11 Cu Ag Au; Zn Cd Hg By J. SILVER Department of Chemistry University of Essex Colchester C04 3SQ 1 Copper Silver and Gold Copper-Copper( I). The stoicheiometry and kinetics of oxidation of dimeric bis(p- halogeno)bis{ (diamine)copper( I)} have been studied.' In polymeric chloro( diethyl- telluride)copper(I) two Et,Te ligands are bridged between two di-p-chloro-dicopper(1) cores. A new tetrathiafulvalenium complex prepared from CuCI is said to contain CU'.~ Monomeric anions are found in [AsPh,][CuCl,] [PPh4]-[CuCl,] and [PP~,][CUB~,].~ The structure of [P( Et)( Ph),][CuBr,] has been repor- ted.5 [N( Ph)Me3],[Cu,Br4] contains discrete centrosymmetric [Cu2Br4I2- anions,6 whereas [NMe,],[ Cu,Br J contains a discrete [Cu,Br,l3- entity with a single bridging Br atom.7 The structures of both [NMe4][Cu,I,] and [SMe3][Cu21,] have been the former contains [Cu,I,]- chains composed of edge- and face-sharing tetrahedra.Aqueous solutions of Cul KI and crown ether have been found to form complexes [CU&][cU8113]K7( 12-crown-4), [Cu416]K2( 15-crown-5), and [Cu314]- K(dibenzo-24-crown-8) depending on the identity of the crown ether. The former contains discrete [Cu41612- (1) and [Cu811$ (2) clusters." The structures of the fluorescent Cu' complexes [Cu414( p-toluidine),- (acetonitrile),] and [Cu212(p-chloroanaline(acetonitrile)l have been presented." From '271-Mossbauer spectra it has been concluded that the Cu-I interaction in a number of CuI-phosphine complexes is largely ionic in nature.' A compound said to be K[Cu(SCN),(NCS-SCN) has been reported13 and the redox properties of bis(phenylazoacetaldoximato)bis(phenylacetaldoxime)dicop-per(r) have been studied.' A Cu-Cu bond has been found in [CU~L$][C~O~]~-H~O M.A. El-Sayed A. El-Toukhy and G. Davies Inorg. Chem. 1985 24 3387. ' R. K. Chadha and J. E. Drake J. Organomet. Chem. 1985 286 121. M. Inoue and M. B. Inoue J. Chem. SOC.,Chem. Commun. 1985 1043. S. Andersson and S. Jagner Acta Chem. Scand. Ser. A. 1985 39 297. S. Andersson and S. Jagner Acta Chem. Scand. Ser. A. 1985 39 515. S. Andersson and S. Jagner Acta Chem. Scand. Ser. A. 1985 39 423. ' M. Asplund and S. Jagner Acta Chem. Scand. Ser. A. 1985 39 47. S. Andersson and S. Jagner Acta Chem. Scand. Ser. A. 1985 39 181. M. Asplund S. Jagner and M. Nilsson Acta Chem.Scand. Ser. A. 1985 39 447. I0 N. P. Rath and E. M. Holt J. Chem. SOC.,Chem. Commun. 1985 665. " N. P. Rath E. M. Holt and K. Tanimura Inorg. Chem. 1985 24 3934. 12 R. J. Batchelor and T. Birchall J. Chem. SOC.,Dalton Trans. 1985 1727. 13 S. K. Tobia F. R. Souaya and W. G. Hanna Polyhedron 1985 4 425. 14 S. Pal D. Bandyopadhyay D. Datta and A. Chakravorty J. Chem. SOC.,Dalton Trans. 1985 159. 321 322 J. Silver 1 i i [L2 = 2,6-di(2'-methoxyethyliminomethyl)pyridine].1s Photoreduction catalysis by [Cu(N-N)(PPh,),]+ (N-N = 2,9-dimethyl-l,l0-phenanthroline(dmp) or 4,4',6,6'-tetramethyl-2,2'-bipyridine)has been studied.I6 The l"1-heterobimetallic adduct of tris(pyrrolidinecarbodithioacto)cobalt(IIr) with copper( I) bromide contains a four-coordinate Cu' atom." The structures of some bis(methy1-substituted pyridine)-copper( r) and silver( I) nitrates and perchlor- ates have been reported,18 as have those of [M(PPh3)4]C104 (M = Cu Ag) CU(PP~~)~(XJC~O,, (X = py or biby) and [CU(BH,)(PP~,),].'~ Structural studies on the 1 :2 dinuclear adducts of Cur halides with some 2(4)-mono- and dimethyl- substituted pyridine bases and quinoline," and also studies on the mononuclear adducts of Cu' halides with pyridine bases have been presented.21 The structures of [Cu4X4L4] (X = halogen; L = N,P base) 'cubane' clusters and those of the adducts [Cu(CN)L,] [L = diethylamine triethylamine 4-methylpyridine or 1,lO-phenanthroline(phen) have been A convenient synthesis of Cu' carboxylates has been described23 and electrochemical evidence for a Cu' intermediate in the formation of Cu" amino-acid complexes has been found.24 Cu' benzenesulphinate and Cu' p-toluenesulphinate compounds have been de~cribed.~' Structural studies on complexes containing 1-methylimidazoline-2(3H)thione(mimtH) have shown that Cu(mimtH),.NO (3) and Cu2(mimtH)$04-3H20 have Cu-S bonds of 2.249 and 2.258 8 respec-tively.26qb I5 M.G. B. Drew A. Lavery V. McKee and S. M. Nelson J. Chem. SOC.,Dalton Trans. 1985 1771. 16 S. Sakaki G. Koga F. Sato and K. Ohkubo J. Chem. SOC.,Dalton Trans. 1985 1959. 17 L. M. Engelhardt P. C. Healy R. I. Papasergio and A. H. White Znorg. Chem. 1985 24 382. 18 L. M. Engelhardt C. Pakawatchai A. H. White and P. C. Healy J.Chem. SOC.,Dalton Trans. 1985 117. 19 L. M. Engelhardt C. Pakawatchai A. H. White and P. C. Healy J. Chem. SOC.,Dalton Trans. 1985 125. 2o J. C. Dyason L. M. Engelhardt P. C. Healy C. Pakawatchi and A. H. White Inorg. Chem. 1985 24 1950. 21 J. C. Dyason P. C. Healy C. Pakawatchai V. A. Patrick and A. H. White Inorg. Chem. 1985,24 1957. 22 (a)J. C. Dyason P. C. Healy L. M. Engelhardt C. Pakawatchai V. A. Patrick C. L. Raston and A. H. White J. Chem. SOC.,Dalton Trans. 1985 831; (b) ibid. 1985 839. 23 T. P. Lockhart and D. A. Haitko Polyhedron 1985,4 1745. 24 G. Thomas and P. S. Zacharias Polyhedron 1985 4 811. 25 S. H. Bertz and G. Dabbagh Inorg. Chem. 1985 24 3488. 26 (a) E. R. Atkinson D. J. Gardiner A. R. W. Jackson and E. S. Raper Inorg.Chim. Acta 1985 98 35; (b) E. R. Atkinson E. S. Raper D. J. Gardiner H. M. Dawes N. P. C. Walker and A. R. W. Jackson Inorg. Chim. Acta 1985 100 285. Cu,Ag Au; Zn,Cd Hg The structure of [CU,(O-(SCH,)~C~H,)~]~-(4) as its [PPh4]+ salt has also been reported.27 The syntheses of [(L)(CPh,P),Cu][HB(O,CH),] and [(L)(Ph,P),Cu]-[H,B(O,CH),] (L = phen or 3,4,7,8-tetramethyl-phen) have been reported28 and the siructures of (PPh3),Cu( ~-S,CSCH,SCS,)CU(PP~~)~, (PPh,),Cu(S,COEt) (PPh3),Cu(S2CNHPh)-CHC13 The llBT and (triphos)Cu( q'-O,CH) de~cribed.~~".~ and 31P n.m.r. spectra of [(Ph),PCHl2CuB5H8,[(Ph),P],CuC2B4H7 [(Ph),Pl2Cu (Me)2C2B4H5,[(Ph)2PCH2]2CuC2B4H7CH2C12 Me),C2B4H5-a'nd [(Ph)2PCH2]2C~( as have those of CU(PP~,)~(B~H,~X) ;CH2Cl2 have been ~tudied,~'"'.~ (X = H NCS NCSe NCBPh3 NCBH, or NCBH,NCBH,) cornplexe~.~~ 27 J.R. Nicholson I. L. Abrahams W. Clegg and C. D. Garner Inorg. Chem. 1985 24 1092. 28 G. La Monica G. A. Ardizzoia F. Cariati S. Cenini and M. Pizzotti Inorg. Chem. 1985 24,3920. 29 (a) C. Bianchini C. A. Ghilardi A. Meli S. Midollini and A. Orlandini Inorg. Chem. 1985 24,924; (b) ibid. 1985 24 932. (a) P. K. Rush and L. Barton Polyhedron 1985,4 1741; (b) Inorg. Chem. 1985 24 3413. 30 31 D. G. Meina and J. H. Moms J. Chem. Soc. Dalton Trans. 1985 1903. 324 J. Silver The synthesis of methyl(tri-t-buty1phosphine)copperhas been reported3' and dithio-o-toluate Cur complexes with bis( dipheny1phosphino)methane described.33 The structures of bis(tripheny1phosphine)Cu' o-and p-nitrobenzoates have been dete~rnined.~~ The thermal decompositions of MeCu and methyl(tricyclohexylphos-phine)copper(I) have been studied.35 In the structures Cu( PPh3)( pptu)Cl and Cu(pptu),Cl [pptu = l-phenyl-3-(2-pyridyI)-2-thiourea]each Cu atom is in trigonal planar coordination and is bonded to a C1- ion (5).36 The behaviour of some functionally substituted a-allenic alcohol derivatives towards organocopper( I) species has been reported,37 as have the reactions of organocopper compounds with chosen boron corn pound^.^^ An efficient synthesis of C6H5C-CCu has been presented.39 Differences in the reactions of electron-deficient olefins with organocopper( I)-Lewis acid reagents have been explored4' and the reactions of a number of lithium organocuprates have been ~tudied.~'~-~ Cu' complexes of olefins produced by olefin chemical ionization of Cu" p-diketones have been rep~rted,~ as have those produced by reaction with unsaturated small molecules.43 Alkene and CO derivatives of Cur and Ag' P-diketones have been prepareda and the reactions of Cur-N,N'-ethylenebis( benzaldimine) com-plexes with CO and isocyanides in~estigated.~~ 32 S.Pasynkiewicz S.Pikul and J. Poplawska J. Organornet. Chern. 1985 293 125. 33 A. M. M. Lanfredi F. Ugozzoli A. Camus and N. Marsich Inorg. Chirn. Acta 1985 99 111. 34 M. A. Cabras L. Naldini M. A. Zoroddu F. Cariati F. Demartin N. Masciocchi and M. Sansoni Inorg. Chirn. Acta 1985 104 L19. 35 S. Pasynkiewicz and J.Poplawska J. Organornet. Chern. 1985 282 427. 36 M. B. Ferrari G. G. Fava C. Pelizzi and P. Tarasconi Znorg. Chirn. Acta 1985 97 99. 37 H. Kleijn and P. Vermeer J. Organornet. Chern. 1985 292 437. 38 E. Kalbarczyk and S. Pasynkiewicz J. Organornet. Chern. 1985 290 257. 39 R. Kumar and D. G. Tuck J. Organornet. Chern. 1985,281 C47. 40 T. Ibuka T. Aoyagi K. Kitada F. Yoneda and Y. Yamamoto J. Organornet. Chern. 