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.-An extremely useful review with 385 references on copper chemistry covering the year 198 1 has appeared. ’ Copper(1).The phase diagrams CuC1-MC1 (M = Cd La or Yb) were studied by d.t.aV2 Tetrabutylammonium dichlorocuprate and dibromocuprate contain anions that are linear. Studies on the thermodynamics of cuprous halide complex formation in acetonitrile have established that the stability decreases in the order C1- > Br-> I-.4 The diamagnetic adducts [CuX(py)],.quinone (X = C1 or Br) are said to be olefin complexes.’ CuXL (X = C1 Br or I; L = 2-amino-1,3,4-thiadiazoleor 2-ethylamino- 1,3,4-thiadiazole) have been studied by conductimetric methods and i.r.spectroscopy.6 63Cu and 65Cu n.q.r. spectra of CuCl and CuBr complexes of imi- dazolidine-2-thione and tetrahydro- 1H-pyrimidine-2-thione have been rep~rted.~ Bromo(tri-t-butylphosphine)copper(I) tetramer contains a cubane-type Cu4Br core.* The structures of 1 1 complexes of Cu’I with 2-methylpyridine (A) 2,2,6,6- tetramethylpiperidine (B) and acridine (C) were studied a cubane-type unit [Cu4I,(2Me-py),] was found in A B is a di-p-iodo bridged dimer [Cu2Iz(tmpip),] and C is a ‘split stair’ polymer (-CUL-I-),.~ Structures of five complexes CuIL (L = 2-methylpyridine 2-ethylpyridine quinoline 3,5-dimethylpyridine or 2,6-dimethylpyridine) have been reported. The first four complexes contain Cu atoms pseudotetrahedrally co-ordinated to two N atoms one from each base and two bridging iodine atoms; in the fifth complex the Cu atom is three co-ordinate.” The complexes [RO,P],CuCl (R = Et or Me) and CuC1(RN=PPh3) {where R = P(0) (OPh),} have been characterized.’ ’ Spectrophotometric studies have been reported on the reactions of the phenolic oxidative coupling initiator py4Cu4C1402 and of B.J. Hathaway Coord. Chem. Rev. 1983 52 87. ’I R. Blachnik and Enninga Z. Anorg. Allg. Chem. 1983 503,133. M. Asplund S. Jagner and M. Nilsson Acta Chem. Scand. Ser. A 1983 37,57. S. Ahrland K. Nilsson and B. Tagesson Acta Chem. Scand. Ser. A 1983 37,193. ’ E. Balogh-Hergovich and G. Speier Inorg. Chim. Acta 1983 74,61. A.C. Fabretti G. Peyronel A. Giusti and A. F. Zanoli Polyhedron 1983 2 475.’ J.-M. Bret P. Castan G. Jugie A. Dubourg and R. Roques J. Chem. SOC.,Dalton Trans. 1983 301. R. G. Goel and A. L. Beauchamp Inorg. Chem. 1983 22 395. P. C. Healy C. Pakawatchai C. L. Raston B. W. Skelton and A. H. White J. Chem. SOC. Dalton Trans. 1983 1905. lo P. C. Healy C. Pakawatchai and A. H. White J. Chem. SOC. Dalton Trans. 1983 1917. I’ (a) J. C. Bommer and K. W. Morse Inorg. Chem. 1983 22 592; (b) K. Bartel K. V. Werner and W. Beck J. Organomet. Chem. 1983 243,79. 275 276 J. Silver py4cU4c160 with pyridine.' The cation-radical salt of tetraselenotetracene with the dibromocuprate anion contains CuBr2-anions that have a distorted linear configuration.l3 Bis{ p-chloro-[ N,N'-ethanediylidenebis(1-isopropyl-2-methylpropylamine)]copper(1)} is an unsymmetrically Cl-bridged dimer.' [Ph4P]3[MoOS3(CuC1)3][CuC12] contains a tris[chlorocopper(~)]-oxotrithio-molybdate(vI)2- anion co-crystallizing with a linear [CuCl,]- anion.l5 The vapour deposition of CuO by Cl, HgCl, and 1 transport agents has been studied.I6 CsCuO has been prepared." Cs3Cu504 Rb2KCu504 RbK2Cu504 and K3Cu504 are reported.18 The heterogeneous decomposition of propan-2-01 vapour in the presence of CuO has been induced by i.r.laser radiation." Charge-density distribution in crystals of CuA10 with d-s hybridization has been investigated.,' Mass spectrometric studies of the decomposition and the heat of formation of CuInS have been presented.,' CuGaSe and CuGaTe have been studied., The crystal structure of TiCu,P shows it belongs to the Cu2Sb structure family.23 The structure of tetrabutylammonium dicyanocuprate( I) contains a [Cu(CN),]- chain., Preliminary results of the direct electron transfer rate of Cu+-Mo(CN);- ion-pairs generated by IT excitation of Cu2+-Mo(CN);- association are reported.25 The thermal behaviour of CuSO and Cu,OSO and crystal formation was studied.16 The cubane-like structure of a tetranuclear Cu' carbonyl complex [Cu(q)(CO)] (q = 2-methylquinolin-8-olate) forms in tetrahydrofuran under a pressure of 60 atm of CO at 65 0C.26 The crystal structure of Cu(CO)EtSO shows a Cu atom in nearly tetrahedral ge~metry.~' CO adducts of the Cu' derivatives of the new ligands bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]X (X = amine ether or sulphide) are repor- ted.,* [CuCO(O-t-Bu)] has a CU404 core of cubane form.29 The synthesis has been reported of a series of monolefin complexes containing distorted tetrahedral CU'.~' Evidence for Cu(C&) is found in e.s.r.spectra at 77 K.31 Mesitylcopper(r) (CuMes) was shown to be a cyclic pentameric aryl copper complex in the solid and to undergo ring contraction with tetrahydrothiophene to give [CU,M~S,(C,H~S)~].~~ The struc- l2 G. Davies M. A. El-Sayed and A. E. Fasano Inorg. Chim. Acta 1983 71 95. l3 R. P. Shibaeva V. F. Kaminskii E. B. Yagubski and L. A. Kushch Sou. Phys.-Crystallogr. (Engl. Transl.) 1983 28 48. 14 H. T. Dieck and L. Stamp Acta Crystallogr. 1983 C39 841. l5 W. Clegg G. D. Garner J. R. Nicholson and P. R. Raithby Acta Crystallogr. 1983 C39 1007.l6 L. Bald M. Spiess R. Gruehn and T. Kohlmann Z. Anorg. Allg. Chem. 1983 498 153. H. Klassen and R. Hoppe Z. Anorg. Allg. Chem. 1983 497 70. R. Hoppe and W. Losert Z. Anorg. Allg. Chem. 1983 504 60. " W. D. Farneth P. G. Zimmerman D. J. Hogenkamp and S. D. Kennedy J. Am. Chem. SOC.,1983,105 1126. 20 T. Ishiguro N. Ishizawa N. Mizutani M. Kato K. Tanaka and F. Marumo Acta Crystallogr. 1983 B39 564. 21 H. Wiedemeier and R. Santandrea Z. Anorg. Allg. Chem. 1983 497 105. 22 A. Kraft G. Kiihn and W. Moiler Z. Anorg. Allg. Chem. 1983 504 155. 23 W. Carillo-Cabrera Acta Chem. Scand. Ser. A 1983 37 93. 24 M. Asplund S. Jagner and M. Nilsson Acta Chem. Scand. Ser. A 1983 37 165. 25 H. Hennig A. Rehorek D. Rehorek P. L. Thomas and D. Bazold Inorg.Chim. Acta 1983 77 LII. 26 M. Pasquali R. Faischi C. Floriani and P. F. Zanazzi J. Chem. SOC.,Chem. Commun. 1983 613. 27 G. Doyle K. A. Eriksen and D. Van Engen Inorg. Chem. 1983 22 2892. 28 T. N. Sorrel1 and M. R. Malachowski Inorg. Chem. 1983 22 1883. 29 R. L. Geerts J. C. Huffman K. Folting T. H. Lemmen and K. G. Caulton J. Am. Chem. SOC.,1983 105 3503. 30 J. S. Thompson R. L. Harlow and J. F. Whitney J. Am. Chem. Soc. 1983 105 3522. 31 A. J. Buck B. Mile and J. A. Howard J. Am. Chem. SOC.,1983 105 3381. 32 S. Gambarotta. C. Floriani A. Chiesi-Villa and C. Guastini J. Chem. SOC.,Chem. Commun. 1983 1156. Cu,Ag Au; Zn,Cd Hg 277 ture of tetrakis(is0cyanide)-bis( p-phenoxo)dicopper(I) has been described; two phenoxo and two isocyanide ligands are bound to each CU.~ (PEt3),CuBPh and (PPh3),CuBPh4 react with CS2 generating [(PEf3),-Cu( S2CPEt3)]BPh4 and (PP~,),CU(S~CP~).~~ In [(PPh3),Cu( S2CPEt3)]BPh4 the Cu ion is in four co-ordination to two S atoms and two triphenylphosphine groups.34 In [(PPh,),Cu( p-S,CSCH,SCS,)Cu( PPh,),] the bridging ligand is formed from a double head-to-tail condensation of three CS2 molecule^.^^ CS with arylcopper( I) complexes and bis(dipheny1phosphino)methane (dppm) in toluene affords [Cu,(dppm),(CS,),] this consists of a square arrangement of Cu atoms.36 The complexes of [(PhS)CuS2MoS2I2- and [(PhS)CuS2MoS2Cu(SPh)I2-have trigonal planar Cu co-~rdinations.~~ is a thiaether complex [CU~(C~~H~,N,S,)]~+ containing a meta-xylyl dinucleating agent ;both Cu atoms have distorted tetrahedral ge~metries.~~ Isomers of the mixed bimetal complex (t-BuNC),Mo( p-t-B~s)~CuBr have been reported to contain Cu in almost ideal trigonal planar geometry." The structure of (triphos)Cu(O,CH) (triphos = 1,11-tris(diphenylphosphinomethy1)-ethane) and its reactions with C02 CS, and COS has been studied.,' The reaction of mesitylcopper(1) (CrAr) with 172-bis(diphenylphosphino)ethane (dppe) gives [(dppe),Cu2Ar2] which consists of a linear [CuArJ unit with a tetrahedral [Cu(dppe),]+ counter ion.,' The structures of bis(tetramethylammonium)hexa(thiol-ato)tetracuprate(I) polymorphs are reported.42 The formation of 176-bis( N-methyl- benzimidazol-2-yl)-2,5-dithiahexanecopper( I) perchlorate from the CU" compound by photoinduced reduction in dimethylformamide has been reported.43 In tris[2( 1H)-pyridinethione-S]copper(~)nitrate each Cu atom is surrounded by three S atoms in a planar configuration.44 The structure of [2-(Me,Si)2C(Cu)C5H,N]2 contains a Cu-Cu interaction of 2.412( 1) A.45The distorted tetrahedral Cu' structures of [Cu(btz),][PPh] and [C~,(bt),][C10,]~ (btz = 2,2'-bi-4,5-dihydrothiazineand bt = 2,2'-bi-2-thiazoline) have been The photophysical properties of a series of com-plexes of the type Cu(NN),+ {where the (NN) ligands are 2,9-dimethyl-l,10-phenanthroline 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 4,4',6,6'-tetramethyl-2,2'-bipyridine) were characteri~ed.