon K.R. 301 316 335 Author Index 383 Seeley N. J. 118 Shore S. G. 165 168 173 Smith G. D. 159 Seely M. L. 121 313,319 Smith G. K. 8 Seff K. 162 260 297 Shreeve J. M. 240 244 246 Smith I. G. 129 131 310 247 Smith J. D.. 347 Segal B. G. 171,263 Shum W. 279 Smith K. A. 176 257 Segal M. G. 295,303 Shumikhin A. G. 254 Smith K. P. 68 Seidel W. 275 Shurvell H. F. 171 Smith P.D. 305 Seip R. 243 Siddiqi Z. A. 248 Smith R. A. J. 354 Sekizaki M. 308 Siebert W. 193. 194 Smith R. D. 238,240 Sekutowski,J. C. 285,287 Siegebahn K.,257 312 Smith S. D. 52 327,352 Siegel S. 116 Smith T. D. 140 160 Sela M.,5,7 Sieger. H. 159 Smith T. J. 278 Selby R. C. 129 Sieker L. C. 303 Smith W. F. 304 344 Selegue J. P. 335 Severs G. 12 Smolyar A.E. 254,256 Seleznev A. P. 234 Severs R. 226 Smyrl N. R. 201 236 246 Selig H. 235,250,254 Sigel H. 41 254 Sellars P. J. 332 Silverthorn W. E. 360 Smeddon L. G. 177 Sellman D. 312 Sim G. 291 Snow M. R. 308 Semenenko K. N. 202 Simmons N. P. C. 211 So,S. P. 246 Seminara A. 263 Simon A. 158,237 Sobolev E. S. 175 Semprini E. 312 Simones J. A. M. 288 Sofen,S. R. 266 295 Sen A. 328 Simmov M. A. 198 Sohma J. 132 138 Senftleber F. C. 125 Simpson J. 125 166 Solar J. R. 335 Seo E. T. 233 Sims A. L. 184 Soldatov E. N. 206 Seppelt K. 235,246,250,251 Singaram B. 190 Solomon E. I. 303 306,310 258,333 Singbeil D. L. 205 Solov’ev B. V. 128 Serafin M. 272 Singh A. 345 Solovieva 0.N. 8 Sergent M. 281 Singh. B. 160,325 Soltz B. A. 325 Serpone N. 270,323 Singleton E.332 354 Solymosi F. 230 Setser D. W. 80,257 Sinn E. 127 291 Somberg H. 253 Setzler L. M. 11 Sinyanskii V.F. 251 Somersall A. C. 107,113 Seyferth D. 208 209 210 Siol W. 234 Somersall. D. C. 112 211,325,360 Sironi A. 321 Sommer H. 164 Shah V. K. 282 Sjoblom R. K.,264 Sommer J. 245 Shaklai N. 15 Skapski A. C. 199 307 309 Sommerville P. 362 Shalitin Y. 30 340 Somogyvari A. 270 Shamir J. 253 Skell P. S. 361 Sordo J. 204 Shanton K. J. 284 Skelton B. W. 124 Sorensen T. S. 350 Shanzer A. 25 1 Skinner H. A. 312 Sorlie M. 202 Shapley J. R. 318 319 320 Skinner M. 249 Sorokin P. P. 89 328,362 Skoglund M. 147 Sorrel] T. N. 292 Sharp P. R. 276,333,339 Slater R. 81 Sosinsky B. A. 347 Sharts C. M. 232 Slezak V.,92 Soutar I. 106 107 Shatas R.. 165 Slivnik J.258 Sowerby D. B. 221 Shatas S. 165 Small R. W. H. 164 Spangenberg M. 290 Shaw D. B. 334 Smallcornbe S. H. 8 Spangler C. W. 200 Shechter H. 147 Smardzewski R. L. 216 Spartalian. K.,306 Sheldrick G. M.,221,318,319 236 Spaulding L. D. 140 320,324,355,360,362,363 Smart J. C. 357 Speiser. S.. 49,64 Shemyakin N. F. 181 Smart L. E. 343 Spek A. L. 225,328 Shen Y.R. 54,60,71 Smelkinson A. E. 214 Spekkens P. H. 255 Sherman E. O. 347 Smidt K. H. 264 Spencer D. J. 92 Sherren A. T. 300 Smirnov B. M. 251 Spencer J. L. 301 318 339 Sherry E. G. 263 Smirnova T. A. 116 354 Shibahara T. 299 Smith A. K. 315,322,359 Spielvogel B. F. 196 Shiels A. 46 Smith A. L.,257 Spiridonov V. P. 254 260 Shiga K. 15 Smith A. R. P. 283 Spiro T. G. 306 307. 