1985 287 C18. 41 (a) J. J. Eisch M. Behrooz and S. K. Dua J. Organornet. Chern. 1985 285 121; (b) G. Hallnemo T. Olsson and C. Ullenius J. Organornet. Chern. 1985 282 133; (c) J. Drouin and G. Rousseau J. Organornet. Chern. 1985 289 223; (d) J. T. B. H. Jastrzebski G. V. Koten M. J. N. Christophersen and C. H. Stam J. Organornet.Chern. 1985,292 319; (e)B. H. Lipshutz J. A. Kazlowski D. A. Parker S. L. Nguyen and K. E. McCarthy J. Organornet. Chern. 1985 285 437. 42 M. L. Morris and R. D. Koob Inorg. Chern. 1985,24 1769. 43 J. S. Thompson and R. M. Swiatek Inorg. Chern. 1985 24 110. 44 G. Doyle K. A. Eriksen and D. Van Engen Organornetallics 1985 4 830. 45 A. Toth C. Floriani M. Pasquali A. Chiesi-Villa A. G. Manfredotti and G. Guastini Inorg. Chern. 1985 24 648. 325 Cu Ag Au; Zn,Cd Hg 63Cu 13C and 170 n.m.r. spectra of the mixed clusters N~,[CU,F~(CO)~~] N~,[CU~F~,(CO)~,] have been reported.& The structures and N~~[cu~F~,(co)],~ of the pentagonal bipyramidal hexahydride Ir2Cu3H6( Me(",( PMe2Ph):+ has been presented47 as has the structure of [(OC),W( p-Ph2PCH2PPh2]2(p-Cl)(p-CO)C~].48 Copper(11).Local bonding effects and exchange interactions have been studied in A12B112-xC~(N02)6= K Rb TI,Cs; B = Cd Hg) complexes.49 Anhydrous (A transition-metal perchlorates M(C104)2 (M = Ni Co or Cu) and their chloryl and nitryl salts C102M(C104)3 N02M(C104)3 and (N02)2M(C104)4 have been pre- pared.50 The KC1-AlC1,-CuCl2 system has been studied at 300 0C.51 Exchange coupling in LiCuC13.2H20 and (C3HloN)CuC13 has been reported.52 The association constant of the first chloro-Cu" complex has been determined in water in the range 15-100 0c.53 Structural information shows that (C3N6H8)CU&& contains CU,CIZ,-dimer~,~~ whereas the compounds [M(en),],[Cu2Cl8]Cl2.2H2O (M = Co Rh Ir) contain Cu2CI:- dimers (6)? [(Ph),AI2Cu2Cl (A = P Sb) complexes have been prepared.56 The complexes Br(X)Cu" and Cl(X)Cu" (X = 3-dimethylaminopropan-1-olato) have been shown to contain infinite chains of alkoxo-bridged copper( 11) dimers connected by halogen bridges.57 [(DENC)2C~X2]2 (DENC = N,N-diethylnico-tinamide; X = C1 or Br) differ in that the C1 compound is C1 bridged in solu- tion but DENC bridged in the solid while the Br compound is always Br bridged.58 46 G.Doyle B. T. Heaton and E. Occhiello Organometallics 1985 4 1224. 47 L. F. Rhodes J. C. Hoffman and K. G. Caulton J. Am. Chem. SOC.,1985 107 1759. 48 A. Blagg A. T. Hutton B. L. Shaw and M. Thomton-Pett Inorg. Chim. Acta 1985 100 L33. 49 A. Ozarowski and D. Reinen Inorg. Chem. 1985 24 3860.50 J.-L. Pascal J. Potier and C. S. Zhang J. Chem. SOC.Dalton 1985 24 297. 51 J. H. von Barner P. B. Brekke and N. J. Bjerum Inorg. Chem. 1985 24 2162. 52 L. W. Ter Haar and W. E. Hatfield Inorg. Chem. 1985 24 1022. 53 L. A. Aston J. I. Bullock and P. W. G. Simpson Polyhedron 1985 4 1323. 54 A. Colombo L. Menabue A. Motori G. C. Pellacani W. Porzio F. Sandrolini and R. D. Willett Inorg. Chem. 1985 24 2900. 55 S. K. Hoffmann D. J. Hodgson and W. E. Hatfield Inorg. Chem. 1985 24 1194. 56 A. Bencini D. Gatteschi and C. Zanchini Inorg. Chem. 1985 24 704. 57 L. Walz H. Paulus and W. Haase J. Chem. SOC.,Dalton Trans. 1985 913. 58 G. Davies A. El-Toukhy K. D. Onan and M. Veidis Inorg. Chim. Acta 1985 98 85. 326 J. Silver E.p.r.studies of [Cu2(dien),C1,](C10,) have been rep~rted.'~ The structure of [CU(C,~H~~NSO)CI], at 120 K has been solved (7).60 The structure of [N,N-bis(3,5-dimethylpyrazol-l-ylmethyl)aminobenzene]-dibromocopper(11) has been reported61 and the dinuclear complex [Cu,( PAP)- (OH)Cl,]. 1.5H20(PAP = 1,4-di(2'-pyridyl)aminophthalazine)shown to have a hydroxide a chloride and a diazine (N-N) bridge.62 Cu" and Zn" complexes of an aroylhydrazone have been reported.63 Cu(L),X (X = C1 Br NO3; ClO and $SO,; L = benzylmethylketonesemicarbazone) have been prepared.64 CU" bromide complexes have been studied in anhydrous methanol.65 Exchange interactions have been measured in bis[ p-2-diethylamino)ethanolato]dibromodicopper( The II).~~ structures of three dinuclear five-coordinate Cu" complexes with phenolate bridges have been pre~ented.~~ The properties of [{Cu( Mesalen)},Fe(acac)]( NO3) have been The structures of [Cu,Li].9CH30H and [Cu4L:].8EtOH (where both L' and L2 are complex methylpyridine ligands) both contain tetrameric Cu" complexe~.~~ Thermo-dynamic data for the formation in benzene solutions of addition compounds of selected Cu" keto-enolate complexes with heterocyclic bases have been pre~ented.~' Structures of three types of alkoxo-bridged Cu" complexes have been studied.71 Paramagnetic Cu" ions in ethyleneglycol have been studied using H n.m.r.disper- 59 S. K. Hoffman D. K. Towle W. E. Hatfield P. Chaudhuri and K. Wieghardt Inorg. Chem. 1985 24 1307. 60 M. Mikuriay K. Toriumi T.Ito and S. Kida Inorg. Chem. 1985 24 629. 61 H. K. Blonk W. L. Driessen and J. Reeddijk J. Chem. Soc. Dalton Trans. 1985 1699. 62 L. K. Thompson F. W. Hartstock L. Rosenberg and T. C. Woon Inorg. Chim. Acta 1985 97 1. 63 C. Pelizzi G. Pelizzi G. Predieri and F. Vitali J. Chem. Soc, Dalton Trans. 1985 2387. 64 A. Jaggi S. Chandra and K. K. Sharma Polyhedron 1985,4 163. 6s P.G. David Polyhedron 1985 4 437. 66 A. Bencini D.Gatteschi C. Zanchini and W. Haase Inorg. Chem. 1985 24 3485. 67 Y. Nashida H. Shimo H. Maehara and S. Kida J. Chem. Soc. Dalton Trans. 1985 1945. 68 (a) I. Morgenstern-Badarau and H. H. Wickman J. Chem. Soc. Chem. Commun. 1985 176; (6)Inorg. Chem. 1985 24 1889. 69 H. Astheimer F. Nepveu L. Walz and W. Haase J. Chem.Soc. Dalton Trans. 1985 315. 70 D. P. Graddon S. Rochani and H. Way Inorg. Chzm. Acta 1985 104 87. 71 M. Mikuriya H. Okawa and S. Kida Inorg. Chim. Acta 1985 103 217. Cu Ag Au; Zn,Cd Hg sion7 and e.s.r. data of Cu"-oxime chelates have been discussed.73 Cu" has been extracted using long-chain aliphatic dioxime~.~~ Cu ions are five-coordinated in [(Et,dien)Cu(C2H,N,02)Cu( Et,dien)]( PF6)2 .75 Tunable interactions in p-oxamido Cu" dinuclear complexes have been e~tablished'~ and a five-coordinate Cu" complex containing a tridentate thioether-alkoxy ligand has been Cu2( Meiz),( OH),( C104)2.2H20 contains centrosymmetric [Cu,( Meiz),( OH),I2+ cations (8).78While the dinuclear p-pyrazolato-N,N'-bridgeddicopper(11) complex of 1,3-bis(salicylideneamino)propan-2-olis bridged by the secondary alkoxo-group and the pyrazolate moiety.79 N12 In [Cu(NH(py)2)(DTBSQ)]C104.0.5tetrahydrofuran (DTBSQ = di-t-butyl-o-semiquinone) each Cu ion is coordinated to two pyridyl N atoms and to two 0 atoms from the DTBSQ ligand.80 Studies on catecholate coordination to Cu" have appeared.81a,b The kinetics of the reaction between 1,3-dihydroxbenzene H202 and CU" ions have been studied.82 Formation equilibria of Cu" complexes with some pyridinals in various solvents have been presented,83 as have those of Cu" chelates of 1-hydroxypyrazole 2-oxides with substituted pyridine~.~~ More studies based on the classical cupric acetate dihydrate structure have been rep~rted~~'-~ H20)]2-2H20 has been shown to and [(N02C6H40CH2C00)2Cu( contain two Cu" ions bridged by four carboxylate groups.86 [Cu(AE)CH3C00I2 72 L.Banci I. Bertini and C. Luchinat Znorg. Chim. Acta 1985 100 173. 73 C. Kesavulu R. S. Naidu and R. R. Naidu Polyhedron 1985 4 761. 74 L. R. M. Paping C. P. J. Rummens P. H. A. Vriens J. H. M. C. van Wolput and T. P. M. Beelen Polyhdron 1985 4 723. 75 J. Sletten Acta Chem. Scand. Ser. A 1985 39 475. 76 Y. Journaux J. Sletten and 0. Kahn Znorg. Chem. 1985 24 4063. 77 R. T. Boere W. M. Brown D. W. Stephan and C. J. Willis Inorg. Chem. 1985 24 593. 78 A. Bencini D. Gatteschi and C. Zanchini Inorg. Chem. 1985 24 700. 79 W. Mazurek B. J. Kennedy K. S. Murray M. J. O'Connor J. R. Rogers M. R. Snow A. G. Wedd and P. R. Zwack Znorg. Chem. 1985 24 3258.no J. S. Thompson and J. C. Calabrese Inorg. Chern. 1985 24 3167. 81 (a) K. D. Karlin Y. Gultneh T. Nicholson and J. Zubieta Inorg. Chem. 1985 24 3725; (b) E. Balogh-Hergovich and G. Speier Znorg. Chim.Acra 1985 108 59. 82 R. H. Dinus Inorg. Chim.Acta 1985 99 217. 83 R. Bucci V. Carunchio A. M. Girelli and A. Messina Polyhedron 1985 4 1433. 84 F. Kai H. Haraga and H. Kobayashi Polyhedron 1985 4 947. 85 (a) B. Elman and C. Moberg J. Organomet. Chem. 1985 294 117; (b) J. S. Banait and P. K. Pahil Polyhedron 1985 4 1031; (c) L. S. Erre G. Micera P. Piu F. Canati and G. Ciani Inorg. Chem. 1985 24 2297; (d) M. Melnik K. Smolander and P. Sharrock Znorg. Chim.Acta 1985 103 187. 86 V. Adelskold J. Kratsmar-Smogrovic A. Valent P.-E. Werner M.Westdahl and M. Zemlicka Acra Chem. Scand. Ser. A 1985 39 163. 