~~Cu(pze)BF {pze = bis-[2-(3$dimethyl-1-pyrazolylethyl]ether} contains a three co-ordinate Cu' ion.,* 33 M.Pasquali P.Faischi C. Floriani and A. Gaetani-Manfredotti J. Chem. SOC.,Chem. Commun. 1983 197. 34 C. Bianchini C. A. Ghilardi A. Meli and A. Orlandini Inorg. Chem. 1983 22 2188. 35 C. Bianchini C. A. Ghilardi A. Meli S. Midollini and A. Orlandini J. Chem. SOC.,Chem. Commun. 1983 545. 36 A. M. M. Lanfredi A. Tiripicchio A. Camus and N. Matsich J. Chem. Soc. Chem. Commun. 1983,1126. 37 S. R. Acott C. D. Garner J. R. Nicholson and W. Clegg J. Chem. SOC.,Dalton Trans. 1983 713. 38 K. D. Karlin J. C. Hayes J. P. Hutchinson and J. Zubieta Inorg. Chim. Acta 1983 78 L45. 39 N. C. Payne N. Okura and S. Otsuka J. Am. Chem. SOC.,1983 105 245. 40 C. Bianchini C. A. Ghilardi A. Meli S. Midollini and A. Orlandini J. Organornet. Chem.1983 248 C13. 41 P. Leoni M. Pasquali and C. A. Ghilardi J. Chem. SOC.,Chem. Commun. 1983 240. 42 I. G. Dance G. A. Bowmaker G. R. Clark and J. K. Seadon Polyhedron 1983 2 1031. 43 P. L. Verheijdt J. G. Haasnoot and J. Reedijk Inorg. Chim. Acra 1983 76 L43. 44 S. C. Kokkou S. Fortier P. J. Rentzeperis and P. Karagiannidis Acra Crystallogr. 1983 C39 178. 45 R. 1. Papasergio C. L. Raston and A. H. White J. Chem. SOC.,Chem. Commun. 1983 1419. 46 M. G. B. Drew T. R. Pearson B. Murphy and S. M. Nelson Polyhedron 1983 2 269. 47 J. R. Kirchhoff R. E. Gamache jun. M. W. Blaskie A. A. Del Paggio R. K. Lengel and D. R. McMillin Inorg. Chem. 1983 22 2380. 278 J Silver Resonance Raman spectra of a series of Cu' complexes of a-di-imine ligands have been inter~reted.,~Bis(tripheny1phosphine)pyridine and pyrazine-carboxy-latecopper(I) complexes have been shown to contain Cu' tetrahedrally co-ordinated to two molecules of triphenylphosphine to a N atom and a carboxylate group." A mechanistic investigation of Cu-catalysed reactions of diphenyliodinium salts has identified Cu' as the catalytically active species.50 Dioxygen activation by photoexcited copper atoms has been reported the bonding in Cu(0,) is between Cu+ and 0,ions with the odd electron residing mainly on the dioxygen m~iety.~' Second-order rate constants have been determined for the oxidation of Cu(aq)' by various Ru"' complexes in perchlorate solutions at 25 "C and 1.O M ionic strength.52 The photoaddition of alkyl halides to olefins catalysed by Cu' complexes has been Allenylcopper( I) species add to N-sulphinylaniline to give N-phenyl 2-a1 kynyls~lphinamides.~~ Copper(11).Structural and thermodynamic aspects of the phase transition in CU~,,~Z~~,, A number of CSCUM''1F6 complexes SiF6.6H20 have been rep~rted.'~ were studied.j6 Tetragonal distortions and vibronic coupling in CuF2- complexes have been described.57 Cu" chloride complex equilibrium constants have been determined58 and stability constants of Cu(OAc)Cl CuCI, CuCuC13 and LiCuC1 in acetic acid solution calc~lated.'~ Evidence that CuCl+ is the reactive species in the chlorination of cyclohexene by CuC12 has been presented.60 A series of bis(dithiocarbamat0)di-p-chloro(xx) complexes have been synthe- sized.61 The crystal structure of C~F,(3-methyl-5-phenylpyrazole)~( BF4)2 contains dimeric co-square planar cations.62 [Cu(C,H NO)2C12)2,63 [Cu( N,N,N'-triethyl-ethylenediamine)2C1,]264 and [CuCI(C,H,N)(OMe)] 65 contain chloro-bridge$ Cul'dimers.Di-p-chloro-bis[chloro(l,2-cyclohexanedionedioxime-N,~')copper(11) contains Cu in a distorted square pyramid monomer linked as dimers by two chloro-bridges.66 The structures of [CuLC12] and CuL2(OH),.2H,O (L = 2,3-pyrazinedicarboxamide) were determined the former is a dimer containing two bridging chlorines and the latter is a monomeric complex.67 48 P. Leupin and C. W. Schlapfer 1.Chem. Soc. Dalton Trans. 1983 1635. 49 F. Cariati L. Naldini A. Panzanelli F. Demartin and M. Manassero fnorg. Chim. Acta 1983 69 117.50 T. P. Lockhart J. Am. Chem. Soc. 1983 105 1940. 5' G. A. Ozin S. A. Mitchell and J. Garcia-Prieto J. Am. Chem. Soc. 1983 105 6399. 52 K. M. Davies fnorg. Chem. 1983 22 615. 53 M. Mitani I. Kato and K. Koyama J. Am. Chem. Soc. 1983 105 6719. 54 K. Ruitenberg and P. Vermeer J. Organomet. Chem. 1983 256 175. 5s B. Ya. Sukharevskii E. 0.Tsybul'skii G. E. Statalova and I. M. Vitebskii Soo. Phyx-Crystallogr. (Engl. Trans/.),1983 28 288. 56 D. Babel and F. Binder 2. Inorg. Allg. Chem. 1983 505 153. 57 R. Bbca P. Pelikan M. Breza and J. Gaz6 Polyhedron 1983 2 921. 58 R. W. Ramette and G. Fan Inorg. Chem. 1983 22 3323. 59 M. A. Khan J. Meullemeestre M. J. Schwing and F. Vierling Polyhedron 1983 2 459. 60 P. H.Gamlen M. S. Henty and H. L. Roberts J. Chem. Soc. Dalton Trans. 1983 1373. 61 K. K. M. Yusuff K. Muhammad Bashees and M. Gopalan Polyhedron 1983 2 839. 62 W. C. Velthuizen J. G. Haasnoot A. J. Kinneging F. J. Rietmeijer and J. Reedijk J. Chem. Soc. Chem. Commun. 1983 1366. 63 W. E. Marsh D. S. Eggleston W. E. Hatfield and D. J. Hodgson Inorg. Chim. Acta 1983 70 137. 64 W. E. Marsh K. C. Patel W. E. Hatfield and D. J. Hodgson fnorg. Chem. 1983 22 51 1. 65 R. D. Willett and G. L. Breneman Inorg. Chem. 1983 22 326. 66 M. Mtgnamisi-Belombt and H. Endres Acta Crysrallogr. 1983 C39 707. 67 C. L. Klein E. D. Stevens C. J. O'Connor R. J. Majeste and L. M. Trefonas fnorg. Chim. Acta 1983 70 151. Cu Ag Au; Zn Cd Hg 279 A trigonal-bipyramidal Cu"[5,8,5] complex containing a tweezer-type ligand cation and a [cu2c16]2- anion has been reported.68 Studies on the tri-n-actylam- monium chloro complexes of Cu" in benzene solution have been de~cribed.~~ E.s.r.studies have been reported on complexes containing CUCI,~- and CuBr,'- (2-Amino- 1,3-thiazoline),CuCI4 73 and the promaziniumyl free radical cation tetra- chlorocuprate salt.74 contain distorted CUC~,~- ions. An anhydrous theophyllineCu" compound [Cu(C7HsN,O2),CI2] also contains a Cu" ion in a flattened tetrahedral ge~metry.,~ [Et2NH2]2(Cu3Br8)CuBr2.EtOHcontains planar symmetrically dibridged Cu3Brs2- trimers (I) and a neutral CuBr chain.76 Br The magnetic behaviour of a series of tetranuclear copper(I1) halide complexes have been explained in terms of the isotropic Heisenberg The crystal structure of the antiferromagnetic copper(r1) bromide adduct of the tetranuclear cluster (MeC5H4),Cr4( p3-0)(p3-S)3has been described.78 The pseudo-polymeric chain structure of dibromo(cyc1ohexane- 1,2-dione dioxime)copper(I I) has been Eight Cu" C1 and Br complexes with 3-aminopropan- 1-01 and its methyl derivatives have been characterized.80 The structures of two complexes of CuC12 and 1,4-oxathiane have been studied.In one complex (CuCl,) chains are cross- linked by (S-.O)bridging ligands generating both five- and six-co-ordinate Cu sites in the other the CuCI units are joined into layers by the (S...O)bridges and six-co-ordinate environments are generated.8' U.v.-visible and i.r.investigations of tetrahydrofuran-Cu" chloride solutions have been reported.82 The structure of the red Cu"-doped methylammonium tetrachloromanganate(I1) complex contains distorted octahedral The framework of a-NaCuPO is built with isolated PO tetrahedra NaO polyhedra and CuO pyramids.84 In 68 G. R. Newkome V. K. Gupta and F. R. Fronczek Inorg. Chem. 1983 22 171. 69 C. Fischer H. Wagner and V. V. Bagreev Polyhedron 1982 2 1141. 70 A. Bencini and D. Gatteschi J. Am. Chem. SOC. 1983 105 5535. 7' A. C. Massabni 0. R. Nascimento R. H. A. Santos R. H. P. Francisco and J. R. Lechat Znorg. Chim. Acta 1983 72 127. 72 R. D. Willet R. J. Wong and M. Numata Inorg. Chem. 1983 22 3189. 73 T. Glowiak M. Kubiak T. Tatarowski H. Kozlowski and M. Gosilvez Inorg.Chim. Acla 1983,80,67. 74 R. B. Von Dreele and J. Harris Acta Crystaallogr. 1983 C39 170. 75 M. B. Cingi A. M. M. Lanfredi and A. Tiripicchio Acra Crystallogr. 1983 C39 1523. 76 R. Fletcher J. J. Hansen J. Livermore and R. D. Willett Inorg. Chem. 1983 22 330. 77 D. H. Jones J. R.Sams and R. C. Thompson Inorg. Chem. 1983 22 1399. 78 A. A. Pasynokii 1. L. Eremenko Yu. V. Rakitin V. M. Novotortsev 0. G. Ellert V. T. Kalinnikov V. E. Shklover Yu. T. Struchkov S. V. Lindeman T. Kh. Kurbanov and G. Sh. Gasanov J. Organomet. Chern. 