310 Shiller A.M. 272 Smith B. C.. 157,318 Sprague E. D. 137 Shimada H.,12 Smith B. E. 171 Squillacote V. L. 32 35 Shiotani M. 129 130 132 Smith C. G. 305 Sridhara N. S. 346 138 Smith D. E. 242 Stadther L. G. 46 Shipmova N. R. 38 Smith D. R. 118 Stahl I. 244 Shirakawa H. 110 Smith D. W. 289 Stahl L. H. 312 Shmidt F. K.,128 Smith E. A. 145 Stahlbush J. R.. 306 384 Stampf E. J. 199 Stanislawski,D. A. 219 Stanley G. G. 305 Stansfield R. F. D. 289 355 362 Stanzl K. 190 Starkie H. C. 121 Stary F. E. 325 Staudigh R. 188 Stauber S. 258 Staves J. 169 173 174 Stebbings R. F. 257 Steele R. V. 70 Stefani F. 312 Stefanovskaya N. N. 288 Steffen M. 203 Steffen W. L. 269 Steidel J. 237 Stein C. A. 307 Stein L.257 Steinberg I. Z. 13 19 20 21 Steinlmann A. 22 Steiner R. F. 14 23 Steiner. W. 210 Steinfeld J. I. 83 253 Steinhauser H. G. 291 Stelion K. 245 Stenkamp R. E. 303 Stensvad S. 278 Stephens F. F. S. 312 Stephens P. J. 292 294 Stephenson G. R. 353 Stephenson I. C. 90 Stepukhovich A. D. 254 Steudel R. 236 237 Stevens A. E.. 335,352 Stevens S. C. V. 270 Stevie F. A. 254 Stewart C. D. 337,344 Stibr B. 177 Stief L. J. 214 Stiefel E. I. 282 Stille J. K. 328 342 351 Stiller A. H. 305 Stobart S. R. 163,213 Stobbe S. 352 Stoeger W. 252 Stojakovic D. R. 266 Stone F. G. A. 179 289. 301 313,318,324,331,339,345 349,35 1,354,362,363 Storr A. 205 Strach S. J.122 245 Strack H. 338 Strahle J. 353 Strand T. G. 250 Strauss J. U. 352 Strege P. E. 347 352 Street G. B. 238 240 Streit G. E. 215 Stringer M. B. 353 Stroka J. 159 Stromnova T. A. 321 Strosberg A. D. 16 Struchkor Yu. T. 181 321 348,356 Struhle J. 278 Strukov E. G. 251 Strumolo D. 321 Strunin V. P. 93 Stryer L. 18 19 100 Stubbs L. C. 124 Stucky G. D. 271 328 347 350 Stufkens D. J. 3 12,338 340 Stuhl L. S. 352 Stults B. R. 222 Stuntz G. F. 362 Stupin D. Yu. 234 Styles E. 360 Su S. P. 216 Subra R. 270 Subramanian V.. 297 Subrtova V. 184 Sudbo A. A. 54 Sudbo A. S. 59 71 Suss G. 319 Sugai S. 5 Sugiura Y. 141 Sugiyama Y. 132 Suib S. L. 328 Sukhoverkhov V.F. 254 Sullivan J. C. 264 Sullivan S. A. 199 Suna A. 113 Sunder W. A. 235,236 254 Sundermeyer W. 175,202 Suslick K. S. 292 293 298 Sutherland H. H. 206,247 Sutherland J. C. 292 Sutthoff R. F. 40 Sutton H. C. 233 Suzuki K. 256 Svensson S. 257 Svitsyn R. A.. 175 Swaisgood H. E. 10 Swaminathan S. 234 Swanson B. I. 315 Swanwick M. G. 344 Sweeny J. G. 216 Sweigart D. A. 361 Swenson D. 163 Sykes A. G. 39,295,303 308 Sykora J. 252 Symons M. C. R. 