10 Ru Os Rh Ir Pd Pt By W. LEVASON Department of Chemistry The University Southampton SO9 5NH 1 Ruthenium A major review dealing with catalysis by metal cluster compounds has appeared,' and a second short article' summarizes some recent ideas about the structures and reactivity of clusters. A review3 of electron-transfer processes in d 5 d ions includes data on the Creutz-Taube-type complexes. The potential medical applications of Ru isotopes have been disc~ssed.~ A study of the 99Run.m.r. spectra of a range of ruthenium complexes has demonstrated the potential of this technique and the wide chemical shift range (-9000p.p.m.);5 LRu(CN) was proposed as the "Ru reference to replace RuO used in earlier studies. Investigation of ruthenium carbonyl clusters remains the most active area of research in Ru chemistry with increasing emphasis being placed upon the incorpor- ation of other metal atoms.Conditions for the preparation of the unstable M(CO) compounds (M = Ru or 0s) from M3(C0), and CO have been described.6" The [M(CO),(SbPh,)] (M = Ru or 0s) complexes prepared from them have equatorial SbPh groups,6b in contrast to [M(CO),(EPh,)] (E = P or As) when the Group VB substituent occupies an axial position. The reactions of trans-]( SbF6)2 or ci~-[Ru(C0)~( ](SbF,), [Ru(CO),( Ph2PCH2CH2PPh2) Ph2PCH2PPh2)* with Na[HB(OEt),] produces the corresponding formyls [Ru( HCO)(CO)- (diphosphine),]SbF6 without change in stereochemistry. An X-ray of study of the (deuteriated [Ru( DCO)(CO)(Ph2PCH2CH2PPh2)2]SbF6 revealed a long Ru-CDO bond (2.09 A).7The tran3-[Ru(CO),Cl2(L),1( L = PMe2Ph or AsMe,Ph) compounds react with alkynes RO,CC_CCO,R to give alkenyls [Ru(CO),{C(CO,R)= C(C02R)Cl}CI(L)2],8" and for L = PMe,Ph only with HgR (R = Ph or Me) to give [Ru(CO),R(C~)L~],'~ and cis-or tr~ns-[Ru(PMe~Ph)~(CO)~Cl~] LiR give [Ru(PM~~P~),(CO),R,],~~ which have cis-R groups.' E. L. Muetterties and M. J. Krause Angew. Chem. Int. Ed. Engl. 1983 22 135. M. J. McGlinchey M. Mlekuz P. Bougeard B. G. Sayer A. Marinetti J.-Y. Saillard and G. Jaouen Can. J. Chem. 1983 61 1319. ' C. Creutz Progr. Inorg. Chem. 1983 30,1. S. L. Waters. Coord. Chem. Rev. 1983 52 171. C. Brevard and P. Granger Inorg. Chem. 1983 22 532. ' (a) P. Rubhman ti. N. Van Buuren M. Shiralian and R.K. Pomeroy Organometa//ics 1983 2 693; (b)L. R. Martin F. W. B. Einstein and R. K. Pomeroy Inorg. Chem. 1983 22 1960. ' G. Smith D. J. Cole-Hamilton M. Thornton-Pettit and M. B. Hursthouse J. Chem. Soe. Dalton Trans. 1983 2501. (a) P. R. Holland B. Howard and R. J. Mawby J. Chem. Soc. Dalfon Trans. 1983 231; (b)D. R. Saunders M. Stephenson and R. J. Mawby J. Chem. SOC. Dalton Trans. 1983 2473 245 246 W.Levason The diruthenium complexes (1) (R,R' = H,Me; H,Ph; Ph,Ph) can be protonated to give p-vinyl complexes (2) and these react with H-to give p-carbenes (3)."" On boiling in toluene the complexes (1) (R,R' = H,Ph) are converted into the p-vinylidenes (4) (and the corresponding trans isomers) which can be protonated with HBF4 (R' = H) to the p-ethylidene [Ru~(CO),(~-CO)(~-CM~)(~~-C~H~)JBF~.~~ R' R' I The reactions of (1) with allenes have also been described." Photolysis of [RU~(CO),(~-CO)(~-CHR)(~~-C~H~)~] (R = H Me or C0,Et) in the presence of H2 yields the triruthenium material [RU~(~~-H)~(CO)~(~~-C~H~)~] which reacts with unsaturated hydrocarbons with retention of the Ru unit in contrast to RU,(CO)~ which tends to fragment.'d X-Ray studies of [Ru3(CO) ,{P(cyclo-C,H ,),}I [Ru,(CO),,{P(OMe),),] and [RU~(CO)~(PM~,),]'~" which contain equatorial PR groups and of [Ru3(CO),,-,(CNBu'),,1 (n = 1 or 2) with axial CNR groups,loh and of the produced from RU,(CO)~~ [RU~(CO)~&~-NP~)] and PhNO2,IoC have been reported.A series of Au Ru (n = 1,2 or 3) clusters have been synthesized from AuMe(PPh,) and [Ru3( P-H)~(p3-COMe)( CO),] or [Ru3( p-H)( p-COMe)( CO) ;lad the struc- tures of the Au2Ru3 and Au3Ru3 complexes are shown in (5).The structure of the Hg[Ru3(CO),(C,Bu')] involves Hg bridging one edge of each of the Ru triangles."" The bimetallic [FeRu2(p-C1),(C0),(PR3),] (R = Me or Ph) compounds react with Na2C0 in aqueous acetone to give [F~Ru,(~-OH),(CO),(PR~)~], but in Pr'OH for R = Ph only the product is [F~Ru,(~-OH)(~-H)(CO),(PR~)~].~' (a)A. F. Dyke S. A. R. Knox M. J. Morris and P. J. Naish J. Chem. SOC.,Dalton Trans. 1983 1417; (6) R.E. Colborn D. L. Davies A. F. Dyke A. Endesfelder S. A. R. Knox A. G. Orpen and D. Plaas J. Chem. Soc. Dalton Trans. 1983 2661; (c) R. E. Colborn A. F. Dyke S. A. R. Knox K. A. Mead and P.Woodward J. Chem. SOC.,Dalfon Trans. 1983 2099; (d) N. J. Farrow S. A. R. Knox M. J. Morris and A. G. Orpen J. Chem. Soc, Chem. Commun. 1983 234. lo (a)M. I. Bruce J. G. Matisons B. W. Skelton and A. H. White J. Chem. SOC.,Dalton Trans. 1983 2375; (b)M. I. Bruce j. G. Matisons R. C. Wallis J. M. Patrick B. W. Skelton and A. H. White J. Chem. SOC.,Dalton Trans. 1983 2365; (c) S. Bhaduri K. S. Gopalkrishnan G. M. Sheldrick W. Clegg and D. Stalke J. Chem. SOC.,Dalton Trans. 1983 2339; (d)L. W. Bateman M. Green K. A. Mead R. M. Mills I. D. Salter F. G. A. Stone and P. Woodward J. Chem. SOC.,Dalton Trans. 1983 2599; (e)S. Ermer K. King K. I. Hardcastle E. Rosenberg A. M. M. Lanfredi A. Tiripicchio and M. T. Camellini Znorg. Chem. 1983 22 1339." D. F. Jones P. H. Dixneuf A. Benoit and J.-Y. Le Marouille Inorg. Chem.. 1983 22 29. Ru Os,Rh Ir Pd Pt PPh3 Ph,PAu-Au PPh C OMe OMe (5) The reaction'2n of (PPN)N3 [PPN = bis(triphenylphosphine)iminium] with RU,(CO),~ gives the cyanate [PPN][Ru,(NCO)(CO),,] which takes up H2 to form [Ru,(H)~(NCO)(CO),~]- the latter being protonated by CF3S03H to [H3Ru4(NCO)(C0),2] (6). Unexpectedly [Ru,(NCO)(CO),,]- on reaction with KOH 0 C and PPN+ in MeOH gave [PPN][Ru,H(CO),,] which contains a distorted tetrahe- dral Ru4 core with three terminal CO ligands per Ru and one edge-bridging CO.lZb A combined X-ray and neutron diffraction study of [Ru,(CO)~( p-H)4{P(OMe)3}4] showed an Ru4 tetrahedron each Ru carried -(CO),[P(OMe),] and involved in two symmetrical Ru-H-Ru bridges.I2' The capped butterfly clustei [Ru4(p-H),(CO),,( p4-N)] has been obtained from [Ru,H~(CO),~]- and NOBF in CH2C12.12dReaction of [Ru4( p-H)2(CO)12]2- with MX(PPh3) (M = Cu,Ag or Au; X = C1) gave the hexanuclear clusters [MM'Ru4( p3-H)2(CO),2(PPh3)2] (M = M' = Cu Ag or Au; M = Cu M' = Ag or Au; M = Ag M' = Au) which contain Ru tetrahedra bicapped by MPPh3.12e Among the most interesting aspects of carbonyl chemistry described this year is the synthesis and reactions of the Ru carbido cluster RU~C(CO)~,.'~"-~ The 'parent' RuSC(CO), is produced [along with Ru(CO),] from Ru,C(CO), and CO at 70 "C and 80atm and has been shown to be a square-based pyramid with an exposed carbido atom lying slightly below the basal plane.It undergoes substitution reactions with phosphines to give [Ru,C(CO),,-,(PR,),] (R = MePh2 or Ph,; x = 1,2 or 3) and Ru,C(CO),~[P~~P(CH~)~PP~~] which have similar structures to the parent but adds MeCN to give [Ru,C(CO),,MeCN] in which the metal framework has re- arranged to a bridged butterfly. With X-anions (X = F C1 Br or I) it gives '' (a) D. E. Fjare J. A. Jensen and W. L. Gladfelter Inorg. Chem. 1983 22 1774; (b)J. A. Jensen D. E. Fjare and W. L. Gladfelter Inorg. Chem. 1983,22 1250; (c)A. G. Orpen and R. K. McMullan J. Chem. SOC.,Dalton Trans. 1983 463; (d)M. A. Collins B. F. G. Johnson J. Lewis J. M. Mace J. Morris M. McPartlin W. J. H. Nelson J. Puga. and P. R. Raithby J. Chem. SOC.,Chem. Commun. 1983,689; (e)M. J. Freeman M. Green A.G. Orpen I. D. Salter and F. G. A. Stone J. Chem. SOC.,Chem. Commun. 1983. 1332. 248 W.Levason [Ru,C(CO),~X]- which can be protonated reversibly to [RU~(H)C(CO)~~X].'~" Under pressure Ru,C(CO), will reversibly add CO to give RU&(CO)~, and can be electrochemically or chemically (e.g. KOH-MeOH) reduced 13b to [RU~C(CO),~]~-. The reactions of RLI~C(CO),~ with Au(PPh3)X (X = C1 or Br) give Ru-Au clusters 13' e.g. (7) and (8). Other Ru5 clusters described are [RU5(C0)16(p-PPh2)- (p5-P)]produced by heating [RU,(CO),(~-PP~~)(~-H)],I~~ and [RU~(CO)~~(~~-~)~- CCPh)(p- PPh,)] produced by pyrolysis of the phosphinoacetylene complex [RU~(CO),,(P~,PC&CP~)].'~~ Ru(1 Ru(5A) n Systematic syntheses for the anions [Ru,(CO),~]~- [Ru,(CO) ,I2- [Ru,(CO),~]~-and [Ru,(CO)~~]~- and controlled amounts of M+(benzophenone)-, from Ru~(CO)~~ and for the conjugate acids have been reported,15" whilst under different conditions the rare highly anionic clusters [Ru,(CO) [RU,(CO)~~]~- and [RU,(CO)~~]~- [Ru,(CO),~]~-are pr0d~ced.l~~ The anchoring of a variety of Ru3 Ru, Rug and Ru clusters uia Ph2PCH2CH2Si(OEt)3,16" and of the phosphinidene cluster [(p-H),Ru3(CO),(p3 -PCH2CH2Si(OEt)3],16bto oxide supports has been described.The latter complex shows unusual stability under catalytic conditions. The structures of [(r) -C5 H 5) Ru( CO) Br] and [(7 -C Me,Et) Ru(CO) Br] have been determined and compared in an attempt to correlate structural and reactivity difference^,'^ but it appears that data on other examples will be needed before this l3 (a) B.F. G. Johnson J. Lewis J. N. Nicholls J. Puga P. R.Raithby M. J. Rosales M. McPartlin and W. Clegg J. Chem. SOC.,Dalton Trans. 1983 277; (6) B. F. G. Johnson J. Lewis W. J. H. Nelson J. N. Nicholls J. Puga P. R. Raithby M. J. Rosales M. Schroder and M. D. Vargas J. Chem. SOC.,Dalton Trans. 1983 2447; (c) B. F. G. Johnson J. Lewis J. N. Nicholls J. Puga and K. H. Whitmire 1.Chem. SOC.,Dalion Trans. 1983 787; (d)A. G. Cowie B. F. G. Johnson J. Lewis J. N. Nicholls P. R. Raithby and M. J. Rosales J. Chem. SOC.,Dalton Trans. 