1983 248 309. 79 M. Megnamisi-Bt5lombC and H. Endres Acra Crystallogr. 1983 C39 1190. 80 T. Lindgren R. Sillanpaa T. Nortia and K. Pihlaja Inorg. Chim. Acfa 1983 73 153. 81 J. C. Barnes J. D. Paton and A.McKissock Acra Crystallogr. 1983 C39 547. 82 C. Amuli J. Meullemeestre M.-J. Schwing and F. Vierling Inorg. Chem. 1983 22 3567. 83 G. Chapuis G. Brunisholz C. Javet and R. Roulet Inorg. Chem. 1983 22 455. 84 P. M. Quarton and A. W. Kolsi Acta Crvsfollogr.,1983 C39 664. 280 J. Silver Na6[Cu2{B16024(0H)10}]. 12H20 each borate anion is ring-like and encloses two Cu" ions forming a chelate-like ~ornplex.'~ Pb2C~5(Se03)6(U02)2(oH)6.2H20 contains layers of [Cu(O OH H20),] octahedra,86 whereas in CU,(U~~)(S~O~),(~H), [Cu(O OH),] layers are found." Several studies on the preparation and structures of dimeric Cu" carboxylate adducts have appeared.*' C~CU(C~H~O~)~.~H~O contains infinite chains of alternate metal ions linked via H20 rnolecule~.~~ In (2,4,6-trimethylpyridine)2Cu(MeC02)* the co-ordination of Cu is 4 + 2.90 The structure and magnetic properties of CU,L(M~CO~)~~M~OH= anion of N,Nf-bis(2-[(o-hydroxybenzhydry-(L2-lidene)amino]-ethyl}-I ,2-ethanediamine) have been Tunable exchange interactions in poxalatocopper(i1) dinuclear complexes illustrate the possibilities of this field.92 EXAFS structure and magnetic properties of a Cu"Ni" poxalato mixed linear-chain have been reported,93 as have the structures of [Cu2(Me4en),(C2o4)(H20)21(PF,)2.2H20 and [Cu2(Et5dien)2(C204>1(pF6)2*94 Formation constants are determined for the complexes in the Cu"-nitrilotriacetate (NTA3-) parent and in the Cu"-NTA3-glycinate Cu"-NTA3-amrnonia and Cu"- NTA3-methylamine mixed-ligand equilibrium systems.95 The Cu" complex of dihydro-1 H,3 H,5H-oxazolo-[3,4-c]-oxazole-7a-carboxylic acid has been character- i~ed,~~ as have three isonicotinato N-oxide complexes.97 The formation of the esters of N-( 1,3-dioxa-5-azacyclohexyl)aceticacid via the demetallation reaction of the Cu" complex of the acid has been f~llowed,~' as have the kinetics of the Cu"-catalysed oxidation of lactic acid with chloramine T.99 The binding of amino acids to hexahydrated Cu2+ions a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays has been characterized by a semiempirical m.0.method.Io0 The structure of the Cu" complex with a-aminoisobutyric acid consists of alkoxo-bridged dinuclear units."' A study of Cu" propionate adducts with diphenylphosphinoacetylene and bis(dipheny1phosphino)acetylene has been reported.lo* The structure of bis(N-tosylglycinato)bis( N-methylimidazole)Cu" shows Cu" interactions with carboxylic 115 H.Behm Acta Crysrallogr. 1983 C39 20. 86 D. Ginderow and F. Cesbron Acta Crysrallogr. 1983 C39 824. 87 D. Ginderow and F. Cesbron Actn Crvstallogr. 1983 C39 1605. nn (a) V. M. Rao D. N. Sathyanarayana and H. Manohar J. Chem. SOC.,Dalton Trans. 1983 2167; (b) M. Melnik and J. Mrozinski Z. Anorg. Allg. Chem. 1983 500 210; (c) L. C. Porter M. H. Dickman and R.J. Doedens Inorg. Chem. 1983 22 1964. 89 E. A. Klop A. J. M. Duisenberg and A. L. Spek Acta Crysrallogr. 1983 C39 1342. 90 A. Busnot F. Busnot A. Leclaire and M.Bernard Z. Anorg. Allg. Chem. 1983 503 207. 91 B. Chiari W. E. Hatfield 0. Piovesana T. Tarantelli L. W. Haar and P.F. Zanazzi Inorg. Chem. 1983 22 1468. 92 M. Julve M. Verdaguer 0. Kahn A. Gleizes and M. Philocke-Levisalles Znorg. Chem. 1983 22 368. 93 M. Verdaguer M. Julve A. Michalowicz and 0. Kahn Inorg. Chem. 1983 22 2624. 94 J. Sletten Acta Chem. Scand. 1983 A37 569. 95 F. Debreczeni and 1. Nagypal Inorg. Chim. Acta 1983 72 61. 96 S.-B. Teo and M. J. O'Connor Inorg. Chim. Acta 1983 70 107. 97 (a) H. Knuuttila and P. Knuuttila Acta Chem. Scand. Ser. A 1983 37 227; (b) H. Knuuttila Inorg. Chim. &fa 1983 72 1 I. 98 S.-B. Teo and S.-G. Teoh Inorg. Chim. Acfa 1983 68 107. 99 S. Jha P. D. Sharma and Y. K. Gupta Inorg.Chem. 1983 22 1393. I00 A. Gupta G. H. Loew and J. Lawless Inorg. Chem. 1983 22 I1 1. 101 M. M. Kuriya T. Harada H. Okawa and S. Kida Inorg. Chitn. Acta 1983 75 1. I02 M. Melnik. M. Sundberg and R. Uggla Acta Chem. Scand. Ser. A 1983 37 659. Cu,Ag Au; Zn,Cd Hg 281 oxygens at 1.967 and 2.758 A.103Complexes of diaza-crown-N,N'-dialkanoic acids with Cu" and dicopper(r1) have been obtained.lo4 Lead tetra-acetate oxidation of metallic copper to Cu2+ leads to the formation of {CU(O~CM~)~L}~ (where L = pyridine or 2- 3- or 4-methylpyridine).'05 Tetrakis( p-crotonato)bis(quinoline)dicop-per(1i) has a Cu-Cu distance of 2.66(3) &Io6 The He' photoelectron spectrum of bis(acetylacetonato)copper(II) has been measured and its electronic spectrum inter- preted by the Angular Orbital Method and Crystal Field Theory.Io7 Cu(acac) reacts with C2N2 in dichloroethane to give bis[ 1-cyano-2-( 1-iminoethy1)butane- 1,3-dionato]C~",'~~ which contains square planar Cu".Studies on Cu" triflate compounds containing aminopropanol isomers have revealed a number of hydrogen- bridged dimeric and trimeric specie^.'^' The kinetics of the reactions of P-diketones with Cu have been studied."' There is no evidence for ferromagnetic dimers in CU(C~H~NO)~(NO~)~.~" The effect of molecular cage size on the motion and co- ordination of Cu" in cross-linked poly(viny1 alcohol) gels has been studied by e.s.r."' In a series of di-p-hydroxo-bridged Cu" complexes e.s.r. spectra have been used to correlate aminotropic exchange and structure.'13 The CU" complexes of some macrocyclic crown ethers have been studied1I4 and in one complex the Cu'l ion has pentagonal-bipyramidal geometry with two CI- atoms axially co-ordinated.Solvent extraction of Cu" by high molecular weight hydroxyoximes' l5 and Cu2+ uptake by montmorillonite' I6 have been studied. Electron-spin echo spectrometry has been used to locate Cu" in X-zeoiites.II7 X-Ray studies on an aqueous solution of CuSO have established that each Cu2+ ion has a distorted octahedral arrangement of H20 molecules.' I' Electrolytic dissol- ution of Cu with dimethyl sulphoxide in SO2 was shown to give pure copper disulphate.' I9 The structures of the thiometallates [CU,MSCI](PP~~)~S [CU~MS~CI](PP~~)~O (M = W or Mo) and (PPh)3Cu2WS4.0.8CH2C12 have been reported.12' In (Ph3P)2C~( the two Cu atoms and four P atoms are virtually p-sPh),c~(PPh,)~ I03 L.P. Battaglia A. B. Corradi G. Marcotrigiano L. Manabue and G. C. Pellacani Inorg. Chem. 1983 22 1902. 104 R. A. Kolinski and J. Mrozinski Polvhedron 1983 2 1217. IU5 A. Debroy M. P. Mahajan M. N. Bhattacherjee and M. K. Chandhuri J. Chem. SOC. Dalron Trans. 1983 2531. I06 M. Bukaska-Strzyzewska J. Skoweranda E. Heyduk and J. Mrozihski Inorg. Chim.Acfa 1983,73,207. I07 (a) S. Kitagawa I. Morishima and Y. Yoshikawa Polyhedron 1983 2 43; (b) G. St. Nikolov and M. A. Atanosov Inorg. Chim. Acta 1983 12 95. I08 B. Corain M. Basato G. Visentin and G. Zanotti J. Chem. Soc. Dalton Trans. 1983 1217.109 (a)G. Nieuwpoort and J. Reedijk Inorg. Chirn. Acta 1983,71,125;(b)G. Nieuwpoort G. C. Verschoor and J. Reedijk J. Chem. Soc. Dalton Trans. 1983 531. I10 M. J. Hynes and M. T. O'Shea J. Chem. Soc. Dalton Trans. 1983 331. Ill R. L. Carlin R. Burriel R. M. Cornelisse and A. J. van Duyneveldt Inorg. Chem. 1983 22 831. I I2 D. Suryanarayana P. A. Narayana and L. Kevan Inorg. Chem. 1983 22 474. I I3 L. Banci A. Bencini and D. Gatteschi J. Am. Chem. Soc. 1983 105 761. 114 (a) A. GUI and 0. BekProjjlu J. Chem. Soc. Dalton Trans. 1983 2537; (b) A. Horbaczewski and J. F. Biernat Inorg. Chirn. Acta 1983 74 131 ;(c) T. Sakurai K. Kobayashi S. Tsuboyama Y. Kohno N. Azumo and K. Ishizu Acta Crystallogr. 1983 C39 206. llS L. Calligaro A. Mantovani U.Belluco and M.Acampora Polyhedron 1983 2 1189. I I6 P. Monsef-Mirzai and W. R. McWhinnie Inorg. Chirn.Acta 1983 73 41. I I7 T.Ichikawa and L. Kevan J. Am. Chem. Soc. 1983 105 402. 1 I8 A. Musinu G. Paschina G. Piccaluga and M. Magini Inorg. Chem. 1983 22 1184. 1 I9 N. K. Graham J. B. Gill and D. C. Goodall J. Chem. Soc. Dalton Trans. 1983 1363. I20 A. Muller H. Bogge and U. Schimanski Inorg. Chim. Acta 1983 69 5. 282 J. Silver coplanar.121 The Cu" complex of 1,4,7-trithiacyclononanecontains a nearly regular octahedral copper co-ordination. 122 Cu" complexes with 12-1 6-membered cyclic tetrathiaethers have been reported. 