117 118 119,120,121,122,123,125 129,130,131,132,133,135 136,140 142,144,145 147 190,234,243 Sze S. N. 196 Sze Y.K. 38 Szil Z. 207 Szwabski S. 250 Szymanski T. 290 Taarit Y. B. 133 Author Index Tablas F.G. M. 83 Tachibana A. 237 Tachikawa M. 318 362 Tadashi O. 44 Taesler I. 235 Tainturier G. 357 Tajmir-Riahi H. A. 263 Takagi Y.,213 Takahashi K. 161 Takahata Y. 122 Takase K. 18 Takasuka M. 195 Takegami Y. 349,354 Takeshita M. 305 Taketomi H. 6 Takita Y. 231 Tal D. 64 Talzi E. P. 236 Tam W. 313,333 Tamamura T. 109 Tamaru K. 322 Tan S. L. 39 Tanaka K. 237 Tanaka M. 46 Tanaka T. 324 Tanford C. 5,8 Tanimoto O. 103 Tanner S. C. 308 Tantot K. 255 Tarakhanov G. A. 46 Tarasov V. P. 202 Tatehata A. 308 Tatsumi T. 313 Tatsumoto K. 44 Tatsuno Y. 306 Taube H. 307 Taylor D. 203 231,296 306 Taylor G. L. 304 Taylor J. C. 264 267 Taylor N.J.284 333 344 Taylor P. 17,245 Taylor R. C. 220 Taylor S. H. 35 Taylorson D. 166 Tebbe F. N. 336 Teherani T. H. 310 Teitelbaum R. C. 252 Tellgren R. 235 Tellinghuisen J. 257 Tellinghuisen P. C. 257 Tempel. N. 228 Tempest A. C. 265 Tempete-Gaillourdet M. 7 Templeton D. H. 171 172 257,260,264,265 Templeton J. L. 273 Templeton L. K. 171,265 Tenajas M. L. 176 Tench A. J. 133 Tennenbaum-Bayer H. 8 Termes S. C. 279 Tesky F. M. 240 Tetin S. Yu 11 Teuben J. H. 277,332,339 Author Index Tevault D. E. 216 236 Tezikov V. N. 234 Theolier A. 322 Theophanides T. 301 Theveneau H. 170 Thevenot F. 189 Thewalt U. 271 Thiele G. 222 354 Thiele K. H. 271 Thoennes D.158,160 Thomas D. D. 139 Thomas D. W. 318 Thomas J. K. 208,234 Thomas J. L. 340 344 Thomas P. D. P. 170 172 Thomas R. J. W. 283 Thomason T. 233 Thompson A. C. 195 Thompson D. A. 182 Thompson P. A. 232 Thompson P. J. 331 Thompson R. E. 11 Thompson S. J. 360 Thomson A. J. 294 Thorn,D. L. 342,362 Thorn V. 210 Thorne L. R. 195 Thornton E. W. 211,230,231 Thornton P. 286 305 Thorpe F. G. 164 Thunder A. E. 158 Tiee J. J. 250 Tilley R. I. 310 Timasheff S. N. 11 Timchenko T. I. 198 Timmer K. 328 Timms P. L. 291,359 Timney J. A. 314 Tinner V. 39 Tin Win 91 Tinyatova E. I. 288 Tipper C. F. H. 331 Tipton D. L. 362 Tiripicchio. A. 363 Titov L. V. 170 Titov V. A. 249 Titova K. V. 170 175,255 Tobias R.S. 301 Toby B. 352 Todd L. J. 170 174 182,249 Tokushige M. 10 Tola P. 126 302 Tolman C. A. 328,350 Tolpin E. I. 174 Tom G. M. 307 Tondello A. 265 269 Toppen D. L. 293 Toriyama K. 133 135 Tosi L. 310 Tosik A. 263 Totani T. 195 Toth L. M. 247 Touhara H. 253 Tournoux M. 269 Trachenko V. I. 38 Trageser G. 305 Tranquard A. 207 Tranquille M. 87 246 315 Travis D. N. 91 Traylor T. G. 293 Treadaway M. F. 108,110 Trebilco D. A. 229 Tressaud A. 251 Tributsch H. 279 Trifunac A. D. 150 Trigwell K. R. 169 Trkula M. 308 Trogler W. C. 278,284 Troitsky G. V. 11 Trokiner A. 170 Trong A. N. 326 Trooster J. M. 304 Trost B. M. 347,352 Trotman-Dickenson A. F. 216 Trotter J.192 205 288 Truchetet F. 254 Truter M. R. 158 161 Tsang E. 326 Tsang W. 74,80 Tsao Y. P. 281 Tsay W. S. 64 Tsang Y.