1983 23 11. l4 (a) S. A. McLaughlin N. J. Taylor and A. J. Carty Inorg. Chem. 1983 22 1409; (b)S. A. McLaughlin N. J. Taylor and A. J. Carty Organornerallics 1983 2 1194. Is (a)A.A. Bhattacharyya C. C. Nagel and S. G. Shore Organomefallics 1983 2 1187; (b)A. A. Bhattacharyya and S. G. Shore Organomefallics 1983 2 1251. l6 (a) J. Evans and B. P. Gracey J. Chem. SOC.,Chem. Commun. 1983 247 (6) S. L. Cook and J. Evans J. Chem. SOC.,Chem. Commun. 1983 713. H. Adarns N. A. Bailey and C. White Inorg. Chem. 1983 22 1155. 249 Ru,Os Rh Ir Pd Pt is possible. Reduction of [(T~-C,H,)RU(PP~~)~C~] with LiA1H4 produced"" the thermally stable Ru'" hydride [(q 5-C5H5)RuH3] but the corresponding reactions with [(~s-CsH,)Ru(triphos)]+ [triphos = MeC(CH,PPh,),,PhP(CH,CH,PPh,),] resulted in regioselective reduction of the q5-C5H group to an q4-C5H6 ring.'8b Air-stable yellow crystals of the open-chain metallocenes [Ru(pentadienyl),] (pentadienyl = 2,4-dimethyl or 1,2,3,4-tetrarnethylpentadienyl)have been obtained from RuCI3.3H20 zinc dust and the pentadienes.I8" The structure of [Ru(q4-C8Hlo)( ~~-c8H,,)(P(oMe),}] (9) has been determined.'8d The reaction of [RuH,(PP~,)~]with [p-MeOC6H4N=CH-I2 produces air-sensitive black crystals formulated [Ru0(di-imine),J in which the ligands are a-bonded to the Ru via the nitrogen atoms.j9 The [{Ru(arene)X,},] react with MeC02H or CF3C02H to give [RU(~~- arene)X(02CR)] and [Ru( ~~-arene)(O~CR)~] (arene = C6H6 p-MeC,H,CHMe, 1,3,5-Me3C6H etc.).20The dicarboxylates appear to contain one mono- and one bi-dentate 0,CR- group which are equivalent on the n.m.r.time scale and from which the carboxylates are displaced easily by many ligands making these complexes useful precursors.A high spin [Ru"'(NO)CI,]- ion was reported last year but an electrochemical study of the oxidation of [Ru(NO)C15]'- has shown that the [Ru"'(NO)Cls]-ion produced is deep-green and low spin and indicates that the earlier report is in error.''" Sulphite adds to tran~-[Ru(py),Cl(NO)]~+ or cis-[R~(bipy)~X(NO)l"(X = C1 or Br) to give dark green [Ru(py),CI(NOSO,)] and [R~(bipy)~X(NOS0,)1, shown by an X-ray study to contain the new nitrosylsulphito anion [ONSO,]- bonded to the metal uia the nitrogen. The reactions are reversed by aqueous acid.,' Polypyridyl complexes of Ru remain of great interest. The absorption spectrum of the excited state of [Ru(bipy),]'+ (formulated [Ru(bipy);]'+) has been recorded and the promoted electron (M -* L) is localized on one bipyridyl ligand '* (a)S.G. Davies S. D. Moon and S. J. Simpson J. Chem. Soc. Chem. Commun. 1983 1278; (b)S. G. Davies S. J. Simpson H. Felkin and T. Fillebeen-khan Organometallics 1983 2 539; (c) L. Stahl and R. D. Ernst Organometallics 1983 2 1229; (d)P. Pertici G. Vitulli W. Porzio M. Zocchi P. 1.. Barli and G. Deganello J. Chem. SOC Dalton Trans. 1983 1553. 19 B. Chaudret C. Cayret H. Koster and R. Poilblanc J. Chem. Soc. Dalton Trans. 1983 941. 20 D. A. Tocher R. 0. Gould T. A. Stephenson M. A. Bennett J. P. Ennett T. W. Matheson L. Sawyer and V. K. Shah J. Chem. SOC.,Dalton Trans. 1983 1571. 2' (a)V. T. Coombe G. A. Heath T. A. Stephenson and D. A. Tocher J. Chern. SOC.,Chem. Commun. 1983 303; (b)F. Bottomley W.V. F. Brooks D. E. Paez P. S. White and M. Mukaida J. Chem. SOC. Dalton Trans. 1983 2465. 250 W.Levason [Ru"'(bipy),( bipy-)I3+ not delocalized over all three as originally thought.22n Other studies have described the photochemistry of ~is-[Ru(bipy),L,]~+ (L = 4bipy,iphen py pyridazine PMe,Ph etc.),22hand the redox chemistry electronic absorption and emission spectra of [R~(bipy),L,_,,]~~ (n = 0-2; L = 2,2'-bipyrazine or 2,2'-bipyrimidine).22' Polypyridyl complexes of Ru" and 0s" have been electropolymer- ized to produce polymer film coatings on the electrodes.22d7e The arylazopyridines (10) form [RuL,CI2] complexes which can be isolated in two isomeric forms (1 I). These Ru" complexes can be electrochemically oxidized to Ru'" and are converted into [Ru(H?O),L~]~+ by Ag' in water,23a the reaction being reversed by NaCl in both cases without isomerization.Water is dis- placed easily from the aquo complexes to give [Ru1IL,L;In+ (L = bipy en acac or triazine N-oxides)., Arylazo-oximate complexes [Ru(bipy),A]+ (HA = q N=N w (10) (R = Me or H) RC(NOH)N=NR; R = Me Ph or p-MeC&; R' = Ph or p-MeC,H,] have been prepared from [Ru(bipy),Cl( NO)],+ and alkylidene arylhydrazones RCH=NNHR in MeOH in the presence of NaOMe or directly from cis-[Ru(bipy),Cl,] + Na[A].23" Treatment with HClO gives [Ru(bipy),( HA)](ClO,),. Direct reaction of RuCl with HA in ethanol produces cis-[R~(HA),C1,1;~~~ an X-ray study of the (a-phenyl- azo)benzaldoxime complex confirmed the structure to be (1 2).Triazine oxides Rh(O)=NNHC,H,X-p(HL) (R = Et or Ph; X = Me H C1 NO2 etc.) form green- ish-yellow Ru"' complexes [RuL,] (rner-N303 co-ordination) on reaction with RuC13.3H20 and K2C03 in ethanol;23e electrochemical reduction to Ru" and oxidation to Ru'" is possible. The [R~(bipy),L](ClO,)~ complexes are readily reduced to Ru" and two further one-electron reductions probably localized on the bipy (L ligands were observed.23f Air oxidation of [{ Ru"(NH~)~}~L]~+ = meso-4,5-bis(4-pyridyl)-2,2-dimethyl-1,3-dioxolane) produces the Ru"' analogue and hydrogen peroxide., Trifluoroacetamide CF3CONH2 reacts with [Ru,(O,CMe),Cl] to give the RU"~"' complex [Ru,(HNOCCF~),C~].~~ 22 (a)P. S. Braterman A. Harriman G. A. Heath and L. J. Yellowlees J. Chem.Soc. Dalton Trans. 1983 1801 ; (6)J. V. Caspar and T. J. Meyer Inorg. Chem. 1983 22 2444; (c)D. P. Rillema G. Allen T. J. Meyer and D. Conrad Inorg. Chem. 1983 22 1617; (d)C. D. Ellis L. W. Margerum R. W. Murray and T. J. Meyer Inorg. Chem. 1983 22 1283; (e)J. M. Calvert R. H. Schrnehl B. P. Sullivan J. S. Facci T. J. Meyer and R. W. Murray Inorg. Chem. 1983 22 2151. 23 (a)S. Goswami A. R. Chakravarty and A. Chakravorty Inorg. Chem. 1983 22 602; (b)S. Goswami R. Mukherjee and A. Chakravorty Inorg. Chem. 1983,22,2825; (c)A. R. Chakravarty and A. Chakravorty J. Chern. Soc. Dalton Trans. 1983 961; (d)A. R. Chakravarty A. Chakravorty F. A. Cotton L. R. Falvello B. K. Ghosh and M. Tomas Inorg. Chem. 1983,22 1892; (e)R. Mukherjee and A. Chakravorty J. Chem.SOC.,Dalton Trans 1983 955; (-0 1983 2197. 24 D. M. Stanburg D. Gaswick G. M. Brown and H. Taube Inorg. Chem. 1983 22 1975. 25 T. Malinski D. Chang F. N. Feldmann J. L. Bear and K. M. Kadish Inorg. Chem. 1983 22 3225. Ru Os Rh Ir Pd Pt 25 1 Electrochemical oxidation of [Ru"(OEP)(CO)(EtOH)] (H20EP = octaethyl por- phyrin) gives the porphyrin radical compound [Ru"(OEP')+(CO)]+ which forms [Ru"(OEP')(CO)(py)]+ with pyridine but undergoes an Ru -+OEP' electron re- arrangement on treatment with tertiary phosphines to produce [Ru'"(OEP)(PR,),]+.~~ A series of phosphole (L) (13) complexes of Ru" of types cis-and trans-[RuL,(CO),Cl,] and cis-and trans-[RuL,Cl,] have been ~haracterized;,~" the cis-isomers are the more stable thermodynamically.The complex mer-[Ru(L),(CO)Cl,] [L = (13) R = Ph] has been studied by X-ray diffraction. The conversion of cis-and ~~U~~-[RU(M~,PCH,CH~PM~~)~C~~] photochemically into truns-[Ru( Me2PCH2C H2PMe2)2(H20)Cl]f in ethanol and trans-[Ru(Me2PCH,CH2PMe2)z(Me2SO)Cl]+in dimethylsulphoxide has been reported.27b (13) (R= Me Bun But Ph or Bz) X-Ray structures of several Ru" complexes of (f)-o-C6H4( PMePh),( L) have been determined including trans-[RuL2H(CO)]PF6.~Me2C0, cis-[RuL(CO)Cl2(Me2S0)] and trans-[RuL{ (*)-o-C6H4( PMePh)( P(0)MePh)}C12].27c*d The last contains a rare example of a diphosphine monoxide chelating to a metal and was a minor product of the reaction of RuCl with L and HCH0.27d An X-ray study of [(S)-Ru(v5-CSH,)C1(Ph,PCH(R)CH,PPh2)] (R = Me) and some chemistry of the related chiral diphosphine complexes (R = Me cyclo-C6H,, or Ph) has been de~cribed.,~' The Ru" complexes of two triphosphines PhP(CH2CH2CH2PPh,) (ttp) and PhP(CH2CH2CH2P(cyclo-c6Hl,),),(Cyttp) of type [RuLC12] have been prepared,27f the ttp complex is polymeric but the more sterically demanding Cyttp produces a monomeric complex.Both add CO to give monocarbonyls but only [Ru(Cyttp)C12] adds SO2(to form an 7 '-planar adduct) whereas both can be reduced in the presence of CO to [Ruo(CO),L]. Sodium borohydride reduces [Ru(ttp)Cl,], to [RuH(v2- BH,)(ttp)] and this can be converted into various cationic mono and neutral dihydrides by reaction with monodentate P or N donors.27f Ethylenediaminetetra-aceticacid (H,Edta) complexes of Ru" and Ru"' of types [Ru"(H,Edta)L] (L = (p~)~, (4-Mepy), 1,lO-phenanthroline 2,2'-bipyridyl or Ph2PCH2CH2PPh2) and [Ru"'(H,Edta)L'] (L' = (SCN), acetylacetonate- Et2NCS2-) have been prepared and all contain H,Edta as an N202 tetradentate donor.28 The resonance Raman spectrum of [(NH3)5Ru(S2)Ru(NH3)5]4+ is shown 26 M.Barley J. Y. Becker G. Domazetis D. Dolphin and B. R. James Can. J. Chem. 1983 61 2389. 27 (a)L.M. Wilkes J. H. Nelson L. B. McCusker K. Seff and F. Mathey Inorg. Chem. 1983 22 2476; (b) S. F. Clark and J. D. Pedersen Znorg. Chem. 1983 22 620; (c)S. L. Grocott B. W. Skelton and A. H. White Aust. J. Chem. 1983 36 259; (d)S. R. Hall B. W. Skelton and A. H. White Atrst. J. Chem. 1983 36 271 ibid. 1983 36 267; (e)F. Morandini G.Consiglio B. Straub G. Ciani and A. Sironi J. Chem. SOC. Dalton Trans. 1983 2293; (j)J. B. Letts T. J. Mazanec and D. W. Meek Organometallics 1983 2. 695. 2x A. A. Diamantis and J. V. Dubrawski. lnorg. Chem. 1983 22 1983. 252 W Levason to be consistent with the presence of an S$-bridge ruling out the alternative S2-f~rrnulation.~~ undergoes Electrochemical studies have shown that [BU~"N]~[RU~B~,] two reversible one-electron oxidations and one reversible one-electron reduction and [RU~"~'~B~~]~- have been prepared in solution by controlled and [Ru~Vp'VBr9]- ele~trolysis.