328 J. Silver (where AE = the anion of 7-amino-4-methyl-5-aza-3-hepten-2-one) contains two Cu atoms connected by a single atom bridge through one of the oxygen atoms of an acetate ligand.87 The structures of CU~(DCMPTA)~(X)~, (X = acetone or water) have been reported. They each contain tetracarboxylate bridged dimers.88a,b The structures of two complex substituted acetatobis( pyridine)Cu" molecules and two complex(ethanoato)Cu" molecules have been des~ribed.~~"?~ Equilibria between mono- and di-nuclear complexes in Cu( 02CMe),-pyridine derivative-diluent sys- tems have been studied." In the structures of [M(phen)2(02CMe)][X].2H,0 (when M = Cu X = ClO, NO, and when M = Zn X = BF,) complexes the MN402 chromophores all have a cis-octahedral stereo~hemistry.~' The structure of [C~(O~CCCl~)~(proxyl)]~~H~0 has been solved; it contains the stable nitroxyl radical 2,2,4,4-tetramethylpyrrolinyl-1 -oxy (proxyl) .92 The kinetics of ligand substitution in bis( N-R-sa1icyclaldiminato)Cu" com-plexes by bidentate ligands in methanol have been studied9 and spectral studies of Cu" complexes with amide group ligands have been reported.94 CU~(O~C-C~H~F~C~H~)~(THF)~-THF'~ is shown to contain both eclipsed and staggered ferrocenyl fragments.The structures of three { N-tosyl-((Y or p)-a1aninato)Cu" complexes have been pre~ented.~~ The results from a potentiometric study of the Cu2+-4( 5)-hydroxymethylimidazolesystem have been disc~ssed.~' The structure of [CU(~~~)(CF,SO,)H,O]~ (where pbt = Cl2N5H;) consists of dimeric [Cu2L2I2+ units.98 Dimerization of Cu" decanoate in 1,4-dioxane-water mixed solvents has been in~estigated.~~ A CU" complex of a neutral pentadentate Schiff base has been prepared,'" as have the Schiff base Cu" derivative of 1,8-dihydroxy-3,6-dimethy1-2-acetylnaph-thalene"' and the Cu" complexes of 'half-unit' Schiff bases.lo2 The enantioselectivity of Ni" and Cu" complexes of Schiff bases derived from amino-acids has been described" and a number of Cu" complexes with unsymmetrical tetradentate Schiff 87 J.-P.Costes F. Dahan and J.-P. Laurent Inorg. Chem. 1985 24 1018. 88 (a)C. H. L. Kennard G. Smith E. J. O'Reilly T. C. W. Mak and W.-H. Yip Inorg. Chim.Acta 1985 98 L3 1 ; (b) Polyhedron 1985 4 45 1. 89 (a)W. H. Chan T. C. W. Mak G. Smith E. J. O'Reilly and C. H. L. Kennard Polyhedron 1985 4 1443; (6) C. H. L. Kennard S. W. Stewart E. J. O'Reilly G. Smith and A. H. White Polyhedron 1985 4 697. 90 M. Szpakowska I. Uruska and J. Zielkiewicz J. Chem. Soc. Dalton Trans. 1985 1849. 91 W. Fitzgerald B. Hathaway and C. J. Simmons J. Chem. Soc. Dalton Trans. 1985 141. 92 L. C. Porter and R. J. Doedens Znorg. Chem. 1985 24 1006. 93 H. Elias C. Hasserodt-Taliaferro L. Hellriegel W. Schonheir and K. J. Wannowius Inorg. Chem. 1985 24 3198. 94 V. Ravindar S. J. Swamy S. Srihari and P. Lingaiah Polyhedron 1985 4 1511. 95 M. R. Churchill Y.-J. Li D. Nalewajek P. M. Schaber and J. Dorfman Inorg.Chem. 1985 24 2684. 96 L. Antolini L. P. Battaglia A. B. Corradi G. Marcotrigiano L. Menabue and G. C. Pellacani J. Am. Chem. Soc. 1985 107 1369. 97 L. H. J. Lajunen and S. Sjoberg Acta Chem. Scand. Ser. A 1985 39 341. 98 B. Prins P. J. M. W. L. Birker J. G. Haasnoot G. C. Verschoor and J. Reedijk Inorg. Chem. 1985 24 4128. 99 Y. Fujii K. Jimbo H. Yamada and M. Mizuta Polyhedron 1985 4 496. 100 E. Kwiatkowski T. Ossowski and A. Jankowska Polyhedron 1985 4 1191. 101 F. Teixidor L. Escriche A. Llobet and J. Casabo Polyhedron 1985 4 97. 102 N. A. Bailey D. E. Fenton J. R. Tate and P. M. Thomas J. Chem. Soc. Dalton Trans. 1985 1471. 103 Y. N. Belokon V. I. Maleyeu S. V. Vitt M. G. Ryzhov Y. D. Kondrashov S. N. Golubev Y. P. Vauchskii A.I. Kazika M. I. Novikova et al. J. Chem. Soc. Dalton Trans. 1985 17. Cu Ag Au; Zn Cd Hg bases have been ~repared."~"-~ A number of Cu" complexes containing the Schiff -base ligand derived from 2-pyridinecarbaldehyde and histamine have been st~died,"~ as has a flexible phenoxo-bridged dinuclear Cu" complex.'o6 The structure of (CUHAP~~)~VO(C~O~),.~H~O~$C~H~NO~ (where HAPen is a tetradentate Schiff base) contains a trinuclear cation; the chromophores of this are shown in (9).lo7 011 A number of Cu" complexes containing bridging azido-groups have been as has one containing a bridging hydrogencyanamido( 1-) group."' Cu" complexes containing isocyanato and isothiocyanato ligands have been reported.' 10a-c A tetraaminecopper(I1) complex has been studied in zeolite Y.'" Structures of Cu(X)(PPh,)+ (X = phen or dmp) indicate that steric crowding in the dmp structure originates from the 2-and 9-methyl substituents.'I2 The kinetics of quenching *Cu(dpp)i have been ~tudied."~ Proton n.m.r.studies of N,N-diethyl formamide (def) exchange on [Cu( Me6tren)def12+ have been pre~ented,"~ as have chiroptical properties of trigonal-bipyramidal complexes of Cu" containing an optically active tetraamir~e."~ Single-crystal e.p.r. spectra of [Cu,(tmbma),(bta)]( NO3) have been 104 (a) N. Matsumoto M. Asakawa H. Nogami M. Higuchi and A. Ohyoshi J. Chem. SOC. Dalton Trans. 1985 101; (b) N. Matsumoto M. Asakawa and A. Ohyosi J. Chem. SOC. Dalton Trans. 1985 107; (c) R. Atkins G. Brewer E.Kokot G. M. Mockler and E. Sinn Inorg. Chem. 1985 24 127; (d) K. Kasuga T. Nagahara and Y. Yamamoto Polyhedron 1985 4 415. 105 K. Matsumoto S. Ooi K. Nakatsuka W. Mori S. Suzuki A. Nakahara and Y. Nakao; J. Chem. SOC. Dalton Trans. 1985 2095. I06 W. Mazurek A. M. Bond K. S. Murray M. J. O'Connor and A. G. Wedd Znorg. Chem. 1985,24,2484. 107 A. Bencini C. Benelli A. Dei and D. Gatteschi Inorg. Chem. 1985 24 695. lo8 (a) M. A. S. Goher and T. C. W. Mak Inorg. Chim. Act 1985,99 223; (6) M.-L. Boillot Y. Journaux A. Bencini D. Gatteschi and 0. Kahn Znorg. Chem. 1985 24 263; (c) M.-L. Boillot 0. Kahn C. J. O'Connor J. Gouteron S. Jeannin and Y. Jeannin J. Chem. Soc. Chem. Commun. 1985 178. I 09 P. Chaudhun K. Wieghardt B. Nuber and J. Weiss J. Chem.SOC.,Chem. Commun. 1985 265. I10 (a) L. Schwabe and W. Haase J. Chem. SOC. Dalton Trans. 1985 1909; (b) L. Walz and W. Haase J. Chem. SOC. Dalton Trans. 1985 1243; (c) M. Di Vaira and F. Mani J. Chem. SOC. Dalton Trans. 1985 2327. P. K. Dutta and R. E. Zaykoski Znorg. Chem. 1985 24 3490. 112 J. R. Kirchhoff D. R. McMillin W. R. Robinson D. R. Powell A. T. McKenzie and S. Chen Inorg. Chem. 1985 24 3928. 113 R. E. Gamache Jr. R. A. Radar and D. R. McMillin Inorg. Chem. 1985 24 1141. 114 S. F. Lincoln A. M. Hounslow B. G. Doddridge J. H. Coates A. Merbach and D. Zbinden Inorg. Chim. Acta 1985 100 207. 115 S. Utsuno H. Miyamae S. Horikoshi and I. Endo Inorg. Chem. 1985 24 1348. 330 J. Silver recorded."6 Cu" complexes of aminopyridine 2,2'-bipyrimidine propane-1,3-diamine; and iminobis(acetamidoxime) have been rep~rted."~"-~ Several papers describing Cu" complexes in which the ligands bind to copper through both N and S atoms have appeared.118a-e The bis(2-thiopyridine-N- oxide) derivatives of Cu" and Ni' have been compared."' [NMe4]z[Cu(mnt)2] contains a columnar packing of Cu( mnt)q- ions which are unusually non-planar.I2' Cu" complexes containing dithiocarbamate groups dithiolates and diethyldithiocarba- mate groups have been studied.121u-c Two amorphous Cu" complexes of the dithiooxamide ligand (rubeanic acid) have been prepared122 and the role of the inductive effect in stabilizing Cu"-arsine complexes has been in~estigated.'~~ Macrocyclic Systems Containing Copper( 11).A linear trinuclear macrocyclic Cu" complex has been and the structures of two dinuclear macrocyclic Cu" complexes containing N and 0 bonds to copper rep~rted.'~~",~ A tritopic hexaaza- macrocycle has been shown to bond three Cu" ions so that it may be considered as a cryptate of a cationic cluster [CU~(OH)J~+.'~~ The coordination of Cu" by tetraazamacrocyclic ligands with pendant arms has been st~died,~"l",~ as has the dissociation of [Cu(cy~len)]~+.~~~ Preparations of a number of Cu" complexes of 1,4,7,10-tetraazacyclotridecaneand large ring macrocycles have been rep~rted'~'"~ and several studies describe tetraazamacrocyclic Cu" complexes.~30a-c A macrocyc-lic dioxotetraamine has been shown to act as a carrier for the membrane transport of Cu" ions.131 The photochemistry of a tetraene Cu" complex has been pre~ented'~' and the physico-chemical properties of cationic derivatives of phthalocyaninato- 116 A.Bencini D. Gatteschi J. Reedijk and C. Zanchini Inorg. Chem. 1985 24 207. 117 (a) S. Balzamo V. Carunchio R. Galvani and A. Messina Inorg. Chem. Acta 1985 97 13; (6)R. R. Ruminski Znorg. Chim.Acta 1985 103 159; (c) I. M. Vezzosi M. Saladini L. P. Battaglia and A. B. Corradi Inorg. Chim. Acta 1985 100 261; (d) M. Orama H. Saarinen T. Raikas and J. Korvenranta Acta Cfiern. Scand. Ser. A 1983 39 493. 