-H. 194,352 Tse M. W. 213 Tsin. T. B. 306 Tsipis C. A. 301 Tso C. C. 312 Tsong T. Y. 5,6 Tsou T. T. 128 329 Tsuda M. 253 Tsutsui M. 3 11 Tsvetkov V. G. 223,250 Tu S. C. 21 Tuck D. G. 290 Tucker P. A. 298 Tuinstra H. E. 326 Tulip T. H. 349 Tullius T. D. 303 Tumanov 0.A. 82 Tupikov V. I. 128 251 Turner. A. G. 237 Turner G. 305 Turner J. J. 68 87 246 314 315 Turner K. 333 Turner R. F. 314 Turney T. W. 359 Turro N. J. 81 Turova N. Ya. 202 Turtle P. C. 301 308 Tuttle T. R.. 118 Twarowski A. J. 284 Tweedle M. F. 291 292 Tyler B. J. 89 Tyler J. K. 215 216 Tyrer J.D. 237 Uchara K. 46 Uchida Y. 283 313 Udupa M. R. 240 Ueda I. 297 Ueda Y. 6,315 Ugo R. 309,322 Uhlig E. 275 Ukimer M. A. 312 Ulman J. A. 168,177 Umani-Ronchi A. 313 Underhill A. E. 301 323 Ungermann C. B. 179 Upton T. H. 314 Urch D. S. 159 203 278 Urdaneta-PCrez M. 325 Ustynyuk N. A. 356 360 Ustynyuk Yu. A. 360 Usyatinskii A. Y. 180 Vagg R. S. 195 Vahl G. 245 Vahrenkamp H. 284,311.320 Valderram N. J. 205 Valentini G. 315 Valkonen J. 249,259 Valle G. 247 Vallee B. L. 12 21 Vamplew D. 41 van Bronswijk W. 240 van Camp H. L. 140 Van Catledge F. A. 350 Van de Deen H. 141 Van den Berg J. P. 304 Van den Hurk J. W. G. 225 Van der Helm D. 176,359 Van der Put P. J. 127 Van der Stok E.332 van de Sand H. 309 van de Waals J. H. 146 Van Doorn J. A. 219,322 Van Dreele R. B. 275 van Koningsveld H. 297 van Koten G. 225 328 van Kralingen C. G. 297 Van Ooijen J. A. C. 128 van Wazer J. B. 228 Van Zee R. J. 121 Varani G. 308 Varekh V. V. 40 Vargaftig M. N. 321 Vasic P. 211 Vasile M. J. 254 Vedelhoven W. 335 Vedrine J. C. 122 Veeger C. 23 Vega R. 163 Veiga M. L. 249 Veillard A. 338 Veith M. 213 Vejrosta J. 46 Vekris J. E. 236 Velazco J. E. 257 Venikouas G. E. 109 Venkatappa M. P. 303 Verkade C. P. 340 Verma N. C. 150 Verpoorte J. A. 10 Viola J. C. 189 Vicentini. G. 262 263 Vichi E. J. S. 353 Vickery L. E. 12 14 Vickrey T. M. 298 Vidal J. L. 321 Vidali M.264 Viegers M. P. 280 310 Vigato P. A. 264 Vignalou J.-R. 207 Villafranca J. J. 21 Vilminot S.,212 Vincent M. G. 203 Vinter J. G. 240 Visser A. J. W. G.. 23 Vitagliano A. 342 Vivier H. 231 Vlasse M. 165 Vogtle F. 159 Vogler A. 162,315,323 Volini M. 9 Volkov V. V. 167 174 Vollenbroek F. A.. 304 Vollhardt K. P. C. 353 Volpin M. E. 332 Von Felten H. 279 von Kameke A.. 307 von Rumohr A. 202 Vos A. 256 Voulgaropoulos A. N. 240 Vrieze K.,338,340 Vyazankin N. S. 223 Wachtor R. 315 Wada G. 44 Wada Y. 7 Waddington T. C. 228,229 Wade K. 318 