~~" Molecular orbital (Xa)calculations on the ruthenium chloro-anions [RuCl6I3- [Ru2Cl9I3- and [Ru3C11J4- have been carried out and the results com- pared with structural and spectroscopic data.30b 2 Osmium Two reviews concerned with aspects of catalysis by osmium carbonyl clusters have a~peared.'.~' It has been demonstrated that non-bonded distances can be measured and hence the cluster skeleton identified in [os6(co)],] [OS~(CO)~~]~-, and [OS,~C(CO)~~]~-using EXAFS of the 0sL(II1) edge,32a and similarly the structures of Os3 clusters bound to oxide supports or tethered via bridging ligands to silica can be established.32b Osmium pentacarbonyl is obtained in 60% yield from OS~(CO),~ and CO at 200atm and 280-290 oC.6a Diosmium carbonyls are rare; one example is [OS~(CO)~I~] shown by an X-ray study to be a butterfly structure (14).33A detailed study of the vibrational spectra of the vinyl and vinylidene complexes [OS~(CO),~( pH)(p-q2-CH=CH2)]and [Os,(CO),( P-H)~(p3-q2-C=CH)]andthe 'H analogues identified the characteristic vibrations of the C2-hydrocarbon units 29 S.Kim E. S. Otterbein R. P. Rava S. S. Isied J. San Fillippo jun. and J. V. Waszcyak J. Am. Chem. Soc. 1983 105 336. 30 (a) V. T. Coombe G. A. Heath T. A. Stephenson and D. K. Vattis J. Chem. Soc. Dalton Trans. 1983 2307; (b)B. E. Bursten F. A. Cotton and A. Fong Inorg. Chem. 1983 22 2127. 3' R. A. Adams Acc. Chem. Res. 1983 16 61. 32 (a)S.L. Cook,J. Evans G. N. Greaves B. F. G. Johnson J. Lewis P. R. Raithby P. B. Wells and P. Worthington J. Chem. SOC.,Chem. Commun. 1983 777; (b)S. L. Cook and J. Evans J. Chem. SOC. Chem. Commun. 1983 1287. 33 E. E. Sutton M. L. Niven and J.R. Moss horg. Chim. Acta 1983 70 207. 253 Ru,Os Rh Ir Pd Pt which could be useful in identifying similar species on metal surfaces.34a Heating OS,(CO)~~ with SiHCI3 and CO under pressure results in opening of the Os ring to give the linear-chain compound [C1,SiOs(CO)40s(CO)40s(CO)4SiC13], whose structure can be compared with that of [OS,(CO)~(~-H)3(SiC13)3] which has an 0s triangle edge-bridging hydrides and one SiCI3 equatorially substituted onto each Arenes (e.g. C6H6 C,H,Me C,H&I) react with [OS,(CO)~~(NCM~)~] under reflux to give aryne complexes e.g. [os3(p-H)2(co)9(c6H4)] (1 5).34' The formal similarity between a hydride ligand and Au(PR,) both of which donate one electron to the cluster framework has prompted the syntheses and studies of Os3-AuPR3 complexes including [Os,(CO),(PPh3){Au(PPh3)}(2-NHC,H,N)] [OS (co)9{ Au( PPh3))(C 2 ph)1,34d [O~,(CO)II {Au(PPh3))NCOI [os3(co)lo-{Au(PE~~)INOI,~"' in [OsdCO) in{Au(PEt,)IJ ( 16) and [OsdCO)i 1 {A~(PEt3)}21,~~' all of which the AuPR group bridges two 0s atoms.The reaction of [W(_CR)- (CO),( q5-C5H5)] with [OS~(~-H),(~-CH~)(CO),~] gave the bimetallic or RU~(CO)~~ clusters [MW2(p3-RC2R)(CO),(~5-C5H5)2] (M = 0s or Ru) which exist in two isomeric forms35a (17). The 0s-Pt cluster [OS,P~(~-H)~(CO)~~{ P(cyclo-C,H 1)3)] is the first cluster which reversibly adds both CO and H2 (separately) the products being the closo-[O~~Pt( p2-H)4(C0)In( PR,)] and the butterfly [Os,Pt( p-H)2(C0)11(PR3)], both of which revert to the starting material in a Nz In MeCN solution [OS~H~(CO)~~]- and NOBF4 afford the butterfly cluster cation [Os4H3(CO),2(NCMe)z]BF4,36 but in CH2C12 the major product is [Os,H,(CO),,(NO)] and a minor product is [OS~(/A-H)(CO)~~(/A~-N)] which is con- verted into [0s4(CO),,(p4-N)]- by N02-.lZd A series of papers has described the synthesis of larger clusters by the condensation of smaller clusters incorporating (a)J.Evans and G. S. McNulty J. Chem. Soc. Dalron Trans. 1983 639; (b)A. C. Willis G. N. Van Buuren R. K. Pomeroy and F. W. B. Einstein Inorg. Chem. 1983 22 1162; (c) R. J. Goudsmit B. F. G. Johnson J. Lewis P. R. Raithby and M. J. Rosales J. Chem. SOC.,Dalton Trans. 1983 2257; (d) K. Burgess B. F. G. Johnson J. Lewis and P. R. Raithby J. Chem. SOC.,Dulron Trans.1983 1661 ;(e) 1983 1179; (f)K. Burgess B. F. G. Johnson D. A. Kaner J. Lewis P. R. Raithby and S. N. A. B. Syed-Mustaffa 1. Chem. SOC.,Chem. Commun. 1983 455. 35 (a)L. Busetto M. Green B. Hessner J. A. K. Howard J. C. Jeffery and F. G. A. Stone J. Chem. SOC. Dalton Trans. 1983 519; (b) L. J. Farrugia M. Green D. R. Hankey A. G. Orpen and F. G. A. Stone J. Chem. SOC.,Chem. Commun. 1983 310. 36 B. F. G. Johnson J. Lewis W. J. H. Nelson J. Puga P. R. Raithby and K. H. Whitmire J. Chem. SOC. Dalron Trans.. 1983 1339. 254 W.Levason bridging sulphide (p3-S) or (p4-S) gro~ps.~~~-~ For example pyrolysis of [H0s3(CO),,(p-SPh)] in CO produces the butterfly [OS,(CO),,(~~-S)~] and the square pyramidal [OS,(CO),,(~~-S)].~~~ [Os,(CO),,(p3-S),] can also be produced by photolysis of [Os,(CO),(p3-S),] + OS(CO),,~~' whilst condensation of [OS3(CO)dP3-S)~I and [O~~(CO),O(NCM~),J yield [0s6(c0),7(~4-s)21 and [o~~(co)~~(~4~s)(~3~s)] (18).37" An analogous approach can yield cluster hydrides e.g.[H20s,(CO),,(p4-S)(p3-S)] (19). or larger clusters e.g. [OS~(CO)~,,(~~-S)~] The [os,c(cO),,] takes up CO under pressure to give [os,c(co)]6] the cluster core undergoing a rearrangement from square pyramidal to a bridged butterfly with the carbide at the centre.'3h Reduction of [Os,C(CO),,] affords the dianion [OS,C(CO),,]~- which retains the basic geometry of the parent and this is protonated by concentrated H2S04to [Os,(C)H,(CO) 4,also generated directly from the neutral carbonyl and dihydrogen at 50 atm and 120 "C.A very unusual p3-0x0 group is ~3~~~)(~~)~g] present in the purple [~~~(~3~~)( produced by bubbling oxygen into a refluxing toluene solution of [os6(c0)20]. It has a raft structure (20) and reacts with P(OMe)3 with loss of the 0x0 bridge to give [Os6(CO)2,-,{P(OMe)3},] (n = High nuclearity clusters have also received considerable attenti~n.~~~-~ 37 (a)R. D. Adams Z. Dawoodi D. F. Foust and B. E. Segmuller J. Am. Cbem. Soc. 1983 105 831 ; (b) R. D. Adams 1. T. Horvath 6. E. Segmuller and Li-Wu Yang Organometallics 1983 2 1301 ;(c) R. D. Adams I. T. Horvath P. Mathur B. E. Segmuller and Li-Wu Yang Organometaflics 1983 2 1078; (d) R. D. Adams I. T. Horvath and Li-Wu Yang J. Am. Chem. SOC.,1983 105 1533; (e)R.D. Adams I. T. Horvath P. Mathur and B. E. Segmuller Organometallics 1983 2 996; (f)R. D. Adams D. E. Foust and P. Mathur Organometallics 1983 2 990; (g)R. D. Adams and Li-Wu Yang J. Am. Chem. SOC.,1983 105 235. 38 (a)R. J. Goudsmit B. F. G. Johnson J. Lewis P. R. Raithby and K. H. Whitmire J. Cbern. SOC.,Chem. Commun. 1983 246; (b) B. F. G. Johnson J. Lewis W. J. H. Nelson P. R. Raithby and M. D. Vargas J. Chem. SOC.,Chem. Commun. 1983,608; (c)B. F. G. Johnson J. Lewis M. McPartlin. W. S. H. Nelson P. R. Raithby A. Sironi and M. D. Vargas J. Chem. SOC.,Chem. Commun. 1983 1476; (d) D. Braga J. Lewis B. F. G. Johnson M. McPartlin W. J. H. Nelson and M. D. Vargas,J. Cbern.SOC.,Chem. Commun. 1983,241; (e)D. Braga K. Henrick B. F. G. Johnson J.Lewis M. McPartlin W. J. H. Nelson A. Sironi and M. D. Vargas J. Cbem. SOC.,Cbem. Commun. 1983 1131. RIA,Os Rh Ir Pd Pt The bicapped octahedron [OS,(CO)~~]’-rearranges into [OS,(CO)~~(AUPP~,)~] (21) on reaction with [Au(PPh,)Cl] which could be described as an Os octahedron edge-bridged by two more osmium atoms to produce a pseudo Os butterfly with AuPPh capping the open sides of the The first Os clusters [Os,(CO),,(CHC(R)CH)]-(R = Me or Et) with the core shown in (22) are generated in very poor yield by heating OS~(CO),~ in Bu’OH (R = Me) or 2-methylbutan-1-01 (R = Et),38‘ and [OS,~(CO)~~C]’-, the first Osl, is produced along with smaller clusters by pyrolysis of OS,(CO)~~. Disorder has prevented X-ray identification of the light atom positions but reaction with [Cu(NCMe),]+ gave [Os,IC(C0)27Cu(NCMe)]-,which has the geometry shown in (23) with the carbido atom in a trigonal prismatic cavity.38eThe compound [OS~~H~(CO)~~]~-, the first non-carbido Os, cluster,38d is produced by pyrolysis of [HOs3(CO),,C1] or [OS,(CO),,(OE~)~] suggest-in Bu’OH,and has a similar structure to [OS~~C(CO)~~]~- ing that the hydrides may be interestitial.Os( 1 I) Os( 10) [Os I C(CO)27Cu( NCMe)]- Osmium pentachloride reacts with (NSCl) to form [OSC~~(NSC~)~], which on treatment with [Ph,As]CI is converted into [P~,As][OSC~,(NS)~C~]. The latter has octahedral co-ordination about the Os linear NS groups with the fifth chlorine atom 256 W. Leuason associated with the sulphur possibly di~ordered.~~" Treatment with GaCl gives the neutral thionitrosyl compound.The [Ph,PMe][Os( NO)C14] complex contains a square pyramidal anion with a linear nitrosyl A series of di- and tri-thiocarbamate complexes of osmium( 111) have been character- i~ed,~' and the structure of the dithioselenocarbamate complex [0s2(p-SeS2CNMe2)z(SzCNMe2)3]PF6 has been established (24) by an X-ray study. (24) Preliminary data on the osmium 'Creutz-Taube'-type complex [(NH,),O~(pyrazine)Os(NH~),)~+ have been given. The red crystalline OS"-OS''~ complex is produced by Ru" or electrochemical reduction of the OS~~~-OS"' analogue and further reduction to Os"-Os" is possible with Zn/Hg. The mixed valence material is electronically delocalized on the basis of its electronic spe~trum.