123 A Cu" complex of the thiosemicarbazone of a-hydroxy-P-naphthaldehydehas been isolated'24 and a stable bis(thiolate) of Cu" with long axial Cu-S linkages (2.94A) described.'25 A tetrahedrally distorted Cu" environment has been observed in a disulphide-coupled N-(2-ethanethiol)salicy-lideneimine complex.126 The structures and electrochemistry of some Cu"-mercap- tide complexes have been in~estigated.'~' The kinetics of the metal-exchange reaction of bis(8-mercaptoquinolato)nickel(11)chelate with Cu" ion have been studied by an exchange-extraction method.'28 The dinuclear Cu" complexes with 24"-(alkylthio)ethylthio]ethanol and 2-[2-(2-pyridyl)ethyIthio]ethanol both contain alko~o-bridges.'~~ [Cu3S1J3- a sulphur-rich complex has a central Cu3S3 and ring made up from three outer cus6 rings.'30 In [Cu(NH3)JBF4I2 X-ray absorption fine structure studies have provided evidence for five equal bond lengths.13' In trans-dinitratobis(0xamide oxime)cop-per(rr) the Cu has an elongated square bipyrimidal ~o-ordination.'~~ The possibility of an electronic criterion of stereochemistry of bis(chelate)copper( 11) complexes has been disc~ssed.'~~ Anation of [Cu(Me,tren)dmf12+ by NCS- N3- and Br- is charac- terized by kinetic data consistent with the operation of a dissociative interchange mechanism.134 N.m.r.relaxation studies in solutions of Cu" amines have been reported.135 Complex formation constants between 2-amino-2-(hydroxymethyl) 1pro-pane- 1,3-diol or 1 1,l -tris( N-methylaminomethy1)ethane with Ni" Cu'' Zn" and hydrogen ions have been ca1c~lated.l~~ The complexes Cu( NH3),(C5HN306).H20 and give the first evidence that an orotic acid derivative can co-ordinate Cu2+ simultaneously through the two N sites of the completely deprotonated 1igar1d.l~' A number of crystal structures of Cu" complexes containing biby (biby = 2,2'-bipyridine) have been described.They include complexes with dimeric rn~lecules,'~~ with six co-ordin- with five co-ordinated CuN2N2C chrom~phores'~~ 121 I. G. Dance P. J. Guerney A. D. Rae and M. L. Scudder Inorg. Chem. 1983 22 2883. 122 W. N. Setzer G. A. Ogle G. S. Wilson and R.S. Glass Inorg. Chem. 1983 22 266. I23 V. B. Pett L. L. Diaddario jun. E. R. Dockal P. W. Corfield C. Ceccarelli M. D. Glick L. A. Ochrymowycz and D. B. Rorabacher Inorg. Chem. 1983 22 3661. '24 Y. K. Bhoon Polyhedron 1983 2 365. 125 A.W. Addison and E. Sinn Inorg. Chem. 1983 22 1225. I26 D. M. Roundhill Polyhedron 1983 2 959. 127 G. P. Anderson C. M. Perkins and K. K. Brito Inorg. Chem. 1983 22 1267. 12* K. Haraguchi and H. Freiser Inorg. Chem. 1983 22 653. I29 (a) M. Mikuriya M. Nakam_ura H. Okawa and S. Kida Znorg. Chim. Acta 1983 68 111; (b) M. Mikuriya M. Nakamura H. Okawa and S. Kida Inorg. Chim. Acta 1983 70 223. 130 A. Muller and U. Schimanski Inorg. Chim. Acta 1983 77 L187. 131 L. Alagna. T. Prosperi A. A. G. Tomlinson and G. Vlaic J. Chem. SOC.,Dalton Trans. 1983 645. I32 (a) H. Endres N. Genc and D. Nothe Acta Crystallogr. 1983 C39 701 ;(b) H. Endres and N. Genc Acta Crystallogr. 1983 C39 704. I33 A. O'Leary S. Tyagi and B. J. Hathaway Inorg. Chim. Acta 1983 76 L89.134 S. F. Lincoln J. H. Coates B. G. Doddridge A. M. Hounslow and D. L. Pisaniello Inorg. Chem. 1983 22 2869. 135 F. Debreczeni J. PolgPr and I. Nagypd Inorg. Chim. Acta 1983 71 195. I36 (a) L. Bologni A. Sabatini and A. Vacca Inorg. Chirn.Acta 1983,69,71; (b) L. Bologni M. Micheloni A. Sabatini and A. Vacca Inorg. Chim. Acta 1983 70 117. 13' P. Arnzabalaga P. Castan and F. Dahan Inorg. Chem. 1983 22 2245. I38 B. N. Figgis R. Mason A. R.P. Smith J. N. Varghese and G. A. Williams J. Chem. Soc. Dalton Trans. 1983 703. I39 S. Tyagi and B. J. Hathaway J. Chem. Soc. Dalton Trans. 1983 199. Cu Ag Au; Zn,Cd Hg 283 ated CuN402 and CuN4X2 chrom~phores,'~~'~~ and with five co-ordinated square pyramidal Cu.'43 The spin density distributions of one of the complexes has been determined from two-dimensional polarized neutron diffraction data.13* The magnetic and spectro- scopic behaviour of a series of amine adducts of Cu"- N-acetyl-P-alaninate general formula Cu(ac-P-ala),B,. n H20(B = ethylenediamine 4-methylpyridine pyridine biby or 3-methylpyridine) has been reported.Iu Thermodynamic and spectroscopic properties of mixed-ligand complexes of Cu" with py biby 2,2' :6',2"-terpyridyl (terpy) in aqueous solution have been studied. Oxydiacetato(terpy)copper(II) dihy-drate has a distorted octahedral stereochemistry while that in [Cu(terpy)Cl,].H,O is pentaco-~rdinated.'~' The compound catena-[ p-aqua-bis(benzimidazo1e)difor-matocopper(II)] is established as a one-dimensional The binding sites stoicheiometry and thermodynamics of complex formation in aqueous solution of Cu" with 9-substituted purines have been in~estigated.'~' CUN units are found in tetrakis( 1,4,5-trimethylimidazole)copper(11)diperchlorate.14' Cu" is six-co-ordinate in CU(~~),(NCS)~ the pyridine rings can be found in two possible positions.*49 The co-ordination structures of species in the Cu"-methyl- and dimethylhistidine (1 :2) systems in aqueous solutions have been deduced from the pH-dependence of the c.d.spectra comparing the results with those for histi ti dine.'" The structure of Cu(dmpt),( NCS)2 (dmpt = a substituted pyrimidine) contains centrosymmetric dimers with two Cu atoms bridged by two NCS groups.15' Cu" structures containing 1,lO-phenanthroline or substituted varients have been described and rationalized in terms of a pseudo Jahn-Teller f~rmalism."~Rate constants for the one-electron oxidations of some Ru"' and Ru" complexes by the (dmphen),Cu" ion have been e~tablished.~~ [IrCl(PPh,),( p-dppn)( p-No)CUc1][PF& contains a nitrosyl bridging both metals.'53 An S-bonded adduct of cysteine with the [tris(2-pyridyl-methyl)amine]Cu" ion has been prepared.' 54 Cu" complexes of imidazoline ben- zimidazole benzothiazole benzotriazole and related ligands have been prepared'55 I40 C.Simmons A. Clearfield W. Fitzgerald S. Tyagi and B. Hathaway J. Chem. SOC.,Chem. Commun. 1983 189. 141 A. Sedov J. KoiiSek M. KabeSovi M. Dunaj J. J. Gaio and J. Garaj Inorg. Chim. Acta 1983 75 73.142 J. Foley D. Keenefick D. Phelan S. Tyagi and B. Hathaway J. Chem. SOC.,Dalton Trans. 1983 2333. I43 L. Antotini G. Marcotrigiano L. Menabue and G. C. Pellacani Inorg. Chem. 1983 22 141. I44 L. Menabue P. Prampolini M. Saladini and P. Morini Inorg. Chim. Acta 1983 68 157. I45 (a) G. Arena R. P. Bonomo S. Musumeci R. Purrello L. Rizzarelli and S. Sammartano J. Chem. SOC. Dalton Trans. 1983 1279; (6) N. B. Pahor G. Nardin R. P. Bonoma and E. Rizzarelli J. Chem. SOC. Dalton Trans. 1983 1797 (c)T. Rojo T. Vlasse and D. Beltran-Porter Acta Crystallogr. 1983 C39 194. I46 M. Bukowska-Strzyiewska and A. Tosik Acta Crystallogr. 1983 C39 203. I47 (a)S. Arpalahti and H. Lonnberg Inorg. Chim. Acta 1983 78 63; (b)ibid. 1983 80 25. I48 E.Bernarducci P. K. Bharadwaj K. Krogh-Jespersen J. A. Potenza and H. J. Schugar J. Am. Chem. SOC.,1983 105 3860. I49 J. Soidanovi M. KabeSovi and J. Gaio Inorg. Chim. Acta 1983 76 L203. I50 L. Casella and M. Gullotti Inorg. Chem. 1983 22 242. 151 M. B. Cingi A. M. M. Lanfredi A. Tiripicchio J. G. Haasnoot and J. Reedijk Inorg. Chim. Acta 1983 72 81. I52 (a)C. J. Simmons K. Seff F. Clifford and B. J. Hathaway Acta Crystallogr. 1983 C39 1360; (6) S. Tyagi and B. J. Hathaway J. Chem. SOC.,Dalton Trans. 1983 2693; (c) C. Escobar and 0.Wittke Acta Crvstallogr. 1983 C39 1643. I53 (a) P.Dapporto G. De Munno G. Bruno and M. Romeo Acfa Crysfallogr. 1983 C39 718; (6) G. De Munno G. Denti and P. Dapporto Inorg. Chim. Acta 1983 74 199; (c) A.Tiripicchio A. M. M. Lanfredi M. Ghedini and F. Neve J. Chem. Soc. Chem. Commun. 1983 97. I54 H. K. Beak and R. A. Holwerda Inorg. Chem. 1983 22 3452. I55 (a)J. Reedijk A. R. Sieddle R. A. Velapoldi and J. A. M. Van Hest Inorg. Chim. Acta 1983 74 109; (b) G. C. Wellon D. V. Bautista L. K. Thompson and F. W. Hartstock Inorg. Chim. Acta 1983,75271. 16'diamine}. 284 J. Silver and the unusual trimeric Cu" species [C~,(OH)(pz)~(Hpz)~(N03)~].H2O(Hpz = pyrazole) shown to consist of Cu,(OH)(pz) units with an almost flat Cu,N ring.'56 Cu" ions promote the formation of the Schiff bases between 2-formylpyridine and amino acids in neutral aqueous Bis-p-[ N,N'-ethylenebis(pyrrol-2-ylmethyleneaminato)]dicopper(~r) is a dimer where each of the intertwined Schiff bases binds two Cu atoms.'58 Condensation of &&triketone with aliphatic amines and Cur' complexes of the Schiff bases has been studied the products are mono- n~c1ear.l~~ Cyclic voltammetry of four dinuclear Cu" I ,3,5-triketonates and their diamine Schiff-base derivatives has been investigated in DMF with Et,NClO as the supporting electrolyte.'60 Cu" complexes of 5-nonylsalicylaldoxime with pyridine and ammonia form five-co-ordinate adducts.16' A number of studies on (salicylal- diminato)copper(I I) salts have been reported.162 Kinetics of hydrolysis of N-salicy-lidene-2-aminopyridine have been investigated in aqueous 5% MeOH in the presence and absence of CU".'