Wadt W. R. 257 Wagner A. J. 221 Wagner H. G. 232 Wagner H. U.. 244 Wagner R. E. 323 Wagner W. R. 288,334 Wahl Ph. 22 Wahren R. 318 Wainwright K.P. 308 Wako H. 6 Walbergs U. 359 Walder L. 332 Walker E. 281 Walker J. K. 28 Walker P. E. 161 Wallart F. 201 Wallbridge M. G. H. 170,180 185,187 Wallin T. 163 Wallis R. C. 335 Walpole J. N. 63 Walsh J. L. 167 169 170 Walters F. H. 290 Walters T. N. 38 Walton P. D. 206,247 Walton R. A. 278,305 Wamser C. C.. 55 Wan J. K. S. 325 Wanatabe J. 120 Wang H.-Y. 266 Wang. J. T. 306 Wang S.F. 9 Wannagat U. 192 Ward C. R. M. 39 Ward D. L. 257 Ward R. 51 Ward W. W. 22 Wardman P. 118 Warfield L.T. 191 Warren K. D. 352,358 Warren L. F. 296 Warrick C. 282,295 Warten G. A. 220 Washida N. 215 Wasif S.,243 Wasserman E. 146 Watanabe H. 195 Watanabe Y. 349 354 Watkins D.M. 301,323 Watson D. J. 125,318 Watt G. D. 283 344 Watters K. L. 7 Watton E. C. 195 Watz W. L. 314 Wayda A. L. 261,326 Waynant R. W. 257 Webb J. D. 257 Webber M. J. 203 Webber S.E. 107,113,114 Weber D. C. 240 Weber G. 5 Weber L. 347,352 Weber W. P. 208,209 Wege D. 353 Wehner E. 237 Weidlein J. 228 Weiher U. 278 Weil T. J. 31,45 Wein M. 28 Weiss E. 158 160,309,354 Weiss J. 247 Weiss R. 165 169 300 335 344 Weissmann C. 10 Welch A. J. 179,187,260,349 Welch J. 265 Welge K. H. 82 Wells E. J. 248 Wells M. A. 30 Wells R. L. 196 Wellum G. R. 174 Welter J. J. 347 Weltner W. 121 Wendlandt W. W.. 195 Wenner G. 233 Wentworth R. A. D. 283,344 Werber M. M. 30 Werner H. 329 359 Werner R.359 Author Index Wernli B. 279 Wessner D. 262 West D. X. 125 West R. 219 325 West R. J.. 291 Westerhof A. 240 Westhof E. 136 Westland A. D. 250 Weston R. E. 74 Westwood N. P. C. 165,211 Weulersse J. M. 254 Whangbo M.-H.. 309,323 Wharton D. C. 12 Wheatley P. J. 362 Wheeler S. H. 307 White A. H. 124 White C. 360 White D. N. J. 176 White F. H. 5 White F. H. jun. 7 White M. A. 320 White M. N. 31 White N. 343 Whitesides G. M. 331 Whiting S. M. 355 Whitmer J. C. 171 Whitten D. G. 234 Whittingham R.S.,273 Wiberg N. 210 Wichelhaus W. 263 Wiech G. 203 Wiget P. 15 Wigfield K. 229 Wignacourt J. P. 201 Wihler H. D. 228 Wilaynski R. 177 Wild F. R. W. P. 357 Wild J. F. 264 Wilinksi J.201 Wilke G. 352 361 Wilkerson J. L. 121 Wilkins. R. G. 26 Wilkinson G. 271 275 285 288,327,330,340,359 Wilkinson M. 204 Williams D. R. 303 Williams E. H. 259 265 Williams F. 122,129,130,137 Williams J. M..171 301 316 323,328,350,361 Williams J. O. 99 Williams T. F. 131 Willis A. C.. 306 Willis C. L. 40 74 92 Willis G. A. 283 Willner v.,245 Wilmot P. B. 91 Wilms A. 203 Wilson C. J. 338 Wilson L. J. 291 292 306 Wilson N. 200 Wilson P. W. 264 Wilson R.D. 255,306,319 Wilson S. T. 307 Author Index Wilson W. L. 220 Wilson W. W.. 235 Winer A. M. 215 Wingfield J. N. 158 Winter M. J. 289 362 Winter W. 337,353 Winterfield C. 59 Winterstein W. 192 Wisian-Neilson P.196 Wittig C. 250 Wittmann J. M. 150 Woditsch A. 356 Wojcicki A, 314 Wold A. 279 Wolf E. 249 Wolf T. E. 282,295 Wolfrum J. 5569 Wollmann R. G. 126,305 Wolmershauser G. 238 Wong E. H. S. 185. 