~' Treatment of trans-[OsO,X,(PR,),] (below see re$ 44) with carboxylic acids under reflux gave the 0stv complexes [OS~(~-O)(~-O,CR)~X,(PR~')~] (R = Me or Et; R3' = Ph3 or Et,Ph; X = C1 or Br).,," An X-ray study of [Os,(p-0)-(p-02CMe),C1,(PPh3),] revealed the sole established example in a diosmium com- plex of a single bent oxygen bridge.An acetate-bridged 0s"' complex with an Os=Os bond [OS~(~-O~CM~)~C~~] is produced from OSCI,~- MeCO,H and (Me2C0)20.42h Exchange with EtC02H or Pr"C02H gives the corresponding [Os2(p-02CR)4C12] (R = Et or Pr") compounds. Various reactions of the acetate-bridged dimer are shown in Figure 1. The [OsvCl,]- anion originally made from OsCl itself has now been prepared more conveniently by chlorination of [NEt,][Os(CO),X,] and its electronic and resonance Raman spectra reported.43 Osmium is often determined colorimetrically using thiourea and an investigation4" of the reaction of OsO with N,N'-diethyl- imidazolidine-2-thione (L) in H20-HC104 has shown that [Osv'02L4](C104)2 and [OS'~L,C~~](C~O~)~ are intermediates in the reduction ; in the latter complex which was shown to have a trans geometry (S4C12 donors) by an X-ray study the chloride ions presumably arise from reduction of the Ci04-.Further details of the osmium(v1) 39 (a) R. Weber U. Muller and K. Dehnicke 2. Anorg. Allg. Chem. 1983 504 13; (b)B. Czeska K. Dehnicke and D. Fenske 2. Naturforsch. Teil B 1983 38 1031. 40 L. J. Maheu G. L. Miessler J. Berry M. Baraw and L. H. Pignolet Inorg.Chem. 1983 22 405. 4' R. H. Magnuson P. A. Lay and H. Taube J. Am. Chem. Soc. 1983 105 2507. 42 (a)J. E. Armstrong W. R. Robinson and R. A. Walton Inorg. Chem. 1983 22 1301 ;(b)T. Behling G. Wilkinson T. A. Stephenson D. A. Tocher M. D. Walkinshaw J. Chern. SOC.,Dalfon Trans. 1983,2109. 43 W. Preetz and M. Bruns 2. Naturforsch. Teil B 1983 38 680. 44 (a)L. Antolini F. Cristiani F. A. Devillanova A. Diaz and G. Verani J. Chern. SOC. Dalton Trans. 1983 1261; (b)J. E. Armstrong and R. A. Walton Inorg. Chem. 1983 22 1545; (c)G.V. Goeden and B. L. Haymore Inorg. Chim. Acta 1983 71 239. Ru Os Rh Ir Pd Pt tr~ns-Os"Cl~(dppe)~ + 2+ os'Vx,2-t OS"'~(O~CR),C~ y//\y (viii) (vii) trans- 0s'~(acac),C1~ trans-O~"(O~CMe)~(Bu'NC)4 trans- Os"( S,C NMe2)2C12 Os'1'(02CMe)2C1(Bu'NC)3 [OS"(N-NN),]~+ Figure 1 Some reactions of Os2(O2CMe),Cl2 (i) HCl HBr (aq); (ii) RC02H; (iii) 2-hydroxy-pyridine ; (iv) 2,2,2-tr~uoroacerumide Vrom butyrute) ; (v) acetylacetone; (vi) Na[S2CNMe,]; (vii) N-N = 2,2'-bipyridyZor 1,lO-phenanthroline; (viii) Bu'NC; (ix) Na + Bu'NC; (x) PMe,; (xi) Ph2P[CH2I2PPh2 complexes truns-[0~O~(PR,)~X~] = Ph3 MePh2 EtPh, or Et2Ph; X = C1 or (R Br) have been These osmyl complexes are diamagnetic light sensitive readily reduced to trans-[OsX,(PR,),] and rner-[OsX3(PR,),] and can be used as starting materials for the preparation of mixed ligand Os'" Os"' or 0s" complexes.3 Rhodium There have been reviews of catalysis by metal cluster compounds,' and of the enantioselective hydrosilation of olefins by rhodium complexes.45 The synthesis properties and structures of rhodium( 11) carb~xylates,~~ and the platinum metal chemistry of Ph2PCH2PPh2 (mostly Rh Pd and have been critically discussed.The [Rh(porphyrin)(CO)Cl] (porphyrin = octaethyl- or tetraphenyl-porphyrin'-) complexes react with CO and KOH to give the formyls [Rh(porphyrin)(CHO)] + C02.48 Interest in rhodium carbonyl clusters continues to grow and considerable progress in the synthesis of heterometallic clusters has been achieved. An approach to electron counting and structure prediction in high nuclearity Rh and pt carbonyls 45 H. Brunner Angew. Chem. In?. Ed. Engl. 1983 22 897. 46 E. B. Boyar and S. D. Robinson Coord. Chem. Rev. 1983 50 109. 47 R.J. Puddephatt Chem. SOC.Rev. 1983 12 99. 48 B. B. Wayland A. Duttaahmed and B. A. Woods J. Chem. SOC.,Chem. Commun. 1983 142. 258 W.Levason using extended Hume-Rothery rules has been de~cribed.~'" The effects of cation CO pressure and temperature upon the thermal synthesis of rhodium clusters has been examined.49b Direct observation of Io3Rh n.m.r. spectra has recently become possible and this technique has been applied to establish the stereochemistries of [Rh4(CO),2-,{P(OPh)3},] (X = l-~).~~' X-Ray structures of the nitrido cluster [N(PPh,),][Rh,N(CO) 5] and of the carbido [N(PPh3),][Rh,,C,(CO)24] have been The former contains a trigonal prism of rhodium atoms with a central nitrogen atom one terminal CO per Rh and none edge-bridging CO's.The carbido cluster prepared from [Rh,C(C0)15]2- and H2S0 in propan-2-01 has the structure shown in (25a); interestingly it is not isostructural with the isoelectronic [RhI2C2(CO),,]. The new [Rhl l(CO)23]3- anion prepared49f by FeCI oxida?ion of [Rh,(co)l,]3- consists of three condensed octahedral units each sharing a triangular face with both of the adjacent octahedra. Variable-temperature multinuclear (13C 13C{103Rh}, 13C{3'P},31P)n.m.r. studies of [Rh9E(C0)21]2- [Rh,,E(C0),,I3- (E = P or As) and [Rh,2Sb(CO)2,]3- show that at high temperatures both the metal poly- hedra and the carbonyl groups are fluxional; whereas at lower temperatures the Rh and Rhln give spectra consistent with the solid structures although the Rhlz complex is fluxional even at -97 eC.49g Bimetallic Rh-Fe clusters [Fe,Rh(CO),]- 4Y (a)B.K. Teo J. Chem. SOC. Chem. Commun. 1983 1362; (b)J. L. Vidal and R. C. Schoening J. Orgunomeral. Chem. 1983 241 395; (c) B. T. Heaton L. Strona R. D. Pergola L. Garlaschelli U. Sartorelli and I. H. Sadler J. Chem. SOC.,Dalton Truns. 1983 173; (d)R. Bonfichi G. Ciani A. Sironi and S. Martinengo J. Chem. SOC.,Dulfon Trans. 1983 253; (e)V. G. Albano D. Braga P. Chini D. Strumolo and S. Martinengo J. Chem. SOC.,Dalton Trans. 1983 249; (f)A. Fumagalli S. Martinengo G. Ciani and A. Sironi J. Chem. Soc. Chem. Commun. 1983 453; (g)B. T. Heaton L. Strona R. D. Pergolla J. L. Vidal and R. C. Schoening J. Chem. SOC. Dalton Trans. 1983 1941. 259 iiu 29 Rh Ir Pd Pt [FeRk4(C0)15]2- [Fe2Rh,(C0)16]2- (2 isomers) and [FeRh5(CO)16]- have been prepared by reaction of various iron carbonyl anions with [Rh,(CO),,] [Rh(CO),CI], or RhC13.50U The trigonal prismatic cluster [Rh,C(CO)I,]2- adds M(PEt,)+ to give (PEt,)M[Rh,C(CO),,]-(M = Ag or Au) whilst AgBF in acetone gives a series of compounds [Ag,,{Rh6C(CO),5}2]'4-"-(n (n = 1 or 3) [Ag,{Rh,C(C0),5},]'6-'1'-= 2 or 4) in which the Ag atoms cap trigonal faces of the Rh units."' Controlled pyrolysis of [PtRh,(CO),,]- gives [Pt2Rh l(CO)24]3- and [PtRh,2(C0)24]4- the latter containing a 'twinned' cubo-octahedron of Rh atoms with a central Pt the former being similar with the second Pt disordered on the surface.soc The reaction of [Rh(CO),CI] with PPh2H in benzene (1 :4 ratio) gives [Rh(CO)CI(PPh,H),] and in 1 :2 ratio [Rh,(p-PPh,),(p-CI),(p-CO)(CO)3].5'" The latter contains a triangular Rh unit and is readily converted into [Rh3(p-PPh,),(CO),] by NEt2H and CO.When [{Rh( q3-C3H5),Cl},] and [Fe(CO),PPh,H] react in ROH in the presence of CO the product is [RhzFe2(p-PPh2)4(p-CO)2(C0)6] which unusually contains a linear Fe-Rh-Rh-Fe skeleton with single PPh and CO groups bridging the Fe-Rh bonds and two -PPh2 bridging the Rh-Rh When LiPBu' and [Rh(CO),CI] react in THF the product is trimeric [Rh(p- PBu',)CO] which contains a Rh triangular unit with edge-bridging phos- phido groups.51c The [Rh(CO),Cl] has also been encapsulated into a cryptand to give the novel dinuclear complex (25b).51" Phosphido-bridged dimers [M(COD)(p- PPh,)] have been prepared from [M(COD)Cl] (M = Rh or Ir; COD = cyclo-octadiene) and LiPR, and these react with diphosphines (L-L) with stepwise displacement of COD to give [(L-L)Rh(p- PPh,),Rh(COD)] and then [Rh(p-PPh2)(L-L)],.s2" An X-ray study of [Rh(p- PPh2)(Ph2PCH2CH2PPh2)] revealed that the Rh..-Rh separation was 3.47 A too long for a Rh-Rh bond despite the 16e configuration of the rhodium atoms.52h Monodentate phosphines convert [Rh(p-PPh,)(COD)] only into [(PR,),Rh'(p- PPh,)2Rh(COD)] which contain an approximate planar geometry about one Rh (a)A.Ceriotti G. Longoni R. D. Pergolla B. T. Heaton and D. 0. Smith J. Chem. Soc. Dalton Trans. 1983 1433; (b)B. T. Heaton L. Strona S. Martinengo D. Strumolo V. G. Albano and D. Braga J. Chem. SOC.,Dalton Trans. 1983 2175; (c)A.Fumagalli S. Martinengo and G. Ciani J. Chem. SOC. Chem. Commun. 1983 1381. 5' (a)R. J. Haines N. D. C. T. Steen and R. B. English J. Chem. SOC.,Dalron Trans. 1983 2229; (b)R. J. Haines N. D. C. T. Steen and R. B. English J. Chem. Soc. Dalton Trans. 1983 1607; (c)J. L. Atwood W. E. Hunter R. A. Jones and T. C. Wright Inorg. Chem. 1983 22 999; (d)J. P. Lecomte J. M. Lehn D. Parker J. Guilhem and C. Pascard J. Chem. SOC.,Chem. Commun. 1983 296. 260 W.Levason but a distorted tetrahedral one about the other (Rh').52' With dilithium phosphides different products are produced; e.g. [Rh(COD)Cl] and Li2PPh give the phos- phinidene cluster [Rh4(p4- PPh)2(COD)4],52d whilst the bulkier (PBu')~- in the pres- ence of PMe gives [Rh2(p2-PButH),(PMe3),] which contains a Rh=Rh bond the 'extra' hydrogen presumably coming from the solvent (THF).52' Bimetallic materials include [(q5-C5H5)RhFe2Te2(CO)7] produced from Fe,Te2(C0)9 and [(q5-C5H,)Rh(CO),],"" and the unsaturated [CoRh(p-C0)2(C5Me5)2] obtained from [(q5-C5Me5)Rh(C0),] and [CO(C,H~)~(C,M~,)]."~ Irradiation of [Cr(C0),(q6-arene)] and [(q5-C5Me5)Rh(CO),] give [CrRh(p- C0)2(C0)2( q5-CsMe,) (q6-arene)] whereas irradiation of the Rh compound with [Cr(CO),(THF)] [Mo(CO),(MeCN)] or [W(CO),(THF)] give for M = Cr Mo or W [MRh2(p-CO)2(CO),(q5-C,Me5)2].53cAn unusual reaction of [(q5-C,Me,)Rh(CO)] with the phospha-alkyne PzCBu' produced the compound (26).53d The reaction of [RhH(L-L),] compounds with CO produced the active catalysts [{Rh(CO)(L-L)}2(p-CO)2] (L-L = Ph2PCH2CH2PPh2 Two or Ph2P(CH2)3PPh2).53e interconvertable forms of [Rh(RNC),Cl] have been prepared from RNC (R = 2,6-dimethyl-4-bromophenyl) and [Rh(COD)Cl], a purple crystalline material con- taining discrete dimers with Rh-Rh interaction and brown-yellow form with 'isolated' metal centres.54 Numerous small molecules add to planar Rh' complexes; among the interesting examples reported this year is [Rh(o-C6H4(AsMe2),),(q1-CO2)C1] one of the few X-ray established examples of q ' -carbon dioxide binding.55" The yellow-phos- phorus adduct [Rh(P4)(PPh,),C1].2CH2Cl2 was reported some years ago but has now been characterized by an X-ray study which shows a trigonal bipyramidal Rh environment with q2-P4 ~o-ordination.