118 (a)A. Sanco J. Borras L. Soto-Tuero C. Esteban-Calderon M. Martinez-Ripoll and S. Garcia-Blanco Polyhedron 1985 4 539; (b) J. Becher H. Toftlund P. H. Olesen and H. Nissen Inorg. Chirn.Acta 1985 103 167; (c) G. Davies N. El-Kady M. A. El-Sayed and A. El-Toakhy Inorg. Cfiim. Acta 1985 104 131; (d) G.-Z. Cai G. Davies A. El-Toukhy T. R. Gilbert and M. Henary Inorg. Chem. 1985 24 1701; (e) H. K. Baek R. L. Cooper and R. A. Holwerda Inorg. Chem. 1985 24 1077. I19 M. C. R. Symons and D. X. West J. Chem. Soc, Dalton Trans. 1985 379. 120 P. Kuppusamy and P. T. Manoharan Inorg. Chem. 1985 24 3053. 121 (a) A. F. Ellis M. J. Hudson and A. A. G. Tornlinson 1.Chem. SOC.,Dalfon Trans. 1985 1655; (b) G. E. Holdcroft and A. E. Underhill J. Chem. SOC.,Dalton Trans. 1985 1731; (c) T. Ohya K. Iwamoto and M. Sato J. Chem. SOC.,Dalton Trans. 1985 987. M. Abboudi A. Mosset and J. Galy Znorg. Chem. 1985 24 2091. 123 S. S. Parmar H.K. Bharaj and M. L. Sehgal Polyhedron 1985 4 959. 124 G. Ferguson C. R. Langrick D. Parker and K. E. Matthes J. Chern. SOC.,Chem. Commun. 1985 1609. 125 (a) J. Lorosch and W. Haase Inorg. Chim.Acta 1985 108 35; (b) F. Abraham J. M. Capon G. Nowogrocki and S. Saeur Polyhedron 1985 4 1761. 126 J. Comarmond B. Dietrich J.-M. Lehn and R. Louis J. Chem. SOC.,Chem. Commun. 1985 74. I27 (a)N. W. Alcock H. A. A. Omar P. Moore and C. Pierpont J. Chern. Soc. Dalton Trans. 1985 219; (b) N. W. Alcock P. Moore and H. A. A. Omar J. Chem. SOC.,Dalton Trans. 1985 1058. 128 R. W. Hay and M. P. hjari Znorg. Chim. Acta 1985 100 L1. 129 (a) R. W. Hay and M. A. Ali Inorg. Chirn. Acta 1985 103 23; (b) R. W. Hay and M. P. Pujari Inorg. Chim. Acta 1985 99 75.I30 (a) R. M. Clay S. Corr M. M. Chelori and P. Paoletti Inorg. Chem. 1985 24 3330; (b) M. Di Casa L. Fabbrizzi A. Perotti A. Poggi and P. Tundo Inorg. Chem. 1985 24 1610; (c) M. Kwiatkowskii and E. Kwiatkowski J. Cfiem. SOC.,Dalton Trans. 1985 803. 13' E. Kimura C. A. Dalimunte A. Yamashita and R. Machida J. Chem. SOC.,Dalfon Trans. 1985 1041. 132 G. Ferraudi P. Barrera J. Granifo J. H. Ham IV and D. P. Rillema. Inorg. Chem.. 1985 24 281. Cu Ag Au; Zn Cd Hg 331 copper(11) have been examined.133 Studies on substituted tetraphenylporphinato- copper( 11) complexes have been carried OU~.'~~',~ Novel polymer ligands contain- ing tetraazamacrocyclic Schiff bases as highly selective extractant for Cu" have been prepa~-ed.'~~'.~ The synthesis structure and electrochemistry of a large octaaza- cyclotetracosanedicopper( 11) complex has been di~cussed.'~~ The structures of bis( l-thia-4,7-diazacyclononane)copper( 11) and bis( 1,7-dithia-4-thiaheptane)-copper(11) nitrates have been Copper(111).Kinetic evidence supports the formation of a copper(II1) species when the aquocopper(1) ion reacts with H202 in aqueous solution.'38 A series of Cu'" complexes [Cu(SB)]ClO, where SB is a dibasic tetradentate Schiff's base have been synthesi~ed.'~~ Cu"'-imine-oxime complexes have been used as oxidizing agents.140 In the structure of [(Ph,P),N][Cu(Dto),] (where Dto = dithiooxalate) the Cu"'-S bond lengths are 2.164( 1) and 2.178( 1) A.141 Mixed-ualence Complexes. The electrical and magnetic properties of K3Cu8S6 demon- strate that this mixed-valence compound is metallic at high temperature^.'^^ The structure of the polymeric penta-p-chloro-tris-p-tetrahydrothiophenetetra-copper(I 11) has been s01ved.l~~ Structural changes accompanying electron transfer in Cu"/Cu' complexes involving related open-chain and cyclic tetrathiaether ligands have been discussed.It is speculated that the 0.2-0.3 V difference in the CU"L/CU'L potentials is largely attributable to the presumed difference in the number of S atoms coordinated to CU'.'~ Cu"/ Cu"' couples are identified in dinuclear copper( 11) comp~exes.'~~ Copper Compounds of Biological Interest. Cu" complexes of a number of amino-acids have been rep~rted.'~~'-~ The CU" complexes of 2-(trifluoromethyl)-~-histidine have been investigated in aqueous solution.'47 In [Cu(TsGlyH),(bpy)],.H,O the Cu 133 A.Skorobogaty T. D. Smith G. Dougherty and J. R. Pilbrow J. Chem. SOC. Dalton Trans. 1985 651. 134 (a) L. Latos-Grazynski and A. Jezierski Inorg. Chim. Acta 1985 106 13; (b)W. V. Sweeney D. Kuila and D. V. Lavallee Znorg. Chim. Acta 1985 99,L9. 135 (a) N. Kubota M. Fujiwara T. Matsushita and T. Shono Polyhedron 1985,4 1051; (b) M. Fujiwara Y. Nakajima T. Matsushita and T. Shono Polyhedron 1985 4 1589. I36 A. Bianchi S. Mangani M. Micheloni V. Nanini P. Orioli P. Paoletti and B. Seghi Inorg. Chem. 1985 24 1182. I37 J. C. A. Boeyens S. M. Dobson and R. D. Hancock Inorg. Chem. 1985 24 3073. 138 G. R. A. Johnson N.9. Nazhat and R. A. Saadalla-Nazhat J. Chem. SOC.,Chem. Commun. 1985,407. 139 S. M. Abu-El-Wafa R. M. Issa and C. A. McAuliffe Inorg. Chim. Acta 1985 103. 140 N. I. Al-Shatti M. A. Hussein and Y. Sulfab Inorg. Chim. Acta 1985 129. 141 M. G. Kanatzidas N. C. Baenziger and D. Coucouvanis Inorg. Chem. 1985 24 2680. 142 (the late) D. 9. Brown E. Kwiatkowski and Z. Peplinski J. Chem. SOC. Dalton Trans. 1985 2319. 143 E. W. Ainscough A. M. Brodie J. M. Husbands G. J. Gainsford E. J. Gabe and N. F. Curtis J. Chem. SOC.,Dalton Trans. 1985 151. 144 L. L. Diaddario Jr. E. R. Dockal M. D. Click L. A. Ochrymowycz and D. 9. Rorabacher Inorg. Chem. 1985 24 356. 145 P. S. Zacharias and A. Ramachandraiah Polyhedron 1985 4 1013. 146 (a) I.L. Ulanovski A. A. Kurganov and V. A. Davankov Znorg. Chim. Acta 1985 104 63; (b) M. T. L. S. Duarte M.A. A. F. de C. T. Carrondo M. L. S. Goncalves M. 9. Hursthouse N. P. C. Walker and H. M. Dawes Inorg. Chim. Acta 1985 108 11; (c) S.-B. Teo and S.-G. Teoh Znorg. Chim. Acta 1985 107 35; (d) S.-9. Teo S.-G. Teoh and M. R. Snow Inorg. Chim. Acta 1985 107 211; (e) G. Thomas and P. S. Zacharias Polyhedron 1985 4 299; (f)B. Henry J.-C. Boubel and J.-J. Delpuech Polyhedron 1985,4 1069; (g) G. B. Gavioli G. Grandi L. M. Menabue G. C. Pellacani and M. Sola J. Chem. Soc. Dalton Trans. 1985 2363. 147 L. Casella and M. Gullotti Inorg. Chem. 1985 24. 84. 332 J. Silver atom is in a distorted square pyramidal c~ordination.'~' E.s.r. parameters for some Cu"-bis( amino-acid) complexes have been pre~ented.'~~ The Cu" complex formation equilibria of D-ghcosamine were studied in aqueous solution.'50 Complexes of Cu" with di- tri- and oligo-peptides have been di~cu~~ed,'~'~-~ as has the binding of Cu" and Zn" to oxidized gl~tathione.'~' Tetrahedral 1 :1 adducts of guanine with Cu" and Zn" have been prepared.'53 The structures of guanosine 5'-monophosphate and inosine 5'-monophosphate complexes of Cu" have been ~olved'~~~,~ and the Cu" complexes of 9-substituted purines prepared.15' An interesting study showed that adenine N' -oxide is de- graded at a higher pH than expected when Cu" ions are present.'56 The magnetic properties of bis-adenoxine 5'-triphosphato)(2,2'-bipyridine)Cu1']tetrahydrate have been studied.'57 The inhibitory activity of Cu" complexes on the Ca,Mg-dependent ATP-ase substrate has been rep~rted.'~' The synthesis has been reported for a series of Cu" a~pirinates'~~ and the complexation of cefazolin with Cu" ions has beeen investi- gated.'60 Cu" complexes of anti-inflammatory drugs have been isolated'61"*b and antitumour Cu" drugs studied.'62",b Cu" binding by substituted 1,3,5-triazine herbi- cides has been estab1i~hed.I~~ E.p.r.studies on the Cu" complex formation with creatinine suggest that a four-membered chelate is formed.'64 The binding of Cu and Zn to enalaprilat has also been re~0rted.I~~ Reports on dinuclear copper complexes as models for multicopper enzymes have and model complexes for haemocyanin and methaemocyanin have been Intereaction of Cu" and Zn" with humic-like models (2,4-dihydroxybenzoic acid) have been reported.I6' 148 L.Antolini L. Menabue and M. Saladini Inorg. Chim. Acta 1985,24 1219. 149 B. A. Goodman and D. B. McPhail J. Chem. SOC.,Dalton Trans. 1985 1717. 150 G. Micera S. Deina A. Dessi P. Decock B. Dubois and H. Kozlowski Inorg. Chim.Acta 1985 107 45. 151 (a) A. Desideri L.Sportelli R. Bartucci and S. Morante Inorg. Chim.Acta 1985 106 85; (b) M. J. A. Rainer and B. M. Rode Inorg. Chim. Acta 1985,107,127;(c) H. Sapper H.-H. Paul K. Beinhauer and W. Lohmann Inorg. Chim. Acta 1985 106 25. 152 W. S. Postal E. J. Vogel C. M. Young and F. T. Greenaway J. Inorg. Biochem. 1985,25 25. 153 C. M. Mikuski L. Mattuci L.Weiss and N.M.Karayannis Inorg. Chim. Acta 1985 107 81. 154 (a) S. Mangani and P. Orioli J. Chem. Soc. Chem. Commun. 1985 780; (b) M. D. Poojary and H. Manohar Inorg. Chem. 1985,24 1065. 155 J. Arpalahti and E. Oltiola Inorg. Chim.Acta 1985 107 105. 