~~ Aqua-bis(N-salicylidene-P-alaninate)dicopper(I I) monohy-drate contains two differently co-ordinated Cu atoms in a dimeric molecule.'64 A spectroscopic study was reported of 1 :1 Cu" complexes of Schiff base ligands derived from ~alicylaldehyde.'~~ The reaction of P-keto-enolate and Schiff -base complexes of Cu" with cyanogen in chlorinated solvents gives cyanoimino- substituted organometallic rings.'66 A dinuclear complex of Cu" is generated by reaction of bis(salicylaldehyde)copper(Ir) with rn-xylylenebis(2-(propane-1,3-A new type of .rr-molecular complex containing dinuclear triketone Cu" complexes and benzene has been reported.168 A tetrameric Cu" complex with a Schiff base derived from pyridoxal and 2-amino- I -(3',4'-dichlorophenyl)ethanol contains a CU404 core.169 The kinetics of ligand substitution in bis( N-alkylsalicy- lideneiminato)copper(II) complexes have been studied in solvent mixtures.I7O A number of Cu" complexes of Schiff bases derived from 1-(pyrrol-2-y1)butane-1,3-dione heptane-2,4,6-trione 1 -(0-hydroxypheny1)butane- 1,3-dione and 1,2-diaminoethane have been prepared and studied by X-ray crystal structure analysis. 171 E.s.r. studies on the ligation of dimeric and tetramic Cu" complexes with Schiff I56 F. 9. Hulsbergen R. W. M. ten Hoedt G. C. Verschoor J. Reedijk and A. L. Spek J. Chem. SOC. Dalton Trans. 1983 539. I57 L. Casella and M.Gullotti Inorg. Chem. 1983 22 2259. T. Kikuchi C. Kabuto H. Yokoi M. Iwaizumi and W. Mori J. Chem. SOC.,Cbern. Commun. 1983 1306. I59 V. Drevenkar A. Deljac Z. Stefanac and J. Seibl. Polyhedron 1983 2 447. 160 R.L. Lintvedt and L. S. Kramer Inorg. Chem. 1983 22 796. 161 9. McCudden P. O'Brien and K. R.Thornback J. Cbem. SOC.,Dulton Trans. 1983 2043. I62 (a) N. S. Biradar G. V. Karajagi T. M. Aminabhavi and W. E. Rudzinski Inorg. Chim. Acta 1983 77 L107 (b) W. Steurer and W. Adlart Acta Crystallogr. 1983 B39 721 (c) ibid. B39 718; (d) F. C. Priolo E. Rotondo G. Rizzardi G. Bruno and G. Bombieri Acta Crystallogr. 1983 C39 550. 163 A. C. Dash 9. Dash P. K. Mahapatra and M. Patra J. Chem. SOC.,Dalton Trans. 1983 1503. '6.1 P.-E. Werner A. Valent V. Adelskold and 0. Svajlenova Acta Chem. Scand. Ser. A 1983 37 51. M. P. Wagner and A. Walker Znorg. Chern. 1983 22 3021. I66 9. Corain M. Basato A. Del Zotto and G. Zanotti Inorg. Chem. 1983 22 2744. 167 B.C. Whitmore and R. Eiserberg Inorg. Chem. 1983 22 1. I68 J. F. Wishart C. Ceccarelli R. L. Lindvedt J. M. Berg D. P. Foley T. Frey J. E. Hahn K. 0.Hodgson and R. Weis Inorg. Chem. 1983 22 1667. 169 L. Watz H. Paulus W. Hasse H. Langhof and F. Nepveu J. Cbem. SOC.,Dalton Trans. 1983 657. I7O H. Elias H. Miith M. Sahm H. Volz and K. J. Wannowius Inorg. Chim.Acta 1983 68 163. 171 (a) H. Adam N. A. Bailey D. E. Fenton and M. S. L. Gonzalez J. Chem. SOC.,Dalton Trans. 1983 1345; (b)J.-P. Costes and D. E. Fenton J. Chem. SOC.,Dalton Trans. 1983 2235; (c) N. A. Bailey K. C. Cox C. P. Falshaw D. E. Fenton S. E. Grundy P. Haigh C. A. Philips and T. J. King J. Chem. SOC.,Dalton Trans. 1983 2241. Cu,Ag Au; Zn Cd Hg 285 bases in solution have established the presence of both distorted tetrahedron and square pyrimidal co-~rdinations.'~~ Asymmetric synthesis of threonine and partial resolution and retro-racemization of a-amino acids via Cu" complexes of their Schiff bases has been reported.173 MucrocycZic Systems containing Copper(11). E.s.r. spectra of a series of spin-labelled Cu" tetraphenyl porphyrins have enabled electron-electron coupling constants to be ~btained."~ Comparisons of the electronic structure of BsS16 the porphine dianion and their Cu" complexes using extended Hiickel calculations have been made.'75 Studies on metal-protoporphyrin IX iron(II1) complexes are compared with those of Cu"-protoporphyrin IX iron(II1) in which the Cu" is co-ordinated to the propionate groups.76 Electronic environments of Cu" chelates of tetra-2,3- pyridinoporphyrazine and phthalocyanines are found to be similar from e.s.r. data.'77 Cu" phthalocyanines have been incorporated in apomyogl~bin.'~~ The structure of [Cu(cyclarn)(SC,F,),] (SC6FS = pentafluorothiophenolate) is tetragonally elongated in a square arrangement.'79 Dissociation kinetics of (ruc-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane)copper(II) cation in strongly acidic media have shown that at least two factors contribute to the observed rates of the cleavages of the first and second M-N bonds.'" The Cu redox chemistry of a number of Cu" poly-aza macrocylces of varying size and denticity has been studied."' The stabilities of Cu poly-azacrown ether and nitrogen-oxygen macrocyles have been considered."* Seven mixed-valence dinuciear Cuii-Cu' complexes of macrocyclic ligands were used to study factors affecting intramolecular electron transfer.'83 A number of studies on dinuclear Cu" macrocycles have appeared detailing structure and electro- chemical properties. 84 The tridentate macrocyclic ligand tribenzo[b,f;j] [1,5,9]triazacyclododecine forms a bis complex with Cu" that exhibits a dynamic Jahn-Teller di~tortion."~ The distances of the protons of guest molecules to a I72 J. Jezierska A. Jezierska B. Jezowska-Tizebiatowska and A. Ozarowski Inorg. Chim. Acta 1983 68 7. I73 Yu. N. Belokon I. E. Zel'tzer V. I. Bakhmutov M. B. Saporovskaya M. G. Ryzhov A. I. Yanovsky Yu. T. Struchkor and V. M. Belikov J.Am. Chem. SOC.,1983 105 2010. I74 (a) K. M. More G. R. Eaton and S. S. Eaton Inorg. Chem. 1983 22 934; (b) R. Damoder K. M. More G. R. Eaton and S. S. Eaton J. Am. Chem. SOC.,1983 105 2147. 175 B. M. Gimarc and J.-K. Zhu Inorg. Chem. 1983 22 479. 176 B. Lukas J. Silver I. E. G. Morrison and P. W. C. Barnard Inorg. Chim. Acta 1983 78,205. 177 T. D. Smith J. Livorness H. Taylor J. R. Pilbrow and G. R. Sinclair J. Chem. SOC.,Dalton Trans. 1983 1391. 178 L. Trynda Inorg. Chim. Acta 1983 78,229. 179 A. W. Addison and E. Sinn Inorg. Chem. 1983 22 1225. B.-F. Liang and C. S. Chung Znorg. Chem. 1983 22 1017. 181 (a) M. J. Maroney and M. Wicholas Inorg. Chim. Acta 1983 77,L237; (6) L. Fabbrizi A. Poggi and P. Zanello J. Chem. SOC.Dalton Trans.1983 2191; (c) L. Fabbrizi A. Perotti and A. Poggi Inorg. Chem. 1983 22 141 1. I82 (a) V. J. Thom and R. D. Hancock Inorg. Chim. Acta 1983 77,L231; (b) E.Luboch A. Cygani and J. F. Biernot Inorg. Chim. Acta 1983 68 201. R. C. Long and D. N. Hendrickson J. Am. Chem. SOC.,1983 105 1513. I83 I84 (a) V. McKee and J. Smith J. Chem. SOC.,Chem. Commun. 1983 1465; (b)M. Yamashita H. Ito and T. Ito Inorg. Chem. 1983 22 2101; (c) K. D. Karlin J. C. Hayes J. P. Hutchinson and J. Zubieta J. Chem. SOC.,Chem. Comrnun. 1983 376; (d) S. K. Mandal and K. Nag J. Chem. Soc. Dalton Trans. 1983 2429; (e) S. M. Nelson F. Esho A. Lavery and M. G. B. Drew 1.Am. Chem. SOC. 1983 105 5693; (f)S. M. Nelson and C. V. Knox J.Chem. Soc. Dalfon Trans. 1983 2525; (g) C. Y. Ng A. E. Martell and R. J. Motekaites Inorg. Chem. 1983 22 721. 185 R. I. Sheldon A. J. Jircitano M. A. Bero J. M. Williams and K. B. Mertes J. Am. Chem. SOC.,1983 lM 3028. 286 J. Silver paramagnetic Cu" macrobicyclic complex were estimated from ' H n.m.r. relaxation times.IS6 Copper(zi1). The stabilization of co-ordinated Cu"' by the tetra-aza macrocyclic dioxocyclam has been reported. A Cu1''-deprotonated-peptidecomplex of tri a-aminoisobutyric acid contains Cu" in a square planar geometry there is little evidence of axial co-ordination.'" Cu" diethyldithiocarbamates disproportionate into Cu"' and Cu' complexes.'88 The electrochemical production and isolation of tetrakis(pyridine N-oxide)copper(r~~) hexafluorophosphate in liquid SO2 has been inve~tigated"~ and the self-exchange rates for five Cu"'-'' peptides deterrnir~ed.'~' Mixed Vulence Complexes.Studies on the Cu20-CuO-Ta205 system have identified Cu3Ta,09 and Cu5Ta 1030.191 A series of seven dinuclear Cu"-Cu' complexes of macrocyclic ligands have been prepared,Is3 as has CU"CU'(C~H~NS)~C~~.'