~~~ In [{ MeC(CH2PPh2)3}Rh(P3S3)].C6H6 produced from P4S3 and [Rh(COD)Cl], the phosphorus sulphide fragment co-ordinates in an 77 manner (P,S).55' 52 (a)P.E. Kreter and D. W. Meek Inorg. Chem. 1983 22 319; (b)w.C. Fulz A. L. Rheingold P. E. Kreter and D. W. Meek Inorg. Chem. 1983 22 860; (c) R. A. Jones N. C. Norman M. H. Seeberger J. L. Atwood and W. E. Hunter Organometallics 1983 2 1629; (d) E. W. Burkhardt W. C. Mercer G. L. Geoffroy A. L. Rheingold and W. C. Fulz J. Chem. SOC. Chem. Commun. 1983 1251. 53 (a) D. A. Lesch and T. B. Rauchfuss Inorg. Chem. 1983 22 1854; (b) M. Green D. R. Hankey J. A. K. Howard P. Louca and F. G. A. Stone J. Chem. SOC.,Chem. Commun. 1983 757; (c)R. D. Barr M. Green K. Marsden F. G. A. Stone and P. Woodward J. Chem. SOC. Dalton Trans.1983 507; (d)G. Becker W. A. Hernann W. Kalcher G. W. Kreichbaum. C. Pahl C. T. Wagner and M. L. Zeigler Angew. Chem. Int. Ed. Engl. 1983,32,413; (e)B. R. James D. Mahajan S. J. Rettig and G. M. Williams Organometallics 1983 2 1452. 54 Y. Yamamoto Y. Wakatsuki and H. Yamazaki Organometallics 1983 2 1604. '' (a)J. L. Calabrese T. Herskovitz and J. B. Kinney J. Am. Chem. Soc. 1983 105 5914; (b) W. E. Lindsell K. J. McCullough and A. J. Welch J. Am. Chem. SOC. 1983 105 4487; (c) M. DiVaira M. Peruzzini and P. Stoppioni J. Chem. SOC.,Chem. Commun. 1983 903. Ru,Os Rh Ir Pd Pt 26 1 The monoquaternized amine-phosphine Ph2PCH2CH2N+Me3N03- (L+N03-) forms water soluble Rh’ complexes [(NBD)RhClL](NO,) and [(NBD)RhL2I3’ (NBD = norbornadiene) which readily take up dihydrogen and are active olefin hydrogenation catalysts in aqueous solution.56 Several groups have studied bidentate ligands whose steric properties favour the bridging of two-metal centres.The unsymmetrical Ph2PCH2AsPh2 reacts with [Rh(CO),Cl] to give the ‘head to tail’ dimer [Rh2(p-P~,PCH,ASP~~)~(CO)~C~~] and with [Rh(CO),Cl,]- to give [Rh,(p-P~,PCH,ASP~~)~(~-CO)(~-C~)(CO)~] which easily loses CO to form the A-frame [Rh,(p-Ph2PCH2AsPh2)2(p-C1)(C0)2].57a The tridentate PhP(CH2PPh2) forms the trirhodium complex (27),”’ whilst 2,5-bis(diphenylphosphino)furan and 2-{bis(diphenylphosphino)methyl}pyridine bridge two rhodium centres without Rh-Rh Heterobimetallic Rh-Pd(Pt) complexes are discussed below (Pd Pt Section). Mononuclear Rh” compounds are rare and usually very unstable.Examples obtained in solution using electrochemical or pulse radiolysis techniques include [Rh(bi~y)~],+ [Rh(bipy),( H20)2]2+,58a and complexes of several macrobicyclic amine~.~” Electronic spectra were recorded and the disproportionation and oxida- tion studied. The oxygenation of solutions of [Rh{P(cyclo-C,H 1)3}2C1] produces a paramagnetic material suggested to be a Rh“superoxide complex on the basis of e.p.r. spectral studies.58‘ Rhodium(I1) carboxylate dimers are well known and a detailed study of their electronic spectra has been published the main band being attributed to a cr +cr* transition of the Rh-Rh unit.58d The i.r. spectrum of [Rh2(02CCF3)4(C0)2] exhibits v(C0) at -7 cm-’ higher than that observed in free carbon monoxide.56 R. T. Smith R. K. Ungar L. J. Sanderson and M. C Baird Organomefalfics,1983 2 1138. 57 (a) P. D. Enlow and C. Woods Organometallics 1983 2 64; (6) M. M. Olrnstead R. R. Guimerans and A. L. Balch Inorg. Chem.. 1983 22 2474 (c)M. P. Anderson C. C. Tso B. M. Mattson and L. H. Pignolet Znorg. Chem. 1983,22,3267;(d)J. M. Brown and L. R. Canning J. Chem. SOC. Chem. Commun. 1983 460. 58 (a) H. A. Schwarz and C. Creutz Inorg. Chem. 1983 22 707; (b)J. MacB. Harrowfield A. J. Herlt P. A. Lay A. M. Sargeson A. M. Bond W. Mulac and J. C. Sullivan J. Am. Chem. SOC.,1983 105 5503; (c) G. Valentini G. Braca G. Sbrana and A. Colligiani Inorg. Chim. Acta 1983 69 215; (d)T. Sova T. Kawamura T.Shida and T. Yonezawa Inorg. Chem. 1983 22 56. 262 W. Leuason Rhodium-103 n.m.r. spectroscopy has been used to identify all ten possible chlorobromorhodates(rII1) [RhC16- Br,,I3- including isomers) in solution.59" The first X-ray structural characterization of [Rh(H20)6J3+ and [IT(H~O)~]~+ has been reported59b in the a-alums CsM(S0J2.12Hz0 (M = Rh or Ir). Both 0-and N-bonded isomers of [Rh(NH3)s{(H2N)2CO}]3+ have been isolated and their intercon- version and hydrolysis as a function of pH ~tudied.'~' In acidic solution the 0-bonded form hydrolyses to [Rh(NH3)s(HzO)]3' and the N-bonded to [Rh(NH3)J3+. The series of o-methoxyphenylstibine complexes with L = (0-MeOC,H,),-, SbPh,, viz. [RhL,Cl,] [IrL,CI,] [PdL,Cl,] and [PtL,Cl,] contain the ligands bonded via antimony only but L = o-MeOC,H,SbMe gave [RhLr3C13](Sb3C13)or [RhL~C13](Sbz0Cl donor set) depending upon the condi- tion~.~~~ The syntheses and structures of two interesting rhodocarboranes have been reported [Rh(PPh3)(C2B9H and [HPPh,][3-PPh,-3,3-Br2-3,l ,2-RhC2B9H ,I the former containing two icosahedral fragments linked symmetrically at three vertices and the latter containing an octahedrally co-ordinated rhodium bonded to two bromines the phosphine and three vertices of the carborane.60n,h The [RhH,(O,COH)( PPr'3)2] reduces PhCECPh to trans-stilbene and is converted into the novel carbonato-bridged dimer (28) [Rh2H2(OzCO)( PhCECPh)( PPri3)3].61a A particularly interesting complex6" is the 14-electron species (29) produced from NaN(SiMe,) or KH and [CIR~H(P(BU')~CH~C~H~CH~PBU'~>~.The complex (29) forms adducts with HZ CO etc. and metallates benzene pentane octane or internally metallates one of the But groups on the phosphine. Pentamethylcyclopentadienylrhodium complexes have been much studied in recent years. The [Rh(~5-C5Me5)C12] can be reduced with Na/Hg in the presence of tertiary phosphines to [Rh(q5-C5Mes)(PR3),] which will oxidatively add many substrates to give [Rh(q5-C5Me5)(PR3)2X]+Y-(e.g. X = H Me MeCO or I; Y = 59 (a) B. E. Mann and C. M. Spencer Inorg. Chim. Acta Lett. 1983 76 L65; (6) R. S. Armstrong J. K. Beattie S. P. Best B. W. Skelton and A. H. White 1. Chem. Soc. Dalton Trans. 1983 1973; (c) N. J. Curtis N. E. Dixon and A. M. Sargeson J.Am. Chem. SOC. 1983 105 5347; (d)S. J. Higgins W. Levason F. P. McCullough and B. Sheikh Inorg. Chim. Acta 1983 71 87. 60 (a)P. E. Behnken C. B. Knobler and M. F. Hawthorne Angew. Chem. Int. Ed. Engl. 1983 22 722; (b) L. Zheng R. T. Baker C. B. Knobler J. A. Walker and M. F. Hawthorne Inorg. Chem. 1983,22,3350. 6' (a)T. Yoshida W. J. Youngs T. Sakaeda T. Ueda S. Otsuka and J. A. Ibers J. Am. Chem. SOC.,1983 105,6273;(b)S. Nemeh C. Jensen E. Binamira-Soriaga and W. C. Kaska Organometallics 1983,2 1442. 263 Ru,Os Rh Ir Pd Pt PF6-).62U The formally Rh'" complex truns-[Rh,( q5-CSMe5),(p-CH2),Me2] reacts stepwise with 1 or Br (X,)to give first of all [Rh2(qS-C5Me5),(p-CH2),X2]with elimination of MeX and then [a2( with production of CH4 q5-C5Me5)2(p-X)2X2] C2H4 and C3&; the coupling of C1 fragments to C2 and C3 is notable in connection with Fischer-Tropsch reactions.62b Reaction of [Rh,( qS-C5Mes),(p-C1),Cl2] with (LiMe) or Al,Me and air oxidation gives both cis-and truns-[Rh2(qS-C5Me,),(p-CH2)2Me2];cis +trans isomerization can be achieved by treatment with A12Me6.62C 4 Iridium The reaction between [IrC1(C0),(MeC6H4NH2-p)] CO zinc and HC(PPh2)3 gave [Ir,(CO),HC(PPh,),] and a complex [1r3(CO),(Ph)(p3- PPh)(p2- Ph2PCH2PPh2)] which results from fragmentation of the tridentate pho~phine.~~" The latter contains an Ir3 triangle capped by PhP one edge-bridging Ph2PCH2PPh2 and the Ph bonded to the third iridium.Phosphido-bridged [Ir(COD)(p- PPh,)] is produced from [Ir(COD)Cl] and LiPPh2,s2n whilst truns-[Ir(CO)(PPh,),Cll and Li[Fe(CO)1PPh2] give [IrFe(p-PPh,)(CO),(PPh,),l (x = 4-6).63b An X-ray structure determination of the complex with x = 5 showed it to be [(PPh,)(CO)3Fe(p-PPh,)Ir(CO)2(PPh3)] with a long Fe-Ir bond (2.96 A) which breaks on reaction with H, with addition adds P4S3 of two hydride ligands to the iridium tr~ns-[Ir(CO)(PPh~)~Cl] to give the green crystalline dimer [{Ir(CO)C1(PPh3)},(p-P4S3),]63'in which the P4S3 units bridge the metal centres each iridium being bound to two bridging and one terminal phosphorus of the P4S3 molecules.Phosphorus trichloride and rrans-[Ir(CO)(PEt,),Cl] produce [Ir(CO)Cl,( PEt3),PC12] which can be chlorine-oxidized to the unusual [Ir(CO)Cl,( PEt3)2PC14] complex formally PV.63d The trans chelating ligand 2,ll -bis(diphenylphosphinomethyl)benzo[clphenanthrene complex [Ir(CO)LCl] gives a mixture of products upon chlorine oxidation but the Ir"' analogue [Ir(CO)LCl,] is obtained cleanly using CuCI,.Both have been studied by X-ray diffraction and the structural differences compared.63e With 2-bis(dipheny1phosphino)methylpyridine C5H4N[CH(PPh2),] (PNP) the dimeric [Ir,(p-CO)(CO),(PNP)2](BF4)2 is formed. The structure of this and the rhodium complex [Rh2(C0),(PNP),](PF6) are compared in (30a) and (30b).'" The 62 (a)B. Klingert and H. Werner Chem. Ber. 1983 116 1450; (b)A. Nutton A. V. de Miguel K. Isobe and P. M. Maitlis J. Chem. SOC.,Chem. Commun. 1983 166; (c) K. Isobe A. V. de Miguel P. M. Bailey S. Okeya and P. M. Maitlis J. Chem. SOC.,Dalton Trans.1983 1441. 63 (a)M. M. Harding B. S. Nichols and A. K. Smith J. Chem. SOC.,Dalton Trans. 1983 1479; (b)D. A. Roberts G. R. Steinmetz M. J. Breen P. M. Shulman E. D. Morrison M. R. Duttara C. W. De Brosee R. R. Whittle and G. L. Geoffroy Organornetallics 1983 2 846; (c)A. Ghilardi S. Midollini and A. Orlandini Angew. Chem. Int. Ed. EngL Suppl. 1983 22 554; (d) E. A. V. Ebsworth N. T. McManus N. J. Pilkington and D. W. Rankin J. Chem. Soc. Chem. Commun. 