156 E. Sletten T.Martinsen and J. Sletten Inorg. Chim. Acta 1985 106 1. 157 C. Benelli D.Gatteschi and R. L. Carlin Inorg. Chem. 1985,24 3081. 158 L. V. Tatjanenko Yu.Sh. Moshkovsky I. A. Zakarova G. Ponticelli M. Massacesi and G. Devoto Polyhedron 1985,4,159. 159 J. L. Meier C. E. Coughenour J. A. Carlisle and G. 0.Carlisle Inorg. Chim. Acta 1985,106,159. 160 B. Ogorevc V. Hudnik S. Gomiscek M. R. Smyth and J. G. Vos Inorg. Chim. Acta 1985 108 L3. 161 (a) D. 0.Harrison R. Thomas A.E. Underhill J. K. Fletcher P. S. Gomm and F. Hallway Polyhedron 1985,4,681;(b) J. Garcia M. Molla and J. Borras Polyhedron 1985,4,757. 162 (a) P.Lumme and H. D. Elo Inorg. Chim. Acta 1985 107 L15; (b) D.L. Banville W. D. Wilson and L. G. Marzilli Inorg. Chem. 1985,24,2479. 163 P. Decock B. Dubois J. Lerivrey G. Gessa J. Urbanska and H. Kozlowski Inorg. Chim. Acta 1985 107,63. 164 M. Mitewa P. R. Bontchev and K. Kabassanov Polyhedron 1985,4,1159. 165 M. A. Hughes G. L. Smith and D. R. Williams Inorg. Chim.Acta 1985 107 L11. 166 (a) J. M. Latour D. Limosin and S. S. Tandon Inorg. Chim.Acta 1985 107 L1; (b) H. P. Berends and D. W. Stephan Inorg. Chim.Acta 1985,99 L53; (c) M. Rosi A. Sgamellotti F. Tarantelli I. Bertini and C.Luchinat Inorg. Chim. Acta 1985 107 L21. 167 (a)J. Lorosch H. Paulus and W. Haase Inorg. Chim. Acta 1985 106 101; (6) V.McKee M. Zvagulis and C. A. Reed Inorg. Chem. 1985,24 2914. 168 G. Micera L. S. Erne F. Cariati G. Ciani and A. Sironi Inorg. Chim.Acra 1985 108 L1. Cu Ag Au; Zn Cd Hg 333 Many enzymes containing copper have been studied these include superoxide di~mutase,'~~~-~ and ascorbate 0xida~e.l~' plast~cyanin,'~~"'~ The Cu" catalysed hydrolysis of thiaminepyrophosphate has been in~estigated,'~~ as have some of the properties of biologically significant phosphorylated compounds as ligands of cop-per.'73 Polymerization was found when lysozyme is treated with Cu" and H202.174 Silver.-A useful review of silver chemistry has appeared re~ent1y.l~~ Silver Heterometallic Clusters.[a2( q-C5H5)2( p-CO)( p-Ph2PCH2PPh2)( p-AgOPF20)] contains a triangular Rh-Ag cluster,'76 and a planar hexametallic cluster containing a triangle of Ag atoms within a triangle of Rh atoms has been rep~rted.'~~ A wide variety of mixed-metal cluster compounds containing Cu and/or Ag atoms ligated by mono-or bi-dentate phosphine have been prepared.17' [Ag2{p-(R)(S)-1,2-(thi0phene-2-CH=N)~cyclohexane}~](O~SCF~)~ been has shown to contain an Ag'-Ag' separation of 2.909( 1) [Li6Br4(Et20)1ol2' [Ag3Li2Ph6] contains a trigonal-bipyramidal Ag3Li2 cluster (10) with the Li atoms in the axial positions.'*' Silver (I). The structures of adducts of Ag' bromide with monomethyl-substituted pyridine bases have been compared."' Heterobimetallic molecules containing platinum dicyanides terminal or bridging Ph2PCH2PPh2 and AgI Au and HgC12 have been prepared.182 The first stability constant measurements in liquid ammonia solutions for complexation of Ag+ by CN- and SCN- have been rep~rted."~ Chemical and structural aspects of Ag-triphenylarsine complexes and silver-tin complex salts have been pre~ented.''~ Macrocyclic Systems containing Silver Ions. The structure of [Ag( RS)-1,2-(5-R-thio-2- CH=N)2-c-Hx)2](03SCF3)(R = Me thio = thiophene c-Hx = cyclohexane) has been refined; the structure of the cation is shown (ll).185 Ag" and Pd" metalloporphyrins are found to be homogeneous catalysts for the electrochemical reduction of C02 in CHC1 A self-exchange rate constant for 169 (a) A.Bencini D. Gatteschi C. Zanchini J. G. Haasnoot R. Prins and J. Reedijk Inorg. Chem. 1985 24 2812; (b) I. Bertini C. Luchinat and R. Monnanni J. Am. Chem. SOC.,1985 107 2178; (c) U. Deuschle and U. Weser Inorg. Chim. Acta 1985 107 275; (d) A. Gartner M. Schroth-Pollmann and U. Weser Inorg. Chim. Acta 1985 107 117. I70 (a) F. A. Armstrong P. A. Cox H. A. 0. Hill B. N. Oliver and A. A. Williams J. Chem. Soc. Chem. Commun. 1985 1236; (b) B. S. Brunschwig P. J. Delaive A. M. English M. Goldberg H. B. Gray S. L. Mayo and N. Sutin Inorg. Chem. 1985 24 3743. 171 L. Casella M. Gullotti and A. Marchesini Inorg. Chim. Acta 1985 107 19. 172 B. T. Khan and P. N. Rao Znorg. Chim. Acta 1985 106 97. 173 S. Amani L. J. Theriot and L.S. Daley Inorg. Chim. Acta 1985 100 L23. 174 J. 0. Kang P. C. Chan and L. Kesner Inorg. Chim. Acta 1985 107 253. 175 W. E. Smith Coord. Chem. Rev. 1985,67 297. 176 G. Bruno S. Lo Schiavo P. Piraino and F. Faraone Organometallics 1985 4 1098. 177 F. Bachechi J. Ott and L. M. Venanzi J. Am. Chem. SOC.,1985 107 1760. 178 S. S. D. Brown I. D. Slater and B. M. Smith J. Chem. SOC.,Chem. Commun. 1985 1439. 179 G. C. Van Stein G. Van Koten F. Blank L. C. Taylor K. Vrieze A. L. Spek A. J. M. Duisenberg A. M. M. Schreurs B. Kojic-Prodic and C. Brevard Inorg. Chim. Acta 1985 98 107. 180 M. Y. Chiang E. Bohlen and R. Bau J. Am. Chem. SOC.,1985 107 1679. 181 P. C. Healy N. K. Mills and A. H. White J. Chem. SOC.,Dalton Trans. 1985 111. 182 F.S. M. Hassan D. P. Markham P. G. Pringle and B. L. Shaw J. Chem. SOC.,Dalton Trans. 1985,279. 183 Y. M. Cheek P. Gans and J. B. Gill J. Chem. Soc. Dalton Trans. 1985 628. 184 M. Nardelli C. Pelizzi G. Pelizzi and P. Tarasconi J. Chem. Soc. Dalton Trans. 1985 321. I85 G. C. van Stein G. van Koten K. Vrieze A. L. Spek E. A. mop and C. Brevard Inorg. Chem. 1985 24 1367. 186 J. Y. Becker B. Vainas R. Eger and L. Kaufman J. Chem. SOC.,Chem. Commun. 1985 1471. 334 J. Silver Ag"/Ag"'-tetra(4-sulphonatophenyl)porphyrins has been mea~ured'~' and the monomer-dimer reaction of tetrakis [{p-(trimethy1ammonio)phenyl)por-phinato]Ag"' in aqueous medium has been studied.18' Silver( 111). The kinetics of Ag"' reduction by the octacyano-complexes of MotV and WiV have been rep~rted"~ and the reaction of the tetrahydroxoargentate( 111) ion with thiosulphate investigated.'" Complexes of Ag"' with the oxoanions (phos- 187 R.Langley P. Hambright and R. F. X. Williams Znorg. Chim. Ac~Q, 1985,104,L25. 188 M.Krishnamurthy and J. R. Sutter Inorg. Chem. 1985,24,1943. 189 E.T. Borish L. J. Kirschenbaum and E. Mentasti J. Chem. SOC.,Dalton Trans. 1985 1789. 190 J. D.Rush and L. J. Kirschenbaum Inorg. Chem. 1985,24 744. Cu Ag Au; Zn Cd Hg phate carbonate borate pyrophosphate and arsenate) have been reported in aqueous solution.lg1 Gold.-A useful review of gold chemistry has appeared.lg2 Evidence for the gold anion in ethylenediamine has been reported.'93 Gold Heterometallzc Complexes.A number of papers concerning gold atoms in heterometallic clusters including structural have been reported (Table)-the structure of the anion [Au3Cu2(C2Ph)J is shown (12).203 Substitution of Au(PPh3) for hydrogen in [RU~H~(CO)~~] has been shown to activate the cluster.204 Gold Clusters. The structures of several gold clusters have been including those shown in (13)205 (14).206Studies of gold cluster compounds using high resolution 31P solid-state n.m.r. spectroscopy209 have also been reported. 191 J. D. Rush and L. J. Kirschenbaum Polyhedron 1985,4 1573. 192 W. E. Smith Coord. Chem. Rev. 1985 67 311. 193 R. Jagannathan D. W. Wallace and J. J. Lagowski Inorg. Chem. 1985 24 113. 194 M. I. Bruce E. Horn 0. B. Shawkataly and M.R. Snow J. Organomet. Chem. 1985 280 289. 195 M. I. Bruce 0. B. Shawkataly and B. K. Nicholson J. Organomet. Chem. 1985 286 427. 196 K. Henrick B. F. G. Johnson J. Lewis J. Mace M. McPartlin and J. Moms J. Chem. Soc. Chem. Commun. 1985 1617. 197 M. I. Bruce E. Horn J. G. Matisons and M. R. Snow J. Organomet. Chem. 1985 286 271. 198 C. M. Hay B. F. G. Johnson J. Lewis R. C. S. McQueen P. R. Raithby R. M. Sorrel] and M. J. Taylor Organometallics 1985 4 202. 199 C. F. Barrientos-Penna F. W. B. Einstein T. Jones and D. Sutton Inorg. Chem. 1985 24 632. 200 A. L. Casalnuovo T. Laska P. V. Nilsson J. Olofson and L. H. Pignolet Znorg. Chem. 1985 24 233. 20 1 A. L. Casalnuovo T. Laska P. V. Nilsson J. Olofson L. H. Pignolet W. Bos J.J. Bour and J. J. Steggerda Znorg. Chem. 1985 24 182. 202 A. L. Casalnuovo J. A. Casalnuovo P. V. Nilsson and L. H. Pignolet Znorg. Chem. 1985 24 2554. '03 0. M. Abu-Salah A.-R. A. Al-Ohaly and C. B. Knobler J. Chem. Soc. Chem. Commun. 1985 1502. 204 J. Evans and G. Jingxing J. Chem. Soc. Chem. Commun. 1985 39. 205 H. H. Murray 111 J. P. Fackler Jr. and D. A. Tocher J. Chem. Soc. Chem. Commun. 1985 1278. 206 B. Chiari 0. Piovesana T. Tarantelli and P. F. Zanazzi Inorg. Chem. 1985 24 366. 207 H. H. Murray J. P. Fackler Jr. and B. Trzcinska-Bancroft Organometallics 1985 4 1633. 208 H. H. Murray A. M. Mazany and J. P. Fackler Jr. Organometallics 1985 4 154. 209 N. J. Clayden C. M. Dobson K. P. Hall D. M. P. Mingos and D. J. Smith J. Chem.Soc. Dalton Trans. 