~~ The mixed valence cluster CU~(BTA)~(~-C~H~NC)~ [BTA = benzotriazolato( 1-)] has a compressed octahedral Cu" surrounded by four tetrahedrally co-ordinated Cu' ions.193 Simple electron-transfer reactions involving Cu"'*"( N4) couples have been examined (N4 = a tetra-aza macrocyclic ligand).'94 The complex [Cu,O(n-PrL'),]- (C104),.2H20 is isolated by electrolytic oxidation of the corresponding Cu"13 com- plex in acetonitrile and has a nearly planar triangular Cu1''Cu2"O core /"-cr N\* \ /*\ cu 1 (N CU "'& 'N Bioinorganic and Biological Copper.The tight binding of mono-olefins characteristic of the ethylene receptor site of plants has been found in some Cu' complexes.30 Tetranuclear Cu' thiolate complexes (3) have been examined in relation to the metal binding site of yeast copper thi0nei11.I~~ [Cu(dmphen),]+ forms complexes with some biologically relevant sulphur amino acids.I9' I86 W.-L. Kwik N. Herron K. Takeuchi and D. Busch J. Chem. SOC.,Dalton Trans. 1983 409. I87 L. L. Diaddario W. R. Robinson and D. W. Margerum Inorg. Chem. 1983 22 1021. I88 J.-P. Barbier R. P. Hugel and C. Kappenstien Inorg. Chim.Acta 1983 77 L117. I89 P. R. Sharp and A. J. Bard Inorg. Chem. 1983 22 3462. 190 J. M. Anast A. W. Hamburg and D. W. Margerum Inorg. Chem. 1983 22 2139. 19' P. N.W. Ilunga Acta Chem. Scand. Ser. A 1983 37 117. I92 W. E. Marsh W. E. Hatfield and D. J. Hodgson inorg. Chem. 1983 22 2899. I93 G. F. Kokoszka J. Baranowski C. Goldstein J. Orsini A. D. Mighell V. L. Hines and A. R. Siedle J. Am. Chem. SOC.,1983 105 5627. I94 K. Kumar F. P. Rotzinger and J. F. Endicott J. Am. Chem. SOC.,1983 105 7064. 195 D. Datta and A. Chakravorty Znorg. Chem. 1983 22 161I. 196 M. Linss M. G. Weller and U. Weser. Inorg. Chim. Acta 1983 80 201. 19' W.-L. Kwik K.-P. Ang and P.-C. Lau 1. Chern. SOC.,Dalton Trans. 1983 2269. Cu Ag Au; Zn Cd Hg Bis[4(n-propylmercaptomethyl)imidazole]copper(rr) diperchlorate contains Cu" co-ordinated by two thioether S atoms and two imidazole N atoms and is used as a model for blue copper ~r0teins.l~~ Cu" complexes of macrocyclic ligands are suggested as models for square-pyrimidal metal active-sites of CU" complexes of bleomycin and g1~tathione.l~~ Dicopper complexes of macrocyclics have been pro- posed as models for copper protein^."^ Diaquabis(2,6-dihydroxybenzoato)cop-per(r1) has a polymeric nature each Cu being in tetragonally distorted octahedral co-ordination;'OO it is claimed as a model for metal ions in humic acids."' Complexes of Cu" dipeptides with hexacyanoferrate(rr1) are proposed as models for the reaction of galactose oxidase with ferricyanide.20' A refined model that mimics the type I1 Cu" site in galactose oxidase has been reported.202 The Cu"-semiquinonato complex as a redox intermediate may be pertinent to the chemistry of related systems in biology.203(P-SP~)~CU~(PP~~)~ has a structure which is pertinent to the conforma- tions of metallo-cysteine proteins.204 Cu" complexing by the growth stimulating tripeptide glycylhistidyllysine has been studied in blood pla~rna.~" Research continues into vitamin B6 chemistry; quarternary complexes and the structures of two complexes of bis(N-t-butyl- pyridoxylideneiminato)copper(r I) have been described.206 The effect of Mg+ ions on Cu"-alkaline phosphatase has been investigated with respect to the Cu co- ordination in the presence and absence of inorganic phosphate at ~H6.0.~" The interaction of Cu" with human lactoferrin has been studied.208 Derivatives of the I 98 N.Aoi G. Matsubayashi and T. Tanaka J. Chem. SOC.,Dalton Trans. 1983 1059. 199 K. Miyoshi H. Tanaka E. Kimura S. Tsuboyama S. Murata H. Shimizu and K. Ishizu Inorg. Chim. Acta 1983 78 23. 200 F. Cariati L. Erre G. Micera A. Panzanelli C. Ciani and A. Siron Inorg. Chim. Acta 1983 80 57. 20 1 T. S. Srivastava and S. V. Deshpande Inorg. Chim. Acta 1983 78 37. 202 R.D. Bereman G. D. Shields J. R. Dorfman and J. Bordner J. Inorg. Biochem. 1983 19 75. 203 S. Harmalker S. E. Jones and D. T. Sawyer Inorg. Chem. 1983 22 2790. 204 I. G. Dance L. J. Fitzpatrick and M. L. Scudder J. Chem. Soc. Chem. Commun. 1983 546.205 P. M. May J. Whittaker and D. R.Williams Inorg. Chim. Acta 1983 80 L5. 206 (a) H. M. Marafie M. S. El-Ezaby and A. S. Shawali Polyhedron 1983 2 775; (b) F. Bigoli M. Lanfranchi E. Leporati and M. A. Pellinghelli Inorg. Chim. Acta 1983 80 135. 207 I. Bertini C. Luchinat A. Scozzafava A. Maldotti and 0.Traverso Inorg. Chim. Acta 1983 78 19. 208 E. W. Ainscough A. M. Brodie S. J. McLahlan and V. S. Ritchie J. Inorg. Biochem. 1983 18 103. 288 J. Silver red-violet cluster of Cu and penicillamine have been prepared209 and Cull' complexes of thyrotropin releasing factor The Cu binding centre of Cu-thioein from Saccharomyces cerevisiae has been investigated using EXAFS2" The effects of pH and redox inactive complexes on reactions of parsley plastocyanin with different inorganic redox partners have been Cytochrome-f binds at the negative patch on pla~tocyanin.~'~ In cyto- chrome oxidase the secondary structure of subunit I1 has been assigned and a Cu-binding site A 'H n.m.r.study of Cu" carbonic anhydrase in the presence of bicarbonate has been reported.215 The type-3 Cu site in metal-depleted Rhus vernicifera laccase has been Enzyme-bound Cu of dopamine p-mono-oxygenase has been studied catalytically after addition of an excess of Cu A Cu" tris-complex of a pyrimidine-derived ligand is reported to have [CuN,] in D3symmetry; the ligand may be an anti-tumour agent."' The oxygen co-ordinating uracil complexes of Cull and other MI1 ions have been Co-ordination structures in the Cu"-L-histidine (1 :2) system have been deduced220 and conforma- tion analysis and studies on hydration models of Cu threoninates and isoleucinate carried out.22' The hydrogen bonding in the Cu"-saccharin complex is significantly different to that of the analogous Fe Co and Ni complexes.222 The Cu" complex of 2'-deoxyguanosine 5'-monophosphate (5'-dGMP) has been studied to establish a corre- lation between spectral changes and the N(7) co-ordination site perturbation on the 5'-dGMP Ternary 2,2'-bipyridine and phen with Cu" dipeptide com- plexes have square pyrimidal geometries and the possible modes of their action with cancer cells have been The thermal decomposition of L-tryp-tophanatocopper(I1) has been examined to try to obtain tryptamine more economi- ally.^^^ The spectral properties of Cu" complexes of barbiturates have been reported.226 Silver.-A useful source of reference on silver chemistry can be found in 'Silver summaries' from the current world literature.227 20Y M.E. Cooke M. E. McDaniel S. R. Janes S. L. Jones N. Trobak B. C. Craytor D. R. Bushman and J. R. Wright J. Inorg. Biochem. 1983 18 313. 210 G. Formicka-Kozlewska M. Bezer and L. D. Pettit J. Inorg. Biochem. 1983 18 335. 21 I J. Bordas M. H. J. Koch H.-J. Hartmann and U. Weser Inorg. Chim. Acta 1983 78 113. 212 (a) S. K. Chapman A. D. Watson and A. G. Sykes J. Chem. SOC.,Dalton Trans. 1983,2543 (b) S. K. Chapman I. Sanemasa and A. G. Sykes ibid. 2549. 213 D. Beoka-Bets S. K. Chapman C. V. Knox and A. G. Sykes J. Chem.SOC.,Chem. Commun. 1983,1150. 214 (a) M. Lundeen J. Inorg. Biochem. 1983 18 I; (b) ibid. 1983 19 179. I. Bertini E. Canti C. Luchinat and E. Borgi J. Inorg. Biochem. 1983 18 221. B. Reinhammar J. Inorg. Biochem. 1983 18 113. T. Skotland and T. Ljones J. Inorg. Biochem. 1983 18 I I. N. Saha and D. Mukherjee Polyhedron 1983 2 47. A. R. Sarkar and P. Ghosh Inorg. Chim.Acta 1983 78 L39. L. Casella and M. Gulloti J. Inorg. Biochem. 1983 18 19. N. Raos and V. J. Simeon J. Inorg. Biochem. 1983 18 135. S. K. Haider K. M. A. Malik K. J. Ahmed H. Hess H. Riffel and M. B. Hursthouse Inorg. Chim. 215 216 217 218 219 220 22 I 222 Acta 1983 72 21. 223 Ajmir-Riahi and T. Theophanides Inorg.Chim. Acta 1983 80 223. 224 S. V. Despande and T.S. Srivastava Inorg. Chim. Acta 1983 78 75. 225 P. Gili and K. de la Fuente Inorg. Chim. Acta 1983 78 L5. 226 A. Pezeshk F. T. Greenaway and J. R. J. Sorenson Inorg. Chim.Actu 1983 80 191. 227 The Silver Institute. Suite 1138 1001 Connecticut Avenue N.W. Washington D.C. 20036. Cu Ag Au; Zn,Cd Hg 289 Silver Heterornetallic Clusters. Heterometallic adducts of [Rh6(co)15c]'- including the double- and triple-decker sandwich compounds [Ag,{Rh,(CO)i5C}2]4-" (n = I and 3) and [Ag,{Rh,(C0)iSC}3]6-" (n = 2 or 4) and the X-ray structure of [PPh4]3[Ag{Rh6(CO)l 5C}2] have been reported.228 [Ag{Rh(CO)(PPh3)( T-C~H~)}~] [PF,].C,H,Me contains a near linear Rh-Ag-Rh framework.229 The synthesis and characterization of [Ag2Pt( p-S)4(PPh3),](BF4)2.0.25CHC13has been described both Ag+ ions are linearly co-ordinated to the S atoms the small bite distance of the [R2(P-S)~(PP~~)~] ligand leads to an Ag.