191 Wong G. B. 306 Wong K. L. 306 Wong K. P. 5 Wong K. S. 188,315 Wong M. 234 Wong S. S. 13 Wong V. K. 236 Wong W. H. 40 Wood C. D. 276,333,334 Wood D. E. 129 130,131 Wood D. J. 301,323 Wood J. M. 211 Wood J. S. 263 Wood J. T. 44 Wood R. D. 28 Woode K. A. 307,309 Woodruff W. H. 303 Woodward P. 289 318 349 355,362 Woody R. W. 11 hoolf R. A. 251,350 Woollard D. C. 266 Woolley P. 46 Woolley R. G. 297 Wooton D. L. 247 Wormsbaher D. 359 Worrall I. J. 204 Worsham P. R. 234 Wrackmeyer B.165,200 Wreford S. S.. 274 Wright A. F. 308 Wright M. J. 307 Wright R. B. 200 Wright R. D. 107 Wright W. F. 170 182 Wrighton M. S. 315 317 362 wu c.w. 21 WU,S.M; 319 Wiirstl P. 354 Wulff W.D.. 208,325 Wunderlich H. 253 WUSSOW. H.-G. 253 Wyatt J. R. 240 Yablokov V. A. 223 Yablokova N. V. 223 Yablonovitch E. 56 59 Yagi T. 306 Yahav G. 81 Yakel H. L. 162 Yakibovich 0.V.,198 Yakovlev I. I. 254 Yamabe T. 237 Yamada K. M. 6 Yamamoto A. 343 Yamamoto H. 311 Yamamoto T. 330,343 Yamamoto Y. 41,324 Yamanaka K. 7 Yamano T. 15 Yamanouchi K. 281 Yamaoka H. 147 Yamase T. 279 Yamazaki H. 324,353 Yanagida S. 161 Yang T. P. 257 Yarbrough L. W. 312 Yarkov S. P. 138 Yasuhiro Y. 44 Yasumura T.237 Yatsento B. P. 46 Yeh. H. J. C. 306 Yim. M. B. 129 Yogev A. 75,76,77 Yokota M. 103 Yokota Y. 230 Yokoyama M. 109 Yokoyama T. 41 Yon J. M. 7 Yonezawa T. 132,216 Yong D. J. 224 Yoroki M. 213 Yoshida T. 308 345 Yoshida Y. 315 Young D. C. 220 Young G. B. 331 Young. I. M. 249 Young J. P. 264 Young W. J. 276,334 Yu S.-Y. 223 235 Yuasa F. 132 Yuen C.-K. 218 Zaidi S. A. A. 248 Zakharkin L. I. 181 Zakzhevskii V. G. 256 Zalkin A. 171 172,257,260 264,265 Zamashchikov V. V.. 40 Zanazzi P. F. 313 Zanderighi G. M. 322 Zanella A. W..36 37,298 Zanobini F. 222 296 Zanotti G. 247 Zanuzzi C. F. 324 Zanzari A. R. 313 Zapata J. P. 305 Zasorin E. Z. 260 Zavyalov V. P. 11 Zaworotko M.J. 288 330 Zehnder. E. J. 237 Zehner H. 133 136 ZeMna E. 34,46 Zellner R. 232 Zemva B. 258 Zenneck U. 360 Zentgray R. 200 Zhigach A. F. 175 Zhitneva G. P. 254 Zilberman E. N. 38 Zimmer. R. 226 Zimmerman G. J. 177 Zimmermann-Telschow H. 8 Zink J. I. 315 Zinner K. 262 Zinner L. B. 262 Zobrist M. 293 Zocchi M. 337 Zompa L. J. 308 Zoubek G. 222 Zubarev V. E. 138 Zuccaro C. I. 309 319 Zuev M. B. 254 Zupan M. 258 Zurback E. P. 312 Zvezdina V. V. 249 Zwanzig R. 103 Zyontz L. 352

ISSN:0308-6003    

DOI:10.1039/PR9787500364

出版商:RSC    

年代:1978

数据来源: RSC