1983 484; (e) E. Baumgartner F. J. S. Reed L. M. Venanzi F. Bachechi P. Mura and L. Zambonelli Helv. Chim. Acta 1983 66 2572. 264 W.Levason [Ir(d~pe)~E,]+ (dppe = Ph2PCH2CH2PPh2 E = S or Se) can be alkylated by CF3S03Me to give [Ir(d~pe)~(~~-E~Me)]+ compounds which for E = S are potent S atom and Me$+ transfer reagents e.g.with PPh both Ph3PS and Ph,PSMe+ are Conversely64b oxidation with 3-C1C6H4C0,H of [Ir(dppe),S,]+ forms [Ir(dppe),S,O]+ which alkylates at 0 on treatment with MeS03F and subsequent treatment with MeNC gives the sulphenate ester [Ir(dppe),(CNMe)(SOMe)]’+. Selenium adds to Ir(Me,PCH2CH2PMe2)2C1 to give [Ir(Me2PCH,CH2PMe2),- (Se4)]C1 which contains an Se4’-ligand which has a ‘half-chair’ conformation. Reaction of this complex with PPh3 extracts selenium to give the [Ir(Me2PCH2CH2PMe2),(Se2)]C1complex.64c Two interesting iridium nitrosyls have been reported; the [Ir(PPh,),Cl(p- L)(p-No)c~cl](PF,)~ L = 3,6-bis(2’-pyridyl)pyridazene contains the first example of a nitrosyl group bridging two different metals.65“ Treatment of [Ir(NO)(MeCN)3(PPh,)2]2+ with 9,lO-phenan- threnequinone-di-imine (H,L) gives the expected [Ir(NO)(H,L)(PPh,),]’+ complex which in the presence of a weak base (NaHCO,) unexpectedly rearranges into the phosphazene-imido complex (3 1) by transfer of a PPh from iridium to nitrogen.65b (31) A unique Ir-Cu cluster [{(MeC(CH2PPh,),)IrP3}3Cu5Br4]CuBr2 has been isolated from the reaction of [Ir(triphos)P,]’ and CUB^.^'" It consists of a central Cu trigonal bipyramid the lower edges of which are bridged by bromine whilst each upper triangular face is capped by an [Ir(triphos)P,]+ unit.Three tris(2,2’-bipyridyl)iridium(111)complexes are known; one (yellow) is the expected IrN6,+ and a combined X-ray and I3C n.m.r. study has shown the orange form to be [Ir(bipy),(C-N-bipy)I2+ with one 2,2’-bipyridyl ligand co-ordinated via one nitrogen atom and a metallated carbon.The third form obtained from the orange one in acid solution is [Ir(bipy)2(C-N-bipy)(H30)]3+.66a Several macro-cyclic amine complexes of Ir”’ of types cis-[IrLX,]+ (L = 1,4,8,1I-tetra-azacyclotetradecane;X = Cl, Br2 or BrCI) truns-[IrL’X,]+ (L’ = L or 1,4,8,12-tetra-azacyclopentadecane,c-meso or c-ruc-5,5,7,12,12,14- hexamethyl- 1,4,8,11-tetra-azacyclotetradecane,X = C1 or Br) have been prepared from the tetramines and IrX6’- in Extensive studies on secondary phosphite complexes of iridium(rr1) have been reported.66c Treatment of [{IrCl(COD)},] with 64 (a) J. E. Hoots and T. B. Rauchfuss Inorg. Chem. 1983 22 2806; (b)J. E. Hoots T.B. Rauchfuss and S. R. Wilson J. Chem. Soc. Chem. Commun. 1983 1226; (c)A. P. Ginsberg J. H. Osborne and C. R. Sprinkle Inorg. Chem. 1983 22 1781. 6.5 (a)A. Tiripicchio A. M. M. Lanfredi M. Ghedini and F. Neve J. Chem. SOC.,Chem. Commun. 1983 97; (b)P. Dapporto G. Denti G. Dolcetti and M. Ghedini 1. Chem. Soc. Dalton Trans. 1983 779; (c)F. Cecconi C. A. Ghilardi S. Midollini and A. Orlandini Angew. Chem. Int. Ed. Eng!. 1983,22,554. 66 (a) G. Nord A. C. Hazell R. G. Hazell and 0. Farver Inorg. Chem. 1983 22 3429; (b)C. W. Poon T. W. Tang and C. M. Che J. Chem. SOC.,Dalton Trans. 1983 1647; (c)J. A. S. Duncan T. A. Stephenson W. B. Beaulieu and D. M. Roundhill J. Chem. Soc. Dalton Trans. 1983 1755. Ru Os Rh Ir Pd Pt PPh2Cl and water gives [IrHCl(COD){ (PPh,O),H}] from which bidentate ligands L-L (Ph2PCH2CH2PPh2 Ph2AsCH2CH2AsPh2 or PhSCH2CH2SPh) displace the diene to give [IrHCl(L- L){(PPh,O),H}].Fluoroboric acid protonates the diphenylphosphinous acid to give [IrHCl(L-L){PPh,(OH)},]BF, which loses HF to give =BF capped materials also prepared directly from BF3-[IrHCl(L- L)-{(PPh,O),BF,}]. Bimetallic compounds can be obtained by substitution of the phosphinous acid proton by a second metal ion. The synthesis and structures of alkali-metal salts of [IrC16]3- [IrCl,( H20)l2- [~r~r,]~- [1r2c1913- [1rc1,12- [~r~r,]'- and some related hydrates have been re-e~amined.~'".~ Although exchange of BC13 and OsF resulted in the recent discovery of OsCl, attempts to prepare higher halides of iridium from IrF and BCI3 BBr, B13 or CC14 gave only mixed halides such as Ir2F3C16 or Ir2Br4F5.67C The reaction of [IrCl(PPh,),] with arachno-[CB8H 13]-gives several products one of which contains a closo structure [1-PPh3-2 H-2,2-(PPh3)2-2 lO-IrCB8Hg] and the likely route of rearrangement has been discussed.68" trans-[Ir(C0)C1(PPh3),1 and c~~s~-B,,H,,~-in methanol gave the formally Ir"' complex [(MeCO-O)(PPh,)-{ HIrCB,H,(PPh,)}] whose structure can be compared with that of the 'isoelectronic' iso-nidp IrV ,complex (32).The mixed-metal complex [(Me,P),Pt(PPh,)-(Ph2PC,H,)HIrB9Hlo] has also been characterized.68' (Pentamethylcyclopentadieny1)iridium complexes in oxidation states +1-+5 have been reported. For example [(q5-C,Me,)Ir(CO)2] in freon solution under irridation will activate methane giving [(q5-C,Me5)Ir(CO)H(Me)].69"The iridium(rr1) complex [( q5-C5Me5)IrMe2(Me,SO)] will metallate aryl halides and related complexes form- ing [( q5-C,Me5)IrMe(m,p-C6H,X)(Me2SO)] probably via an IrV intermediate the rate of reaction depending upon X in the order I > NO2 > CF3 > BrI> H > OMe > C1 > F.69b An IrV hydride has been isolated and characterized by a single crystal X-ray study at -150 "C; [IrH4(q5-C5Me5)] is formed as colourless crystals on treatment of [(~5-C5Me5)21r2C12(p-Cl)2] with H2 and PF6- and subsequent reaction of the [(q5-C5Me5)Ir(p-H)31r(q5-C5Me5)]PF6 produced with Li[BHEt3].69C Iridium(v) is also formally present in the silyl [(q5-C5Me5)IrH2(SiEt3)C1] produced from [(q5-C,Me5)21r2C12(p-C1)2]and Et3SiH.69d Finally the reaction of benzene 67 (a)J.E. Fergusson and D. A. Rankin Aust. J. Chem. 1983 36 863; (b) D. A. Rankin B. R. Penfold and J. E. Fergusson ibid. 1983 36 871 ;(c) R. C. Burns and T. A. O'Donnell J. Fluorine Chem. 1983 23 I. (a)N. W. Alcock J. G. Taylor and M. G. H. Wallbridge J. Chem. SOC.,Chem. Commun. 1983 1168; (b) J. E. Crook,N. N. Greenwood J. D. Kennedy and W. S. McDonald ibid. 1983 83; (c)J. Bould J. E. Cook,N. N. Greenwood and J. D. Kennedy ibid. 1983 949. 69 (a)J. K. Hoyans A. D. McMaster and W. A. G. Graham J. Am. Chem. SOC. 1983 105 7190; (b)M. Gomez D. J. Robinson and P. M. Maitlis J. Chem. SOC.,Chem. Cornmun. 1983 825; (c)T. M. Gilbert and R.G. Bergman Organometallics 1983,2 1488; (d)M. J. Fernandez and P. M. Maitlis Organometallics 1983 2 164 (e) D. J. Fisher and R. Eisenberg Organomernllics 1983 2 764. 266 W.Levason and carbon monoxide on photolysis in the presence of [IrH,(CO)- (Ph2PCH2CH2PPh2)]produces PhCH0.69' 5 Palladium and Platinum A review of the co-ordination chemistry of Ph2PCHzPPh2 contains descriptions of much Pd and Pt chemistry.47 The physics and chemistry of partially oxidized tetracyanoplatinates have been re~iewed,~' and a short article describes the selective oxidation of olefins catalysed by palladi~m.~' An unusual Pt7 cluster [Pt,(RNC),,] (R = 2,6-Me2C6H3) has been prepared by sodium amalgam reduction of [PtC12(RNC)2].72u Its structure can be described as a Pt trigonal bipyramid with two edge-bridging platinum atoms.The reaction of Pd(02CMe), Ph2PCH2PPh2 CO and CF,C02H produces the [Pd,(p3-CO)-(p2-Ph2PCH2PPh2),I2+ which contains a Pd triangular unit with a capping carbonyl and edge-bridging dipho~phines.~~' PEt3)4] cluster A [Pd4Hg2Br2(C0)4( produced from the reaction of [Pd,(CO),(PEt,),] with 8(a-bromomercury-ethyl)quinoline contains a butterfly Pd4(p2-C0)4(PEt3)4 unit capped by HgBr.72' In contrast the [Pd2M2(q5-C,H,)2(p3-C0)2(p-C0)4(PEt3)2] (M = Cr Mo or W) compounds have coplanar Pd2M2 units and a Pd-Pd bond.72d The reduction of [Pt(CO)X,]-with HC02H and Pr",N in THF gives [Pt2X4(CO)2]2- complexes which have been characterized by 13C and 195Pt n.m.r. studies. Exchange reactions in these compounds to produce mixed-halide complexes have also been e~arnined.~," On reaction with PPh the complex X = Br gives [Pt,Br,(p-CO)(PPh,),] an X-ray study of which showed structure (33) with an unsymmetrical carbonyl bridge.73b A 0 cp '\ / P-Pt-Pt-Br variety of syntheses for [ClPd( p-Ph2PCH2PPh2)2PdC1] includes reduction of [PdC12(Ph2PCH2PPh2)] with Zn dust HC02H or N2H4 reaction of [Pd,C12(q3-allyl),] with the diphosphine or comproportionation of [Pd( PPh3)J [PdC12( PhCN)2] and Ph2PCH2PPh2.73' The reaction of [Pd( PPh3)4] [PtCI2( NCBU~)~] and Ph2PCH2PPh2 gave the heterometallic [ClPd( Ph2PCH2PPh2),PtC1] which adds SO2 CO etc.to give 'A-frames' often rever~ibly.'~' A series of dithiophosphinite-bridged complexes of type [M2( p-SPPh,),L,] {M = Pd or Pt;L = CNMe CNBu' PR, P(OPh), or P(OPh),Ph} have been prepared and shown to have 'head to tail' bridged structures (34).73d 70 J.M. Williams Ado. Inorg. Chern. Radiochem. 1983 26 235. 7' J. E. Backvall Acc. Chem. Rex 1983 16 335. 72 (a) Y. Yamamoto K. Aoki and H. Yamazaki Organornetallics 1983 2 1372; (b) L. Manojlovic-Muir K. W. Muir B. R. Lloyd and R. J. Puddephatt J. Chem. SOC.,Chem. Commun. 1983 1336; (c)E. G. Mednikov V. V. Bashilov V. 1. Sokolov Ya. L. Slovokhotov and Yu T. Struchkov Polyhedron 1983 2 141 ; (d) R. Bender P. Braunstein J.-M. Jud and Y. Dusausoy Inorg. Chem. 1983 22 3394. 73 (a) N. M. Boag P. L. Goggin R. J. Goodfellow and I. R. Herbert J. Chem. Soc. Dalton Trans. 1983 1101 ; (6)R. J. Goodfellow 1.R. Herbert and A. G. Orpen J. Chem. Soc. Chem. Comrnun. 1983 1386; (c) P. G. Pringle and B. L. Shaw J. Chem. SOC. Dalton Trans. 