-.Ag contact distance of only 2.8 15 A.230 Triangular Fe- Ag clusters of the type [Fe,Ag(Co),{CHC(C,H,)( NRR')}P(C,H5)2]X have been reported.231 Silver(I). The structure of silver pyrovanadate Ag4V207 is described as the C.C.P. silver metal structure in which some Ag atoms are replaced by V207 groups and others are shifted.232 Di-silver(I) decachlorodioxotetra-aluminate(rII) Ag2[AI4CIi0O2],contains [A14C1,002]2- and Agf ions the latter are co-ordinated by five chlorines in a distorted trigonal-bipyramidal arrangement.233 Precipitation reac- tions between silver nitrate and sodium tungstate have been studied by poten- ti~metry.'~~ Ag(NH,)2N03 contains linear diamine Ag moieties at 223 K235and in CsAgCI at 170"C the Ag' has a trigonal-bipyramidal ~o-ordination.'~~ Structures of eleven melts of different compositions in the systems (Ag.K.Na)(I NO3) have been studied.237 Structures of [Ag(L)X] where L = 2 I 1-bis(diphenylphosphino)-methyl-benzo[c]phenanthrene and where X = C1 (A) SnCI (B) NO3 (C) and C104 (D) have been rep~rted.'~' The Ag atom in A shows a distorted trigonal co-ordination to two P atoms and one CI atom.238 The Ag atoms in B-D are formally four co-ordinated.Electrochemical studies of chloro-complex formation in chloroalumi- nate melts indicated that Ag' forms stable mononuclear complexes of the type AgCl,'-P(2 d p d 4) in the chloride ion-rich compositions.239 The reaction of (CF3C02)Ag with LiR gives [Bu4N][AgR2](R = C6F5 or c6c1s).240 Reaction of Ag C 1O4 with 2,5 -di met h y1-2,5 -di -isocy ano he xan e (TM B) inmethano I-t oni t ril e yields [Ag2(TMB)]3(C104)3.It consists of pairs of -..AgCN NCAgCN NCAg... infinite chains containing the TMB ligand in an extended form.24i Both I 1 and 2:3 adducts of cyclo-octotatetraene and AgN03 have been reported the former 228 B. T. Heaton L. Strona S. Martinengo D. Strumolo V. G. Albano and D. Braga J. Chem. SOC.,Dalton Trans. 1983 2175. 229 N. G. Connelly R. LUCY,J. D. Payne A. M. R. Gahas and W. E. Geiger J. Chem. SOC.,Dalron Trans. 1983 1879. 230 C. E. Briant T.S. A. Hor N. D. Howells and D. M. P. Mingos J. Organomet. Chem. 1983 256 C15. 23 I G. N. Matt N. J. Taylor and A. J. Carty Organomerallics 1983 2 447. 232 R. Masse M. T. Averbuch-Pouchot A. Durif and J. C. Guitel Acta Crystallogr. 1983 c39,1608. 233 D. Jentsch P. G. Jones E. Schwarzmann and G. M. Sheldrick Acta Crystallogr. 1983 C39 1173. 234 J. B. Jensen and J. Lou Acta Chem. Scand. Ser. A 1983 37,617. 235 T. Yamaquchi and 0. Lindqvist Acta Chem. Scand. Ser. A 1983 37,685. 236 H.-C. Gaebell G. Meyer and R. Hoppe Z. Anorg. Allg. Chem. 1983 497,199. 237 B. Holmberg and G. Johansson Acfa Chem. Scand. Ser. A 1983 37,367. 238 M. Barrow H.-B. Burgi M. Camelli F. Caruso E. Fisher L. M. Venanzi and L. Zambonelli Inorg. Chem. 1983 22 2356.239 T. M. Laher and C. L. Hussey Inorg. Chem. 1983 22 1279. R. Uson A. Laguna and J. A. Abad. J. Organorner. Chem. 1983 246 341. A. Guitard A. Mari A. L. Beauchamp Y.Dartiquenave and M. Dartiquenave Inorg. Chem. 1983,22 240 24 I 1603. 290 J. Siluer Q consists of strongly bonded Ag'-C8H8 units linked by weaker Ag-ligand interac- tion~.~~~ Bis(1,2:5,6-7-cyclo-octatetraene)silver(~)nitrate exists as discrete molecules in the crystalline state (4).242' Benzocyclo-octatetraensilver(1) perchlorate is an example of a silver ion co-ordinated to an arene and an olefin ligand simultane~usly.~~~ Structures of [{Ag[C,(C02Me)s](OH)2}n]-1.5nH20,[{Ag[Cs(C0,Me)s](PPh3)}2] and [Ag{C,(C02Me),}(PPh,),1 have been reported Ag-C bonding interactions are found in the first two complexes.244 The structure of mesitylsilver(1) shows it to be tetranuclear [Ag(2,4,6,-Me3C6H2)I4 in the solid state.245 The interaction of Ag' with P-disulphone carbanions in aqueous alkaline media have been reported; a P-(5) 242 (a) W.C. Ho and T. C. W. Mak 1.Organomet. Chem. 1983 241 I31 ;(b) ibid. 1983 246 331;(c) ibid. 1983 243 233. 243 T. C. W. Mak W. C. Ho,and N. Z. Huang J. Organomet. Chem. 1983 251 413. 244 M. I. Bruce M. L. Williams B. W. Skelton and A. H. White J. Chem. SOC.,Dalton Trans. 1983 799. 245 S. Garnbarotta C.Floriana A. Chiesi-Villa. and C. Guastini J. Chem. Soc. Chern. Commun. 1983. 1087. Cu,Ag Au; Zn Cd Hg 29 1 disulphone carbanion with Ag' is an example of an sp3 carbon bonded to Ag' (5).,, Silver alkene-complexes their stoicheiometries stabilities and ' H n.m.r.bound shifts have been reported.247 Some silver(1) complexes [Ag(am),]NO (where am = phen or biby) have been studied using secondary ion mass spectrometry248 and the stability constants of Ag' complexes of N-methyl substituted 4-methyldiethylenetriamines in aqueous solution at 25 "C determined.249 [Tetrakis(tetrasulphur tetranitrogen dioxide)sil- ver((r)]+[AsFJ contains the Ag atoms 0.53 8 below a square of 4N atoms.250 catena-Bis( p-benzoato-O,O',p-O)bis(pyridine)disilver(I) contains Ag co-ordinated in a distorted tetrahedron to one N and three 0 atoms a similar environment is found in bis[ p-phthalato(tri pyridine)disilver(~)] for one Ag but the other forms almost a plane with the nearest two N and two 0 atoms.25' Single-crystal e.p.r.spectra of two spin-labelled Ag porphyrins doped in Zn tetraphenylporphyrin have been obtained.252 (PPh,),Ag2MoS,~0.8CH2C12 contains a doubly bridging MoS,~-ligand generating a nearly linear Age. eM0.a .AgP moiety with one tetrahedrally and one trigonal-planar co-ordinated Ag atom.253 [Ag,{ S(NSO),},][AsF,],.SO contains two crystallographically independent Ag atoms.254 The structure of (cyclo-L-methionylglycine)silver( I) nitrate consists of infinite linear arrays of Ag atoms doubly bridged by methionine S atoms and nitrate The intertwined double (-Ag-SR-),-strand chain-structure of crystalline (3-methylpentane-3-thio1ate)sil-ver has been described in relation to (AgSR)s molecules in solution.256 Silver(1) salts have been used as one-electron and two-electron oxidants in their reactions with [Fe2(~-C5H5)2(C0)4-n(CNMe)n] derivatives (n = O-2).257 Silver-catalysed macrocyclic ether formation has been studied.[(CH2O),Ag2][Ag][AsF,] contains a novel twelve-membered macrocyclic ether.258 The mechanism of the Ag-catalysed epoxidation of ethylene has been investigated.259 Studies of the precipitation of Ag20 within unilamellar vesicules have been reported.260 Evidence has been presented against ion-pair formation in the reaction of ethyl halides with Ag salts in ethanol2,' and the salts Z[AuR2] (Z = Ag(C4HgS) or Ag R = C6F3H2or C,F5) have been prepared.262 246 J. R. DeMember H. F. Evans F. A. Wallace and P.A. Tariverdian J. Am. Chem. SOC.,1983 105 5647. 247 W. Offerman and U. Fritzsche Inorg. Chim. Ana 1983 73 113. 248 J. L. Pierce K. L. Busch R. G. Cooks and R. A. Walton Znorg. Chem. 1983 22 2492. 249 J. Yperman J. Mullens J.-P. Francois and L. C. Van Poucke Inorg. Chem. 1983 22 1361. 250 H. W. Roesky M. Thomas H. G. Schmidt W. Clegg M. Noltemeyer and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1983 405. 25' (a) M. Hedrich and H. Hartl Acta Crysrallogr. 1983 C39 533; (b) ibid. 1983 C39 1649. 252 R. Damoder K. M. More G. R. Eaton and S. S. Eaton Inorg. Chem. 1983 22 3728. 253 A. Muller H. Bogge and U. Schirnanski Inorg. Chim.Acta 1983 69 5. 254 H. W. Roesky M. Thomas P. G. Jones W. Pinkert and G. M.Sheldrick J. Chem. SOC. Dalton Trans.1983 1211. 255 G. Valle and R. Eltore J. Chem. SOC.,Dalton Trans. 1983 453. 256 I. G. Dance L. J. Fitzpatrick A. D. Rae and M. L. Scudder Inorg. Chem. 1983 22 3785. 257 B. Callan and A. R. Manning J. Chem. SOC.,Chem. Commun.,1983 263. 258 H. W. Roesky E. Peymann J. Schimkowiak M. Noltemeyer W. Pinkert and G. M. Sheldrick J. Chem. SOC.,Chern. Commun.,1983 981. 259 R. €3. Grant and R. M. Lampert J. Chem. SOC.,Chem. Commun.,1983 662. 260 S. Mann and R. J. P. Williams J. Chem. SOC.,Dalron Trans. 1983 31 1. 26 1 D. N. Kevill and E. K. Fujimoto J. Chem. SOC.,Chem. Commun.,1983 1149. 262 K. Moss R. V. 'D'Parish. A. Laguna M. Laguna and R. Uson J. Chem. SOC..Dalton Trans. 1983,2071. 292 J. Silver Silver( 11). Secondary ion mass spectrometry was used to study [Ag(biby)2]S208 and [Ag(~y)~]S~o~.~~* and the structure of the [2.2.2] paracyclophane (C24H24) complex of Ag" has been reported.263 Silver(1rz).Both the kinetics and mechanism of H202oxidation by Ag"' in aqueous alkaline media,264 and the kinetics of reduction of the tetrahydroxoargentate(lI1) ion by arsenite have been studied by stopped-flow ~pectrophotornetry.