1985 1811. 336 J. Silver Table Gold-containing cluster complexes Complex Structure of Cluster R ej [Ru,Au~( p-C=CHBu')( CO),( PPh,),] Asymmetric trigonal-194 bipyramidal Ru3Au2 core Trigonal-bipyramidal Ru3Au 195 core Butterfly AuRu core 195 Butterfly AuRu core 195 Both isomer cluster occur in the 196 same crystal both have a square- pyramidal Ru arrangement but distinctly different bonding of the AuPEt group Both clusters similar differ in 197 orientation of PPh group. The Os3Au core is a butterfly Open bicapped Os,Au butterfly 198 Diedge-bridged tetrahedral 198 Os4Au2 framework Re-Au bond = 2.615(1) 8 199 Ir-Au bond = 2.625( 1) A 200 Equilateral AuJr triangle 201 IrAu core (distorted trigonal- 202 bip yramidal) Au3CuZ core 203 Au-Au bond = 2.653( 1) A 205 Au cluster Au atoms at the ver- 206 tices of a rhombus Au-Au bond = 2.681(1)8 207 Au-Au bond = 2.684(4) 8 207 Au-Au bond = 2.637(2)A 208 Gold(I).[Au2(Ph2PCH2CH2PPh2)C12](15) contains Au atoms in linear coordina- tion with pairs of molecules being held together by weak intermolecular Au...Au interactions of 3.189 A.21oDinuclear and polymeric Au' complexes have been subjected to qualitative molecular orbital studies.211 The synthesis and properties of aurated derivatives of dicyclopropyl ketone have been reported.212 [{Au( PPh,)},{p-C( PPh,)COEt)]ClO contains a short Au- ..Au contact of 2.892(2) A.213 Gold (zzz). [Au( NH3),Br2]Br contains a planar trans-complex Tri-chloro[ (dimethylamino)ethoxycarbene]gold(111) and its triiodo-derivative and two other gold( 111) carbenes have been prepared.215 Square planar coordinated gold (16) is found in tetrabutylammonium tetraphenylaurate( III).~'~ In [Me2AuSC2H5I2 210 P.A. Bates and J. M. Waters Znorg. Chirn. Acta 1985 98 125. 211 Y. Jiang S. Alvarez and R. Hoffman Inorg. Chern. 1985 24 749. 212 E. G. Perevalova I. G. Bolesev Yu. T. Struchkov I. F. Leschova Ye. S. Kalyuzhaya T. I. Voyevodskaya Yu. L. Slovokhotov and K. I. Grandberg J. Organornet. Chern. 1985 286 129. 213 J. Vicente M. T. Chicote J. A. Cayuelas J. F. Baeza P. G. Jones G. M. Sheldrick and P. Espinet J. Chern. Soc. Dalton Trans, 1985 1163. 214 K. Kaas and L. H. Skibsted Acta Chern. Scand.Ser. A 1985 39,1. 215 E. 0. Fischer and M. Bock J. Organornet. Chern. 1985 287 279. 216 A. J. Markwell J. Organornet. Chern. 1985 293 257. Cu,Ag Au; Zn Cd Hg 33 8 J. Silver the Au.-.Au distance is 3.457(3) 8 suggesting little evidence for an Au-Au bond.217 Steric and electronic effects on the tertiary phosphine ligand on the dissociative reductive elimination from cis-aryldimethyl(triarylphosphine)gold(111) have been reported.21s (p-CH,)[Au(CH2),PPh,l,(CN) is formally a Au"' 'complex with an Au.-.Au distance of 3.167(3) In the structure of truns,truns-[Ph2P(CH,),AuBr2] no evidence for a metal-metal has been found.219 Various Au"' derivatives of pyrazoles have been characterized.,,' The coordination chemistry of dimethylgold(111) has been studied with pyridyl and N-methylimidazoyl ketones and polydentate ligands.221".b Miissbuuer Spectroscopy.Parameters have been reported for [Au( C6F5)X( L- L)]C104 and [Au(C6F5)(PPh3)(L-L)](CIo,) complexes (where L-L = phen o-pheny lene-bis( dimethylarsine); X = C1 Br).222 Mixed-valence Chemistry. The synthesis of trinuclear Au' and Au"' complexes containing the tridentate bis(dipheny1phosphine)methanide ligand has been described223 and the isomerization of a symmetrical Au"-Au" bonded ylide dimer to a mixed-valence Au"'/Au' species has been reported.224 Gold Compounds ofBiologicul Interest. Au"' and Rh"' chloride adducts with adenine have been Tertiary phosphine complexes of Au' and Au"' with imide ligands have been prepared226 and the (imido) Au' triethylphosphine complexes have all been found to be orally active anti-inflammatory agents.The (imido)Au"' phos- phines were not tested as anti-inflammatory because of their high chemical reac- tivity.226 Gold-binding sites in the plasma of patients with rheumatoid arthritis undergoing treatment with myocrisin have been studied.227 2 Zinc Cadmium and Mercury As large a covering of the 1985 papers dealing with Zn Cd and Hg as possible is attempted here but papers covering more than one element in the group are cited in the first occasion only viz. a paper covering Zn Cd and Hg is cited only in the zinc section. Zinc.-The compounds LiZn2N0308 Zn3M0305 and ScZnMo,O all have been shown to contain reduced cluster Mo3OI3units.228 The syntheses of MSn(OH) and 217 H.W. Chen C. Paparizos and J. P. Fackler Jr. Inorg. Chim. Acta 1985,96 137. 218 S. Komiya and A. Shibue Organometallics 1985,4 684. 219 D. S. Dudis and J. P. Fackler Jr. Znorg. Chern. 1985,24 3758. 220 A. L.Bandini G.Banditelli F. Bonati G. Minghetti and M. T. Pinillos Inorg. Chim. Acta 1985,99,165. 22 1 (a) P. K. Byers A. J. Canty L. M. Engelhardt J. M. Patrick and A. H. White J. Chem. SOC.,Dalton Trans. 1985 981; (b) P. K.Byers A. J. Canty N. J. Minchin J. M. Patrick B. W. Skelton and A. H. White J. Chem. Soc. Dalton Trans. 1985 1183. 222 R. Uson A. Laguna M. U. De La Orden R. V. Parish and L. S. Moore J. Organomet. Chem. 1985,145. 223 R. Uson A. Laguna M. Laguna B. R. Manzano P. G. Jones and G. M. Sheldrick J.Chem. Soc. Dalton Trans. 1985 2417. 224 J. P. Fackler Jr. and B. Trzcinska-Bancroft Organometallics 1985,4 1891. 225 C.M. Mikulski D. Braccia D. Delacato J. Fleming D. Flemming and N. M. Karayannis Inorg. Chim. Acta 1985,106 L13. 226 S. J. Price M. J. DiMartino D. T. Hill R. Kuroda M. A. Mazid and P. J. Sadler Lnorg. Chem. 1985 24 3425. 227 W.E. Smith D. H. Brown and H. A. Cappell Inorg. Chim. Acta 1985,106 L23. 228 C. C. Toradi and R. E. McCarley Inorg. Chem. 1985,24 476. Cu Ag Au; Zn Cd Hg MSnO (M = Zn Cd) have been described229 and Zn3Rb2(P207) shown to contain a 3D network of ZnO and PO4 tetrahedra.230 A number of known zinc thiocyanate complexes have been prepared by direct electrochemical synthesis.231 Zinc( 11) carbonate complexes have been studied in acid solution.232 A general method for the synthesis of the p~lysulphido[M(S,),]~- complexes (M = Zn x = 4-6; M = Cd x = 5) has been described.z33 The stability constants of zinc halide complexes in DMSO-water and DMF-water mixtures have been determined.234 V[Zn(Cl),(THF)(PPh,)],.2CH,C16 is a d lo-d3-d" trinuclear bimetallic linear complex of zinc and vanadium (Zn-V = 3.289(1) while ([Zn(H,O),]-[Zn2{P(CH2CH2C02)3}2]~7H20),, consists of [Zn{P(CH2CH2C02)3}]- anions con- taining tetrahedrally coordinated zinc atoms.236 Thermochemical data for adducts of Zn Cd and Hg halides with hexamethylphosphoramide have been reported.237 [V(NCMe),ZnCI,] contains [V(NCMe),] species with a formal charge of 2+ and a tetrachlorozincate moiety.,,* (THF),V( p-C1),ZnC12 also contains Zn atoms in virtually tetrahedral geometry.239 The syntheses of [Zn(ML,),] (M = K Rb or NH4) (L = an open chain polyether) complexes were described and the structure of the NH4 complex reported.240 [(C1,(MeOCH2CH,OMe)Ta(p-CCMe3)},Zn( p-Cl),] reacts with acetylates to form products in which two acetylene molecules and one alkylidyne moiety have formed a cyclopentadienyl ligand.241 The generation of ZnS from zinc dithiolenes has been described.242 The crystal structure of the salts of [M4(SPh)lo]2- anions (M = Zn Cd) have been The anion consists of a tetrahedron of metal atoms bridged by SPh groups (17).243 229 M.Inagaki T. Kurosichi Y. Yamashita and M. Urata Z. Anorg. Allg. Chem. 1985 527 193. 230 M.T. Averbuch-Pouchot 2. Kristallogr. 1985 171 113. 231 C. Oldham M. J. Taylor and D. G. Tuck Znorg. Chim. Acta 1985 100 L9. 232 D. Ferri I. Grenthe S. Hietanen E. Neher-Neumann and F. Salvatore Acta Chem. Scand. Ser. A 1985 39,347. 233 D. Coucouvanis P. R. Patil M. G. Kanatzidis B. Detering and N. C. Baenziger Inorg. Chem. 1985 24 24. 234 F. Gaizer H. B. Silber and J. Lazar Polyhedron 1985 4 1467. 235 F. A. Cotton S. A. Duraj W. J. Roth and C. D. Schmulbach horg. Chem. 1985 24 525. 236 J. Podlahova B. Kratochvil J. Podlaha and J. Haset J. Chem. SOC. Dalton Trans. 1985 2393. 237 J. C. de Querioz C. Airoldi and A. P. Chagas J. Chem. Soc. Dalton Trans. 1985 1103. 238 P. Chandrasekhar and P. H. Bird Znorg. Chim. Acta 1985 97,L31. 239 P.D. Smith J. L. Martin J. C. Huffman R. L. Bansemer and K. G. Caulton Znorg. Chem. 1985,24,2997. 240 D. L. Hughes and J. N. Wingfield J. Chem. SOC. Dalton Trans. 1985 459. 241 H. van der Heyden A. W. Gal P. Pasman and A. G. Orpen Organometallics 1985 4 1847. 242 N. Zeug J. Bucheler and H. Kisch J. Am. Chem. SOC. 1985 107 1459. 243 J. L. Hencher M. A. Khan F. F. Said and D. G. Tuck Polyhedron 1985 4 1263. 