1983 889; (d)8. Messbauer H. Meyer B. Walther M. J. Heeg A. F. M. Maqsudur Rahman and J. P. Oliver Inorg. Chem. 1983 22 272. Ru Os Rh Ir Pd Pt Ph, PLS II L-Pp-Pd-L The addition of SO2 02,or CS2 to [{P(cyclo-C,H ,)3}2Pt] has been studied and the structure of the 1 1 sulphur dioxide adduct established as being of the TI-pyramidal type with the P-E-P = 166".74" The [Pt(PBu',),] is much less reactive than the tricyclohexylphosphine analogue. Palladium(0) phosphine complexes [Pt(PPr',) or 3] and [Pd(PPh,),] add CSSe to form (PR3)2Pd(CSSe) in which the CSSe is q2-co-ordinated via C and Se; replacement of the monodentate phosphines occurs on treatment with o-C,H~(PP~~)~ The reaction of or O-C,H,(CH~PP~~)~.~~~ [Pt(CS2)(Ph2PCH2CH2PPh2)]with,[Pt(q2-C2H4)(PPh3)2] cleaves one C-S bond to -give [(Ph2PCH2C H2PPh2)Pt(p- S)Pt(PPh3)(CS)].74' Sulphur adds to [Pt(PPh3),] to give a mixture of [Pt,(p-S),(PPh,),] and [PtS4(PPh3)2];74d the former can be alkylated at S even by CHICll or CHCl?.[Pt,(p-S),(PPh7),] behaves as a bidentate sulphur donor 'ligand' towards Pd" Ni" Hg" and Au'' as for example in compound (35).74e The X-ray structure of [PtS,(Ph2PCH2CH2PPh2)] has confirmed74f the tetrasulphido(2 -) ring structure originally proposed. The first example of v2-co-ordination by a phospha-alkene P(mesity1) =CPh2 is reported in [Pt{MeC(CH2PPh2)3}{P(mesityl)=CPh,}].In [Pt{P(me~ityl)=CPh,)~] and [Pt{P(mesityl)=CPh,},( PECBU')] however 7 '-co-ordination is present.748 The diarsines Ph2As(CH2),AsPh2 (n = 6-12 or 16) (L-L) form trans-[Pd(L-L)X2] (X = halide) complexes which were shown to be monomers for n = 12 16 with trans chelating diarsines but complexes with the shorter-chain (a) J. M. Ritchey D. C. Moody and R. R. Ryan fnorg. Chem. 1983,22,2276; (b)W. Werner M. Ebner W. Bertleff and U. Schubert Organometallics 1983 2 891; (c) W. M. Hawling A. Walker and M. A. Woitzik J. Chem. SOC.,Chem. Commun. 1983 11; (d)R. R. Gukathason R. H. Morris and A. Walker Can. J. Chem. 1983 61 2490; (e)C. E. Briant T. S. A. Hor N. D. Howells and D. M. P. Mingos J. Chem. Soc. Chem. Cornrnun. 1983 1148; (f)C. E. Briant M.J. Calhorda T. S. Hor N. D. Howells and D. M. P. Mingos J. Chem. SOC.,Dalton Trans. 1983 1325; (g)S. I. Al-Resayes S. I. Klein H. W. Kroto M. F. Meidine and J. F. Nixon J. Cbem. Soc. Chem. Commun. 1983 930. 268 W Levason ligands were too insoluble tor molecular weight mea~urements.'~~ These ligands react with [PtCI4l2- to give cis-[Pt(L-L)X,] and with [Pt(C2H4)C13]- to give trans-[Pt(L-L)X,]; the cis complexes are dimeric with bridging L-L but the trans complexes are monomeric.75b An X-ray structure of the complex [Pd3(PhzPCH2CH2PPh2)3(p-CN)3](C104)3 has shown an unexpected trimeric unit based upon -CN-bridges with the 31P and 13C n.m.r. spectra suggesting a Pd-CN-Pd-NC-Pd-NC sequence rather than the more symmetric arrange- ment.75c Although it has usually been found that nitrogen donor ligands form only four-co-ordinate Pd" complexes the tetramine N(CH2CH2NMe2) has been shown to give [PdLXIY (X = CI Br I or NCS; Y = PF or BPh4) which in solution exhibit an equilibrium between four and five co-ordinate (N3X and N4X) pallad- i~m.~'~ Palladium(11) complexes of macrocyclic tetraphosphines have been ~ynthesized~~ by template routes from Pd" complexes of the di-secondary phosphines MeHP(CH,),PHMe (n = 2 or 3) and dialdehydes or diketones [e.g.(36)]. X-Ray structures of two isomers obtained from acetylacetone and Pd{MeHP(CH2)2PHMe)2C12 were both found to contain the 14-membered ring system (36a) one being the planar [PdL]C12 of the RSSR-ligand the other square pyramidal [PdLCl]CI of the RSRS djastereoisomer.The phosphine But2PCH2CHCH2CH2 (L) reacts with [Pt(PhCN),Cl,] in toluene to give [PtL2C12]( P2C12) which on heating in 2-methoxyethanol undergoes a novel rearrangement of one ligand to form a o-ally1 complex [hCl{But PCH =CH( CH3)k H2}L]. 77 The 'A-frame' platinum(I1) complexes [Pt2(p-Ph2PCH2PPhz)2(p-Y)X2]+ when Y = H are fluxional on the n.m.r. time scale and a possible mechanism for inversion 75 (a)W. E. Hill D. M. A. Minahan and C. A. McAuliffe Inorg. Chem. 1983,22,3382; (b)W. E. Hill D. M. A. Minahan C. A. McAuliffe and K. L. Minten Inorg. Chim. Acta 1983 14 9; (c) J. A. Davies F. R. Hartley S. G Murray and M. A. Pierce-Butler 1. Chem. SOC. Dalton Trans. 1983 1305 (d)S. N. Bhattacharyya and C. V. Senoff Inorg. Chem.1983 22 1607. 76 R. Bartsch S. Hietkamp S. Morton,H. Peters and 0. Stelzer Inorg. Chern 1983 22 3624. 77 W. J. Youngs and J. A. Ibers Organometallics 1983 2 979. 269 Ru,Os Rh Ir Pd PI of the A-frame involving a linear Pt-H-R intermediate has been disc~ssed.~~" Treatment of [Pt(Ph2PCH2PPh,)C1,] with LiCECR (R = Ph p-MeC,H, CH,CH,Ph or C(Me)=CH,) produces the face to face dimers (37a) which react with Ph2PCH2PPh2 to give fluxional mononuclear truns-[Pt(Ph,PCH,PPh,),(C-CR),] with monodentate diph~sphines.~~' The latter can be oxidized or quaternized at the unco-ordinated phosphorus to [Pt(C zCR),( Ph2PCH2P(0)Ph2),] and [Pt(C=CR)2(Ph2PCH2PPh2Me)2]12. Direct reaction of [Pt(Ph2PCH2PPh2),]C12 with LiCrCPh gives [Pt(Ph,PCHPPh,),] as well as the acetylide whilst reaction with Hg(C=CR) gives the bimetallic complexes (37b) also obtained from [Pt(Ph2PCH2PPh2),]C1, Hg(O,CMe), and RCECH.~" It is also possible to deprotonate the methylene bridge in [PtX2(Ph2PCH2PPh2)] with LiN(SiMe3), and then to alkylate with Me1 to give [PtX,(Ph,PCH(Me)PPh,)]; repetition of the process produces [PtX2(Ph,PCMe,PPh,)2].78' The ligand 2-diphenylphosphinopyridine, 2-Ph2PC5H4N (Ph,Ppy) readily bridges two-metal centres to produce binuclear For example reaction of [Pt(Ph,Ppy),Cl,] with [Rh(CO),Cl] gives [Pt(Ph2Ppy),C1][Rh(CO)2C12] which con- tains a cis-planar anion and the cation contains one chelating and one monodentate (P-co-ord) Ph,Ppy and one chloride.On heating in benzene it rearranges into [RhPt(Ph2Ppy),(C0)Cl3] (38) which on chlorine oxidation is converted into '' (a)R.J. Puddephatt K. A. Azam R. H.Hill M. P. Brown C. D. Nelson R. P. Moulding K. R. Seddon and M. C. Grossel 1.Am. Chem. SOC.,1983,105,5642; (b)C. R. Langrick D. M. McEwan P. G. Pringle and B. L. Shaw J. Chem. SOC. Dalton Trans. 1983 2487; (c)S. Al-Jibori and B. L. Shaw Inorg. Chim. Acta 1983 74 235. (a)J. P. Farr M. M. Olmstead F. E. Wood and A. L. Balch J. Am. Chem. Soc. 1983 105 792; (b)J. P. Farr M. M. Olmstead and A. L. Balch Inorg. Chem. 1983 22 1229; (c) J. P. Farr F. E. Wood and A. L. Balch Inorg. Chem. 1983 22 3387; (d)M. M. Olmstead R. R.Guimerans J. P. Farr and A. L. Balch. Inorg. Chim. Acto 1983 75 199. 270 W.Levason [RhPt(Ph2Ppy)2(CO)Cl,1 both chlorines being added to the platin~m.~~" The reac- tions of [Rh(Ph,Ppy),(CO)Cl] with [Pd(COD)Cl,] or of [Pd(Ph,Ppy),CI,] with [FUI(CO)~C~] give [RhPd(Ph,Ppy),(CO)Cl,] and both 'head to head' and 'head to tail' isomers of [RhPd(Ph,Py),(MeCN),Cl,] have been obtained the latter being more stable.79* Palladium(1) or platinum(1) complexes are obtained from [Pt(Ph,Ppy),Cl,] and Pd,(dba) or Pt(dba) (dba = dibenzylidene acetone) viz.[PtPd(Ph,Ppy),CI,] and [Pt2(Ph2Ppy)2C12]79' which exist as 'head to tail' isomers. Both 'head to head' (P on Pt) and 'head to tail' isomers of [PdPt(Ph2Ppy),CI2] have been isolated but the 'head to head' (P on Pd) has not been (39). The . P-N P-N NnP II II II X-Pt-Pd-X X-Pt-Pd-X X-Pt-Pd-X Head to head Head to tail Head to head (P-Pt) (P-N= PhzPpy) (P-Pd) (39) ligand PhP(CH2PPh2) (L) also readily bridges metal for example it binds through the terminal phosphines only in [PdLCI,] which then co-ordinates via the central phosphorus to a second metal e.g.in [Cl,Pd{(Ph2PCH,),PPh}Pd(MeCN)Cl2].Removal of the chlorine from [PtHCI(PBu',),] with AgY (Y = PF, BF, etc,) generates the three-co-ordinate hydrides [PtH(PBu',),]Y which will add small neutral ligands (CO MeCN or NH3) to give [PtHL(PBu',),]Y but on reaction with PBu' or P(cyc10-C,H *), the proton is removed to give [P~(PBU~,)~].~'" Dinuclear hydrides are prepared from 'RH,(PR,),' (itself made in situ from [Pt(COD),] PR, and hydrogen) and [PtH(Me,CO)(PR',),].+ The products [( PR,),Pt(p-H),PtH(PR',),]+(R R' = Et Ph or cyclo-C,H ,) are air have the structure (40a) and interestingly show no evidence of exchange between the terminal and bridging hydrides.Other preparations for [(PEt,),Pt(p- H),PtH(PEt3),]+ include photolysis of [Pt(PEt3),C204] in the presence of hydrogen and reaction of [PtHCl(PEt,),] with NaBH,. Analogues with diphosphine ligands are produced by two routes either from [Pt(dimethylpyrazole),(L-L)] HBF, and subsequent treat- ment with KBH, or from [Pt(L-L)CI,] and AgBF4 in methanol followed by addition of KBH,.80d The products have the structure (40b) (L-L = Ph2PCH2CH2PPh2 10 (a)R. G. Goel and R. C. Srivastava Can. J. Chem. 1983 61 1352; (b)F. Bachechi G. Bracher D. M. Grove B. Kellenberger P. S. Pregosin L. M. Venanzi and L. Zambonelli Inorg. Chem. 1983 22 1031 ; (c) R.S. Paonessa and W. C. Trogler Inorg. Chem. 1983 22 1038; (d)C. 8. Knobler H. D. Kaesz G. Minghetti A. L. Bandini G. Banditelli and F. Bonati Inorg. Chem. 1983 22 2324; (e) G. Minghetti A. L. Bandini G. Bonditelli F. Bonati R. Szostak C. E. Strouse C. B. Knobler and H. D. Kaesz Inorg. Chem. 198.7 22 2332. Ru,Os Rh Ir Pd Pt 27 1 Ph2P(CH2),PPh2 Ph2P(CH2)4PPh2 cis-Ph,PCHCHPPh2) and in marked contrast to those with monodentate phosphines the hydrides are fluxional. Treatment with CO or CNR displaces one hydride bridge to form [(L-L)Pt(p-H)-(~-L)P~(L-L)]+ (L = co or CNR).~~' Crown-ethers form adducts with platinum(I1) amines for example {[Pt(PMe,)- (NH,)Cl,].(dibenzo-18-crown-6)) and {2[Pt(PMe3)(NH,)C12]( 18-crown-6)} both of which have been characterized by X-ray crystallography and in each case the interaction is via bifurcated hydrogen bonds between the amine group and the crown oxygen atoms." The reaction of [Pt,(COD)(PEt,),] with nido-5,6-C2B8H 1z affords [9H-9,9-(Et3P)2-plo,l -H-7,8,9-C2PtB8Hlo] which on heating transforms into [9H-9 10-(Et3P),-7,8,9-C2PtB8H9], both of which have been characterized by X-ray studies.82" The 17-vertex platinaborane [(PhMe2P)4Pt3B,4H ,6] has also been pre- pared.82b The reaction of cis-or trans-[PdR2(PR3),] (R = Me Et or Ph) with R'Li in ether or THF results in stepwise replacement of PR3 by R' with stereochemical retention to afford Li[PdR2R'(PR3)] and Li2[PdR2R'2].83a A rare example of 6-hydrogen abstraction has been observed on refluxing C~~-[P~(PR~)~(CH,C~H~M~),] (R = Et or Ph) in xylene when the benzoplatinacyclopentenes [h(C H2C6H4c H2)(PR3)2] are formed.83b In contrast to the extensive studies of (C5H5)- and (C,Me5)- complexes few pentaphenylcyclopentadienyl complexes are known ; a series [(q5-C5Ph5)-(q3-allyl)Pd] (ally1 = various substituted allyls) have now been prepared from NaC5Ph and [(q3-allyl)PdC1],.83' Treatment of [Pd(q3-allyl)(q5-C,Me5)]with PR3 proceeds stepwise uia [Pd(q3-ally1)(q3-C5Me,)(PR3)] to form [Pd(PR3),(q2-CH2=C5Me4)] containing 1,2,3,4-tetramethyl f~lvalene.~~~ Bis(cyc1open-tadieny1)magnesium reacts with [Pt2(p-CI)2(C2H4)2C12] to give [Pt(q-CzH4)-(q'-C5H5)(q5-C5H5)] the latter containing a Pt-Pt and [Pt2(p-C,oH10)(q5-C5H5)2] bond and coupled CsHs rings (41).83e " H.M.Colquhoun D. F. Lewis J. F. Stoddart and D. J. Williams 1. Chem. SOC. Dalton Trans. 1983,607. 82 (a)G. K. Barker M. Green F. G. A. Stone W. C. Wolsey and A. J. Welch 1. Chem. SOC. Dalton Trans. 1983 2063; (6) M. A. Beckett J. E. Crook N. N. Greenwood and J. D. Kennedy J. Chem. SOC.,Chem. Commun. 1983 1228. 83 (a)H. Nakazawa F. Ozawa and A. Yamamoto Organomerallics 1983 2 241 ; (6) S. D. Chappel and D. J. Cole-Hamilton J. Chem. Soc. Dalron Trans. 1983 1051; (c)J. Powell and N. I. Dowling Organometollics 1983 2 1742; (d)H. Werner G. T. Crisp P. W. Jolly H.-J. Kraus and C. Kruger Organometallics 1983,2 1369; (e) N. M. Boag R. J. Goodfellow M. Green B. Hessner J. A. K. Howard and F. G. A. Stone J. Chem. SOC.,Dalton Trans.. 1983 2585. 272 W.Leuason Binuclear Pt"' compounds have attracted considerable recent work.The [Pt''2(P205H2)4]4- species [P205H2 = diphosphite(2 -)] have been studied in some detail by electronic absorption and emission spectroscopy and by i.r. and Raman and their halogen oxidation to produce [Pt11'2(P205H2)4X2]4- described.84"-' The latter compounds have structure (42) and with X = C1 the L-L L-L = H02POP02H2-, HPOi-elc. (42) Pt-Pt bond is 2.695 A consistent with a single Pt-Pt 0 bond. If a deficit of halogen (Cl Br or I) is used in the oxidation [Pt2(P2O5H2),XI4- compounds with a formal Pt oxidation state of 2.5 are produced and these have anomalous conduction properties along the infinite linear chain [-X-Pt- ~t-],,.~~' Phosphate bridged Pt'" materials [Pt2(HPO4),I2- add heterocyclic amines to form [Pt2(HPO4),L2I2- (L = pyridine 2-Mepy or 3,4-Me,Q) and in an attempt to grow crystals of the pyridine adduct [pyH][Pt,H,PO,)( HP04)3(py)s].H20 was produced and struc- turally ~haracterized.',~ In continuing studies aimed at clarifying the nature and chemistry of platinum blues it has been shown that cis-[Pt(NH,),( H20),I2+ and a-pyridone (C5H4NOH) produce several species on reaction in aqueous solution including c~s-[P~(NH~)~(C~H,NOH),]~+ and 'head to head' and 'head to tail' a-pyridonate bridged [Pt2(NH3)4(C5H4N0)2]2+.The 'head to tail' form has two a-pyridonates bridging cis-Pt(NH3) units (Pt-Pt = 2.898 A) whilst the head to head is dimerized in the crystal via stacking and intercation hydrogen-bonding (43).85a Related a-pyridonate-bridged compounds of Pt" with other amines (e.g.ethy-lenediamine),85b of Rlrl and of partially oxidized [Pt(2.25)] materials have been 85b3c characterized and the relationships between the structures (especially Pt-Pt bond lengths) and spectroscopic properties discussed. A mononuclear Pt'" a-pyridone complex mer-[Pt(NH3)2(C5H4NO)C13]has also been prepared and studied by X-ray diffraction methods.85d Halogen oxidation of the palladium( 11) analogues produces [Pd( L- L)Cl,] (L-L = Me2NCH2CH2NMe2 bipy 1,lO-phenanthroline Ph2PCH2CH2PPh2 Me2PCH2CH2PMe2, o-C,H,(AsMe,), or Ph,AsCH,CH,AsPh,) and [Pd(L-L)Br,] (L-L = Me,PCH,CH,PMe, O-C,H,(ASM~,)~) whilst tr~ns-[Pd(L'-L')~X~]-(C104)2 (L'-L' = o-C6H4( Me2PCH2CH2PMe2 o-C6H,(AsMe2)( PMe,); 04 (a) S.F. Rice and H. B. Gray J. Am. Chem. Soc. 1983 105 4571 ;(b)P. Stein M. K. Dickson and D. M. Roundhill J. Am. Chem. SOC.,1983 105 3489; (c)C.M. Che F. H. Herbstein W. P. Schaefer R. E. Marsh and H. B. Gray J. Am. Chem. Soc. 1983, 105,4604; (d) H. L. Conder F. A. Cotton L. R. Falvello S. Han and R. A. Walton Inorg. Chem. 1983 22 1887. a5 (a)L. S. Hollis and S. J. Lippard J Am. Chem. SOC.,1983 105 3494; (b)L. S. Hollis and S. J. Lippard Inorg. Chem. 1983,22 2600 2605 (c) L. S. Hollis M. M. Roberts and S. J. Lippard Inorg. Chem. 1983 22 3637 (d)L. S. Hollis and S. J. Lippard Inorg. Chem. 1983 22 2708. Ru Os Rh Ir Pd Pt 1*+ 3.129 A I X = C1 or Br) are obtained by HN03-HC104 oxidation. X-Ray structures of [Pd(bipy)Cl,] and [Pd{ O-C~H~(ASM~~)~)~C~~](C~O~)~, the first on PdIV complexes of neutral ligands were also In contrast I2 converts [Pd(L-L)I,] {L-L = cis-Ph,PCH=CHPPh or O-C&(SPh)2} into Pd" polyiodides Pd(L-L)12.12 which contain planar Pd" environments with neighbouring molecules linked Pd- I-1-1--I -Pd by di-iodine.866 Threeofthe possible isomers of[R(NH,)2(OH2)2C12]2+namely trans-cis-cis trans-trans-trans and cis-trans-cis have been separated and characterized by i.r.I5N,and 19'Pt n.m.r. spectroscopy and X-ray cry~tallography.~~" Condensation of [Pt(en),J4' with HCHO and NH or MeNO has produced octahedral substitu- tion-inert Ptlv complexes of several macrobicyclic hexamine~~~~ (44) which have been characterized by X-ray diffraction (44a) and by electronic and n.m.r.spectros- copy. Pulse radiolysis or electrochemical reduction provides evidence for transient Ptl'' complexes. Nitrosation of [Pt(en)(bipy)Cl,]Cl with KN02 in aqueous solution produces [Pt(bipy)(ONNCH2CHzNNO~Cl(N02)].E7c Y NH NH HN (,,CHHN) (NH(N HN) (R=HorMe) NH NHHN (4 R (44) (b) 86 (a)L. R. Gray D. J. Gulliver W. Levason and M. Webster J. Chem. SOC., Dalton Trans. 1983 133; (b)ibid. Inorg. Chem. 1983 22 2362; Acta Crystallogr. 1983. C39 822. 87 (a)R. Kuroda S. Neidle I. M. Ismail and P. J. Sadler Inorg. Chem. 1983 22 3630; (b)H. A. Boucher G.A. Lawrence P. A. Lay A. M. Sargeson A. M. Bond D. F. Sangster and J. C. Sullivan J. Am. Chem. Soc. 1983 105 4652; (c)W. A. Freeman J. Am. Chem. SOC. 1983 105 2725; (d)K.Wieghardt M. Koppen W. Swiridoff and J. Weiss 3. Chem. SOC.,Dalton Trans. 1983 1869. 274 W.Leuason 1,4,7-Triazacyclononane HNCH2CH2NHCH2CH2NHCH2CH2, (L) behaves as a mono- or bi-dentate ligand towards Pt",and as a tridentate ligand towards PtIV for example in [Pt(L)Br,]Br [Pt(L),](CIO,),; the [Pt1v(L)2]4+ ion is formed by bubbling oxygen into a hot aqueous solution of [Ptl'(L)2]2+.X7d A multinuclear ("C 77Se,195Pt)n.m.r. study of [PtMe,X(MeE(CH,),,EMe)] (E = S or Se; X = C1 Br or I; n = 2 or 3) has been reported and correlations between the various chemical shifts and coupling constants are discussed. The 77Se n.m.r. spectra clearly indicate the different invertomers present.88 Mixed-valence and partially oxidized materials continue to attract a growing amount of effort.A preliminary communication has described the synthesis and (L structures of [Pd"LI2+ [Pd1VLC12]2+ and [Pd11L][Pd1VLC12](C104)4 = 1,4,8,11-tetra-azacy~lotetradecane).~~" The long-known Magnus green salt [Pt(NH,),][PtCl,] is converted into a one-dimensional conductor by treatment with HC104 and hydrogen Resonance-Raman spectra have been recorded for [Pt(pn)2][Pt(pn)2X2]Y489e (X = C1 Br or I Y = CIO, pn = 1,2-diaminopropane) and [Pt(dien) I][ Pt(dien) 13]12x9d (dien = diethylenetriamine) along with X-ray structural data on these and on [Pt(tn)2][Pt(tn)2X,]Y2 (Y = ClO or BF,; tn = 1,3-diamin0propane).~~~-' Although the reactions of PtI or H2PtC16 with the appropriate MI (M = Rb Cs or NH,) in water give the expected hexa-iodoplatinates(Iv) M2Pt16,90athe unexpec- ted products from the corresponding reactions using [PtC1,I2- were of type M2[PtI,].2H20 (M = K Rb or NH,) which are linear chain mixed-valence materials and no evidence for crystalline materials containing [PtI,l2- was found.90b Halogens oxidize the dithioacetate compounds [Pt,(MeCS,),] to [Pt1'12(MeCS2)4X2] (45) but with a deficit of iodine the product was [Pt,(MeCS2),I] again an infinite s-s chain mixed-valence materialg0' Other significant developments in 'molecular metal chemistry' include the synthesis of [NH4- Me,12- [Pt(C204)2],90d Pb,K1-,[Pt(CN),].1.5H20 (x -0.77),90' A 73M027[Pt(CN)4]C10 5.3H20 (M = Pb or Ba and A = K M = Ba and A = Rb).90f xn E.W. Abel K. G. Orrell and A.W. G. Platt J. Chem. Soc. Dalfon Trans. 1983 2435. 89 (a)M. Yamashita H. Ito K. Toriumi and T. Ito Inorg. Chem. 1983 22 1566; (b)J.-P. Catinat T. Robert and G. Offergeld J. Chem. SOC.,Chem. Commun. 1983 1312; (c) R. J. H. Clark and M. Kurmoo J. Chem. Soc. Dalton Trans. 1983 761; (d)R. J. H. Clark M. Kurmoo A. M. R. Galas and M. B. Hursthouse J. Chem. SOC.,Dalton Trans. 1983 1583; (e)M. Cannas M. B. Lucchesini and G. Marangiu Acta Crystallogr. 1983 C39 15 14; (f)M. Cannas G. Marongiu K. Martin and H. J. Keller 2.Nalurforsch. Ted B 1983 38 1346. 90 (a)G. Thiele C. Mrozek D. Kammerer and K. Wittman Z Natut$orsch. Ted B 1983 38 905; (b) G. Thiele and K. Wittrnan 2.Anorg. Allg. Chem. 1983 507 183; (c)C. Bellitto A. Flamini L. Gastaldi and L. Scaramuzza Znorg.Chem. 1983 22 444; (d) M. Mizuno A. E. Underhill and K. Carniero J. Chem. SOC.,Dalton Trans. 1983 1771 (e)G. S. V. Coles. A. E. Underhill J. M. Williams and A. J. Schulz ibid 1983 2529; (f)G. S. V. Coles A. E. Underhill and K. Carniero ibrd 1983 141 1.