340 J. Silver The structure of sulphato-bis(thiosemicarbazide)zinc(11) has been described244 and [Zn,( p-SEt),( SEt),12- anions shown to be edge-shared tetrahedra.245 The Zn-S bond enthalpy has been determined in bis(diethyldithiocarbamato)zinc(11)~~~ and the electrochemical oxidation of zinc bis( 0,O-dialkylphosphorodithioates-S,S’) reported.247 The trinuclear complex [Zn3(MeCH=CHC02)6(C9H7N)z]contains a linear array of Zn atoms bridged by crotonate ligand~.’~* The structures of three monomethyl carbonato Zn” complexes have been reported,249u and a number of (monoalkyl carbonato)(tetraazacycloalkane)zinc(II) complexes have been characterized.249b Molecular orbital calculations on the model complex H,ZnC2H4 have been reported;250 Et,Zn contains infinite chains of zinc atoms with bridging cyclo- pentadienyl groups.It appears that both cr-and wtype interactions contribute to the cyclopentadienyl-zinc bonds.251 In [p-Ni(C5H5)PPh3][p-C5H5][ZnC5H5]2 (18) the Zn atoms are bridged by both the Ni atom and a C5H5 ring.252 The molecular structure of (Me5Cs),Zn (19) has been determined using electron diff ra~tion.’~~ The reaction of (C,Me5),Zn with bis(cyc1oocta-1 ,Sdiene)nickel gives (C5Me5Ni)2C16H24 via a novel zinc-induced ligand coupling.254 Pentadienylmetal compounds including (C5H7),Zn have been reviewed.255 C-C bond formation in reactions between tolylmethylidyne(dicarbonyl)(cyclopentadienyl)tungsten and di- organozinc reagents have been presented.256 2M S.Larsen and F. S. Nielsen Acta Chem. Scand. Ser. A 1985 39 441. 245 A. D. Watson C. H. Pulla Rao J. R. Dorfman and R. H. Holm Znorg. Chem. 1985 24 2820. 246 C. Airoldi J. Chem. Soc. Dalton Trans. 1985 369. 247 R. L. Blankespoor Inorg. Chem. 1985 24 1126. 248 W. Clegg I. R. Little and B. P. Straughan J. Chem. SOC.,Chem. Commun. 1985 73. 249 (a) M.Kato and T. Ito Inorg. Chem. 1985 24 509; (b) ibid 1985 24 504. 250 0. Gropen A. Haarland and D. Defrees Acta Chem. Scand. Ser. A 1985 39 367. 251 P. H. M. Budzelaar J. Boersma G. J. M. van der Kerk A. L. Spek and A. J. M. Duisenberg J. Organomet. Chem. 1985 281 123. 252 P. H. M. Budzelaar J. Boersma G. J. M. van der Kerk A. L. Spek and A. J. M. Duisenberg J. Organomet. Chem. 1985 287 C13. 253 R. Bloom A. Haaland and J. Weidlein J. Chem. SOC.,Chem. Commun. 1985 266. 254 B. Fischer J. Boersma B. Kojic-Prodic and A L. Spek,J. Chern Soc. Chem. Commun. 1985 1237. 255 H. Yasuda and A. Nakamura J. Organomet. Chern 1985 285 15. 256 J. C. Jeffery A. L. Ratermann and F. G. A. Stone J. Organomet. Chem. 1985 289 367. Cu Ag Au; Zn Cd Hg 341 Radical formation in the exchange interactions of some Zn Cd and Hg com- pounds has been investigated.257 Treatment of silyl-protected terminal alkynes con- taining an allylic alcohol moiety with Me,Al Bu',AlH ZnCl, and a catalytic amount of Pd(PPh,), induces cyclization in cases where the reaction can lead to the formation of five-membered rings via a-or y-The regioselectivities of vinylstannanes obtained from the reaction of terminal acetylenes with (Bu;Sn)2Zn in the presence of transition metal catalysts has been described,259 as have those of organozinc compounds derived from y-bromocrotonic and y-bromosenecioic trimethylsilyl esters.260 Substituted bis-( N-isopropylsalicylaldiminate)complexes of Zn" have been studied using 'H n.m.r.spectroscopy261 and a 13C n.m.r.study of the complexes formed between Zn" and trimethylentetraamine have been reported.262 Bis[ p-(tetracarbonylcobalt)zincio]( p-carbonyl)hexacarbonyldicobaltconsists of two trigonal Co(CO) units in an eclipsed configuration and bridged by one carbonyl ligand and two ZnCo(CO) Spectroscopic evidence for a new surface carbonyl species on a Cu/ZnO catalyst has been Mucrocylic Zinc Compounds. In the structure of ZII(TPP)(THF)~ the Zn atom is precisely in the mean porphyrin plane of the centrosymmetric Electrochemical redox properties and spectral features of supermolecular porphyrins including Zn(TCP) have been reported.266 The structure of chloro(phtha1ocyaninato)-zinc shows both an exceptionally large outward axial shift of the zinc and a rigorous planarity of the Pc ring.267 Zinc Compounds of Biological Interest.The synthesis of the biologically active complexes of 4-acetyl-2-( acety1amino)-5-dimethyl-A2-1,3,4-thiadiazole with Zn" Hg" Cd" and Cu" has been described.268 Captopril forms complexes with Zn" and Cd".269 The interactions between N-tosylamino-acids and Zn" ions in aqueous solutions and in the solid state have been in~estigated~~' and formation constants for the N-(2-mercaptopropionyl)glycine,Zn and Cd complexes have been report- ed.271 Mixed ligand complexes of zinc( 11) with glycine and uracil or 2-thiouracil have been prepared.272 257 Yu. A. Alexandrov S. A. Lebedev and N. V. Kuznetsova J. Organomet. Chem. 1985 292 39. 258 S. Chatterjee and E.-I. Negishi J.Organomet. Chem. 1985 285 C1. 259 S. Matsubara J.-I. Hibino Y. Morizawa K. Oshima and H. Nozaki J. Organomet. Chem 1985 285 163. 260 M. Bellassoned M. Gaudemar A. El Borgi and B. Baccar J. Organomet. Chem. 1985 280 165. 26 1 F. A. Bottino and P. Finocchiaro Polyhedron 1985 4 1507. 262 S. P. Dagnell D. N. Hague M. E. McAdam and A. D. Moreton J. Chem. Soc. Dalton Trans. 1985,2381. 263 J. M. Burlitch S. E. Hayes and J. T. Lemley Organornetallics 1985 4 167 264 G. Ghiotti F. Boccuzzi and A. Chiorino J. Chem. SOC.,Dalton Trans. 1985 1012. 265 C. K. Schauer 0. P. Anderson S. S. Eaton and G. R. Eaton Znorg. Chem. 1985 24,4082. 266 G. B. Maiya and V. Krishnan Znorg. Chem. 1985 24 3253. 267 M. Mossoyan-Deneux D. Benlian M. Pierrot A.Fournel and J. P. Sorbier Znorg. Chem 1985,24,1878. 268 K. N. Thimmaiah G. T. Chandrappa W. D. Lloyd and C. Parkanyi Inorg. Chim. Acta 1985 107 1. 269 M. A. Hughes G. L. Smith and D. R. Williams Znorg. Chim.Acta 1985 107 247. 270 L. P. Battaglia A. B. Corradi L. Menabue M. Saladini M. Sola and G. B. Gavioli Znorg. Chim. Acta 1985 107 73. 27 1 M. Filella and D. R. Williams Znorg. Chim. Acta 1985 107 49. 272 M. Gupta and M. N. Srivastava Polyhedron 1985 4 475. 342 J. Silver Zinc-containing haemoglobin hybrids have been as has the binding of zinc by the tripeptide glycyl-~-histidyl-~-lysine.~~~ The interactions of calmodulin with Zn2+ and an antagonist have been followed using 67Znn.m.r.275 Zinc adsorption in anorexia nervosa has been studied.276 The mechanism of action of zinc therapy may not be solely the restoration of a nutritional Cadmium.-In (NH2CH2CH2NH2),Cd12 the Cd atoms have distorted octahedral coordination.278 Luminescence and absorption properties of Cdl-,V,C12 crystals have been investigated.279 CdGe0 has the largest value of c/a yet recorded among compounds with the ilmenite structure.**' The photohydrogenation of acetylene and ethylene by Pt and Rh supported on CdS semiconductor particles has been studied281 and the semicon- ducting properties of MS-poly( acrylonitrile) composites (M = Cd Cu) reported.282 The preparation of active CdS/RuO particles for the photogeneration of H2 has been carried out.283 The synthesis and 'I3Cd n.m.r.spectroscopic characterization of the fully substituted clusters [(~-EPh)~(cdx)~]~- (E = S or Se X = Br or I) has been reported284 and '13Cd '19Hg 77Se and '25Te n.m.r.data for the zintyl anions HgChf- and CdCh:-(Ch = Se and/or Te) have been presented.285 3CdSO4-8H2O single crystals have been studied using e.p.r. and electronic absorption spectra.286 [M(TDPS),](ClO,) {where M = Cd or Zn and TDPS = tris(dimethy1-amino)phosphine sulphide} have been examined using 31 P and 35Cl n.m.r.287 [Cd( BCTA),I,] (BCTA = benzenecarbothioamide) contains tetrahedrally coordin- ated Cd atoms.288 E.p.r. spectra at X and Q band are reported for Mn" ions doped into CdLX2 (L = pyridine or 3-or 4-methylpyridine X = C1 or Br).289 Diaquabis- (phenoxyacetato)Cd" has a distorted trapezoidal bipyramidal coordination around the Cd atom.290 CdL( N03)2{where L = tris(3,5-dimethylpyrazol-l-ylmethyl)amine} contains a CdN403 chr~mophore.~~' 273 K.Simolo G. Stucky S. Chen M. Bailey C. Scholes and G. McLendon J. Am. Chem. SOC., 1985 107 2865. 274 S. A. Daignault A. P. Arnold A. A. Isab and D. L. Rabenstein Inorg. Chem. 1985 24 3984. 275 T. Shimizu and M. Hatano Inorg. Chem. 1985 24 2003. 276 W. W. Dinsmore J. T. Alderdice D. McMaster C. E. A. Adams and A. H. G. Love Lancet 985 1041. 277 G. S. Fell Br. Med. J. 1985 290 242. 278 C. Mahadevan M. Seshasayee S. Sastry and Ch. Subrahmanyam 2.Kristallogr. 1985 171 173. 279 B. Galli A. Hauser and H. U. Gudel Inorg. Chem. 1985 24 2271. 280 J. Susaki M. Konno and S. Akimoto Z. Kristallogr.1985 171 243. 28 1 A. J. Frank Z. Goren and I. Willner J. Chem. SOC.,Chem. Commun. 1985 1029. 282 T. Yamamoto A. Taniguchi K. Kubota and Y. Tominaga Znorg. Chim. Acta 1985 104 L1. 283 D. Harry M. W. Thewissen K. Timimer E. A. van der Zouwen-Assink A. H. A. Tinnemans and A. Mackor J. Chem. SOC.,Chem. Commun. 1985 1485. 284 P. A. W. Dean and J. J. Vittal Znorg. Chem. 1985 24 3722. 285 R. C. Bums L. A. Devereux P. Granger and G. J. Schrobilgen Inorg. Chem. 1985 24 2615. 286 N. Satyanarayana Polyhedron 1985 4 633. 287 K. Alauani M. R. Khaddar L.Rodehuser P. R. Rubini and J. J. Delpuech Polyhedron 1985,4 643. 288 A. Castineiras A. Arquero J. R. Masaquer A. Ruiz-Amil S. Martinez-Carerra and S. Garcia-Blanco Polyhedron 1985 4 143. 289 M. Goodgame and J.N. Okey J. Chem. SOC.,Dalton Trans. 1985 75. 290 T. C. Mak W.-H. Yip E. J. O'Reilly G. Smith and C. H. L. Kennard Inor:. Chim. Acta 1985,100,267. 29 1 G. J. Kleywegt W. G. R. Wiesmeizer G. J. Van Driel W. L. Driessen J. Reedijk and J. H. Noordik J. Chern. SOC.,Dalton Trans. 1985 2177. Cu Ag Au; Zn Cd Hg 343 Cadmium Compounds of Biological Interest. '13Cd n.m.r. studies have been carried out on small dynamically stable Cd2+ complexes used as models for metallo- proteins.292 The structure of dinitratobis(2-methylmercaptoaniline)Cd'r monohy-drate has been solved and the Cd2+ geometry described as trigonal bipyramidal CdSN,02 with an additional weakly bound sulphur. The complex was prepared as a model for Zn metal lo enzyme^.^^^ Mercury.-MNDO has been parametrized for mercury and calculations are reported for a number of compounds of mercury.294 Tetrahedral geometry about the Hg atom has been established in HgC12[P(2- thien~l)~]~ .295 Discrete eight-membered centrosymmetric nearly square (Hg-C1)4 rings have been found in Na4[Hg4(p-C1)4{P(0)(OEt)2}8]-6H20.296 The cis to trans isomerization of [Pt(CrCPh),(PMePh,),] has been reported to be catalysed by Hg" halides.297 The structure and solvation of Hg" halides in pyridine solution has been ~tudied.~~~",~ The Hg" salt-halogen combination HgX,-X; has been utilized as a versatile reagent for stereoselective addition of X'-X to alkene~.,~~ In the presence of (SCN)- mercuric chloride adds to acetylenic compounds.300 The synthesis and solution structure of Hg[ PPh2( CH2)nPPh2] n(03SCF3)2 has been inve~tigated.~'~ The solvation thermodynamics of methylmercury(11) chloride in water have been determined.302 The [(MeHg)3S]+ cation adopts a trigonal-pyramidal structure in the perchlorate Bis[(p-benzotriazolato-N',N2)methylmercury( 11)] has been structurally characterized304 and the radical cation of diethyl mercury studied.305 In the structure of (2-mercaptobenzothiazolato)methylmercury(11) the C-Hg-S group is found to be almost linear306 and the structure of pentachlorocyclopenta- dienylphenylmercury( 11) has been reported (20).307 Redox demercuration and 19F n.m.r.studies of PhHgSC6H4F-4 by Pt(PPh3)4 has been pre~ented.~~~"~ The preparation of bis( a,P-ditrifloxystyry1)mercury has been discussed,309 as has the electrochemical reaction of the preparative electrochemical symmetrization of 292 A.D. Keller T. Drakenberg R. W. Briggs and I. M. Armitage Znorg. Chem. 1985 24 1170. 293 E. A. H. Griffith N. G. Charles P. F. Rodesiler and E. L. Amma Polyhedron 1985 4 615. 294 M. J. S. Dewar G. L. Grady K. M. Merz Jr. and J. J. P. Stewart Organometallics 1985 4 1964. 295 D. W. Allen N. A. Bell S. T. Fong L. A. March and I. W. Nowell Inorg. Chim. Acta 1985 99 157. 296 P. Peringer P.-P. Winkler G. Huttner and L. Zsolnai J. Chem. Soc. Dalton Trans. 1985 1061. 297 R. J. Cross and M. F. Davidson Inorg. Chim. Acta 1985 97 L35. 298 (a) I. Persson M. Sandstrom P. L. Goggin and A. Mosset J. Chem. SOC. Dalton Trans. 1985 1597; (b) I.Persson and M. Sandstrom Acta Chem. Scand. Ser. A 1985 39 519. 299 J. Barluenga J. M. Matinez-Gallo C. Najera and M. Yus J. Chem. SOC. Dalton Trans. 1985 1422. 300 M. Gifford J. Cousseau L. Gouin and M. R. Crahe J. Organomet. Chem. 1985 287 287. 301 P. Peringer and M. Lusser Znorg. Chem. 1985 24 109. 302 I. Iverfeldt and I. Persson Inorg. Chim. Acta 1985 103 113. 303 B. Kamenar B. Kaitner and S. Pocev J. Chem. SOC.,Dalton Trans. 1985 2457. 304 A. L. Spek A. R. Siedle and J. Reeijk Inorg. Chirn. Acta 1985 100 L15. 305 J. Rideout and M. C. R. Symons J. Chem. Soc. Chem. Commun. 1985 129. 306 J. Bravo J. S. Casas M. V. Castano M. Gayosa Y. P. Mascarenhas A. Sanchez C. de 0. P. Santos and J. Sordo Znorg. Chem. 1985 24 3435. 307 A.G. Davies J. P. Goddard M. B. Hursthouse and N. P. C. Walker J. Chem. SOC. Dalton Trans. 1985 471. 308 (a) S. I. Pombrik A. A. Bezrukova L. S. Golovchenko A. S. Peregudov A. Z. Rubezhov and D. N. Kravtsov J. Organornet. Chem. 1985 293 C1; (b) S. I. Pombrik L. S. Golovchenko E. V. Polunkin A. S. Peregudov and D. N. Kravtsov J. Organomet. Chem. 1985 292 81. 309 G. Maas R. Bruckmann and W. Lorenz J. Organomet. Chem. 1985 289 9. 344 J. Silver C-and B-carboranylmercury salts.310 The reaction of 2-bromoarylmercury com- pounds with cu,p-enoles permits a new entry to l-indanol~.~~’ Redox demercuration of chiral 2-bromomercuri-4-dimethylaminobutanehas been observed.312 The single product of bromide-ion catalysed solvolysis of ethyl a-bromomercury p-nitrophenyl- acetate in ethanol has been shown to be ethyl p-nitr~phenylacetate.~’~ MNDO has been applied to topics of interest in organomercury chemistry.314 E.s.r.has been used to study organomercury complexes,315 as has photoelectron The reaction of ethylnylferrocene with mercuric acetate has been investigated317 and the reactivities of X2Sm(THF) (X = C5Me or C5Me4Et) with organomercurial reagents followed.318 {CH,( HgBr),} has been ~ynthesized.~” The reaction of Hg with phenyl( P-carborary1)iodonium salts has been The addition of a mixture of benzaldehyde and BF3.0Et to crotylorganometallic reagents C4H,MLn (M = Cu Cd or Hg) produces predominantly .the erythro homoallyl A new intramolecular C-vinylation induced by Hg“ salts has been and mercurated and telurated Schiff bases and phenylhydrazones have been discussed.323 A new method for the determination of the stability constant of metalloporphyrins uses the catalytic effect of Hg” on metalloporphyrin formation.324 310 A.Ya. Usiatinsky V. A. Shreider T. M. Shcherbina V. I. Bregadze N. N. Godovikov and I. L. Knuniants J. Organornet. Chern. 1985 289 17. 311 S. Cacchi and G. Palmieri J. Organornet. Chern. 1985 282 C3. 312 V. V. Bashilov E. V. Maskeva P. V. Petrovskii and V. I. Sokolov J. Organornet. Chern. 1985 292 89. 313 N. P. Butin and T. V. Magdesieva J. Organornet. Chern. 1985 292 47. 314 M. J. S. Dewar and K. M. Men Jr. Organornetallics 1985 4 1967. 315 A. Alberti F. P. Colonna M. C. Depew and X. Li J. Organornet. Chern.1985 292 335. 316 (a)V. N. Baidin M. M. Timoshenka Yu. V. Chizhov Yu. A. Ustynyuk and I. I. Kritskaya J. Organornet. Chern. 1985 292 55; (b) J. C. Maire J. Organornet. Chern. 1985 281 45. 317 M. Bassetti B. Floris and G. Illuminati Organornetallics 1985 4 617. 318 W. J. Evans I. Bloom W. E. Hunter and J. L. Atwood Organornetallics 1985 4 112. 319 J. W. Bruin G. Schat 0. S. Akkerman and F. Bickelhaupt J. Orgunornet. Chern. 1985 288 13. 320 V. V. Grushin T. M. Shcherbina and T. P. Tolstaya J. Organornet. Chern. 1985 292 105. 32 1 Y. Yamamoto and K. Maruyama J. Organornet. Chern. 1985 284 C45. 322 J. Drouin M.-A. Boaventura and J.-M. Conia J. Am. Chern. SOC.,1985 107 1726. 323 H. B. Singh and W. R.McWhinnie J. Chern. SOC.,Dalton Trans. 1985 821.324 M.Tabata and M. Tanaka J. Chern. SOC.,Chern. Cornrnun. 1985,42. Cu Ag Au; Zn Cd Hg Compounds of the type ( T~-C~H,CH,)(CO)~MOH~X (X = C1 Br I SCN) have been synthesized.325 Formation of an asymmetric Rh-Hg-Rh bridged complex has been reported.326 Mercury Compounds of Biological Interest. Hg" complexes of 6-aminopenicillinic acid have been A linear C-H-N entity is found in the complex of 2-methylpyridine with methylmercury( 11) trifl~oroacetate.~~~ The structure may have significance in the understanding MeHg" binding in biological systems.328 The structures of [Hg3(SCH2CH2S),l2- and {[Hg2(SCH2CH2S)3]2-}n contain isolated trinuclear anions (21) and polymeric anions composed of quasi-isolated dinuclear subunits respectively; it is suggested that both Hg thiolates may reflect structural features of biologically active species.329 325 M.Cano R. Criado E. Gutierrez-Puebla A. Mange and M. P. Pardo J. Orgunomet. Chem. 1985,292 375. 326 A. R. Sanger Znorg. Chim. Actu 1985 99 95. 327 S. Kamrahm G. S. Sodhi and N. K. Kaushik Znorg. Chim. Actu 1985 107 29. 328 R. D. Bach H. B. Vardhan A. F. M. M. Rahman and J. P. Oliver Orgunornetaffics,1985 4 846. 329 G. Henkel P. Betz and B. Krebs J. Chem. Soc. Chem. Cornrnun 1985 1498.