~~~~ Gold.-Gold Heterometallic Complexes. A number of papers dealing with gold atoms in heterometallic clusters and in gold clusters have been p~blished.~~**~~~-~~* Details of the structural information obtained on these clusters is in Table 1. The reactivity of [Aug(PPh3)J3+ and [Au8(PPh3),I2+ towards isopropyl isocyanide has been studied,279 the electrochemical reduction of the former cluster has also been de~cribed.~"~ The e.s.r.spectrum of matrix isolated Au3 has been observed.280 Gold(1).[(C,Me,)Rh( ~U-L)AUP(C~H~)~](CIO~)~.CH~C~~ (where L = N-indolyl) and [(PhP,),Au,( p-bbzim)Rh(cod)][C10,1.CHC13 (where bbzim = dianion of 2,2'-bibenzimidazole and cod = cyclo-octa- 1,5-diene) both contain Au atoms in essen- tually linear co-ordinations.'*' The preparations of heterodinuclear Rh'-Au' or Ir'-Au' indoyl-bridged complexes of the type [(diolefin)M( 77-Tn)AuPR,]+ (M = Rh; diolefin = cod tetrafluorobenzobarrelene = TFB or Me,TFB; M = Ir; 2h3 C. Cohen-Addad P. Baret P. Chautemps and J. L. Pierre Acta Crystallogr. 1983 C39 1346. 264 (a)E. T. Borish and L. J. Kirschenbaum J. Chem. Soc. Dalton Trans. 1983,749; (b)L.J. Kirschenbaum and J. D. Rush Inorg. Chem. 1983 22 3304. 265 L. J. Farrugia M. J. Freeman M. Green A. G. Orpen F. G. A. Stone and I. D. Slater J. Organomet. Chem. 1983 249 273. 266 L. W. Bateman M. Green K. A. Mead R. M. Mills I. D. Slater F. G. A. Stone and P. Woodward J. Chem. SOC.,Dalton Trans. 1983 2599. 267 M. I. Bruce and B. K. Nicholson J. Organomet. Chem. 1983 252 243. 268 B. F. G. Johnson J. Lewis J. N. Nicholls J. Puga and K. H. Whitmire J. C'hem. SOC.,Dalton Trans. 1983 787. 269 A. G. Cowie B. F. Johnson J. Lewis J. N. Nicholls P. R Raithby and M. J. Rosales J. Chem. Sac. Dalton Trans. 1983 23 11. 270 B. F. G. Johnson J. Lewis W. J. H. Nelson J. Puga P. R. Raithby D. Braga M. McPartlin and W. Clegg J. Organornet.Chem. 1983 243 C13. 27 I K. Burges B. F. G. Johnson D. A. Kaner J. Lewis P. R. Raithby S. N. Azman and B. Syad-Mustaffa J. Chem. SOC.,Chem. Commun. 1983 455. 272 K. Burges B. F. G. Johnson J. Lewis and P. R. Raithby J. Chem. SOC.,Dalton Trans. 1983 1661. 273 B. F. G. Johnson J. Lewis W. J. H. Nelson M. D. Vargas D. Braga and M. McPartlin 1.Organomet. Chem. 1983 246 C69. 274 A. L. Casalnuovo L. H. Pignolet J. W. A. van der Velden J. J. Bour and J. J. Steggerda J. Am. Chem. SOC.,1983 105 5957. 275 R. A. Awang G. A. Carriedo J. A. K. Howard K. A. Mead 1. Moore C. M. Nunn and F. G. A. Stone J. Chem. SOC.,Chem. Commun. 1983 964. 276 (a) K. Burgess B. F. G. Johnson and J. Lewis J. Organomet. Chem. 1983,247 C42; (b)J. Chem. SOC. Dalton Trans.1983 1179. 277 C. E. Briant K. P. Hall and D. M. P. Mingos J. Organomef. Chem. 1983 254 C18. 278 J. W. A. Van der Velden J. J. Bow W. P. Bosman and J. H. Noordik Inorg. Chem. 1983 1913. 279 (a) W. Bos J. J. Bour J. W. A. Van der Velden J. J. Steggerda A. L. Casalnuovo and L. H. Pignolet J. Organomet. Chem. 1983 253 C64; (b) J. G. M. van Linden M. L. H. Paulissen and J. E. J. Schmitz J. Am. Chem. SOC.,1983 105 1903. 2un J. A. Howard R. Sutcliffe and B. Mile. J. Chem. Soc.. Dalton Trans. 1983 1449. "' (a) A. Tiripicchio M. Tiripicchio Carnellini R. Uson L. A. Ora and Cabeza J. Organomet. Chem. 1983 244 165; (b) R. Uson L. A. Ora J. Gimeno M. A. Ciriano J. A. Cabeza A. Tiripicchio and M. Tiripicchio Carnellini J. Chem. SOC.,Dalton Trans.1983 323; (c) R. Uson L. A. Ora J. A. Cabeza C. Foces-Foces C. H. Cano and S. Garcia-Blanco J. Organomet. Chem. 1983 246 73. Cu Ag Au; Zn Cd Hg 293 Table 1 Gold heterometallic compounds Complex Structure of Cluster Re$ Au2Ru3( p-s)(co)8( PPh3)3 Au2Ru3(p-H)(pL-COMe)(C0)9(PPh3)2AuRu,( V-COM~)(CO),~(PP~~) A~Ru3(p-H)2(~3-C0Me)(C0)9(pph3) trigonal bipyramidal distorted square-pyramid butterfly metal core Ru triangle (Au edge-bridging one side) 265 265 266 266 AuRu~(~-COM~)(CO)~(PP~,) Au binds to Ru triangle making a tetrahedron two faces of 266 which have triply bridging AuPPh ligands Ru4Au(C0) 1 2(PPh3)3 bicapped trigonal-bipyramidal metal core in which two Ru,Au 267 faces of the Ru4Au fragment are capped by the other two Au atoms Ru~C(CO)I5{ p-Au(PPh,)}CI bridged butterfly configuration 268 Au atom bridges hinge bond distorted square-pyramid of Ru 268 atoms Au bridges two Ru atoms Ru5C core to which an AuPPh 269 is bound RU~C(CO)I,(NO)(AuPPh3) Ru6C core Au(PPh,) tricaps 270 three Ru atoms 0s3(c0)10( p.L-AUPEt3)2 Os3 triangle both AuPEt groups bridge same edges 27 1 ~~3(~~)8(pph3>~A~(pph3~~ Os triangle AuPPh bridges 272 (2-N HC.j H4 N) longest 0s-0s bond [OsloC(C0)24AuPPh3][PPh3Me] Au ligand adds to capping 273 tetrahedron of dianion [OS10c(c0)241~-AuIr tetrahedra 274 Au,Ir(PPh,) planar structural 274 unit WAuW is linear Au also bonds 275 to two C atoms Au sandwiched between two 228 Rh6 trigonal-prismatic units Au6 edge-shared bi-tetrahedral 277 central Au surrounded by seven 278 AuPPh moieties Au6 edge-shared bi-tetrahedral 278 diolefin = cod) have been described.281' The structure of [AuC1(C4Ph4)(phen)](6) and the preparation of related complexes have been reported.28'd The mesitylgold(1) complex (AuMes) (Mes = 2,4,6-Me3C6H2j has a five-pointed star shape.282 Dimethyl gold iodide reacts with alkali-metal amides to form Au-N 28 I (d) R.Uson J. Vicente M. T. Chicote P. G. Jones and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1983 1131. 282 S. Gambarotta C. Flioriani A. Chiesi-Villa and C. Guastini J. Chem. SOC.,Dalton Trans. 1983 1304. 294 J. Silver heterocycles. KNH2 yields the eight-membered ring [Me2AuNH2] whereas with LiNMe2 the four-membered ring [Me2AuNMe212 is obtained.283 Reaction of halide ions with gold phenylacetylide yields the phenylethynyl gold(1) halide anion complexes [N%][XAuC,Ph] (X = CI or Br; Ph = Et; X = I; R = [Au{C5(C02Me),}(PPh,)] contains an Au(PPh,) moiety that interacts with three carbons of the C5 ring such that the co-ordination is intermediate between (T and ~7 In ~nido-[9-(q-C5H5)-p ,-(P~,PAU)~,~,~-C~N~B~H,~] .~~~ the Au bonds to two B and one P atom.286 197Au-Mossbauer parameters were reported for the salts Z[AuR2]{ R = C6F5; Z = [NBu4]+ [Ag(C,H,S)]+ [Au(SbPh3),]+ or [Au(pdma),]+ [pdma = o-phenylenebis(dimethylarsine)]}.The data for the two Au-containing cations are consistent with four co-ordination.262 Tris[bis(diphenylphosphino)methane]di-iodotetragold contains a slightly distorted Au tetrahedron one Au is co-ordinated to an iodine while the remaining Au triangle contains three identical Au environ- ments.Mossbauer spectroscopy shows the presence of both Au sites.287 Structural information of eleven Au' thiolates and twelve phosphine co-ordinated Au' thiolates has been collected.288 Gold(zzr). Kinetics of hypophosphite ion oxidation by Au"' in aqueous HCI to give phosphorus acid and Au' have been obtained and interpreted in terms of the probable formation of intermediate Au".~~~ Kinetics of the substitution of ammonia by bromide in amminetribromidogold( III) in acid solution have been Vibra-tional and 35Cl n.q.r. spectra of some trichlorochalcogen tetrachloroaurates [ACI3] 283 H. N. Adams U. Grassle W. Hiller and J.Strahle Z. Anorg. Allg. Chem. 1983 504 7. 284 0. M. Abu-Salah and A. R. Al-Ohaly Znorg. Chim. Acta 1983 77 L159. 285 M. I. Bruce J. K. Walton B. W. Skelton and A. H. White J. Chern. SOC.,Dalton Trans. 1983 809. 286 G. K. Barker N. R. Godfry M. Green H. E. Parge F. G. A. Stone and A. J. Welch J. Chem. SOC. Dalton Trans. 1983 271. 287 J. W. A. Van der Velden J. J. Bour R. Pet W. P. Bosman and J. H. Noordik Znorg. Chem. 1983 22 3112. 288 D. T. Hill B. M. Sutton A. A. Isab T. Razi P. J. Sadler J. M. Trooster and G. H. M. Calk Znorg. Chem. 1983 22 2936. 289 K. K. Sengupta B. Basu S. Sengupta and S. Nandi Polyhedron 1983 2 983. 290 L. H. Skibsted Acra Chem. Scand. Ser. A 1983 37 613. Cu,Ag Au; Zn Cd Hg 295 [AuCl,] (A = S Se or Te) indicate that the AuC1,- ion is considerably distorted from D4hsymmetry.29' Electronic absorption and m.c.d.spectra are reported for AuX,-(X = C1-or Br-) tran~-Au(CN)~X,- (X = C1- Br- or I-) and trans-Au(CN),BrY-(Y = C1-or I-) in acetonitrile Kinetics of oxidation reactions of trans- and/or cis-[PtC12(NH2R),] compounds by [AuCl,]- in the pres- ence of [NEt,Cl,] have been investigated in a~etonitrile.,~~ Reaction of tetra- bromoaurate with uridine in water occurs with a 1 1 stoicheiometry producing gold(1) and 5-brom0-6-hydroxy-5,6-dihydrouridine.~~~ The structures of cyano- and halogeno-bridged Au"' and Pd" complexes have been compared.29s Reactions of 1,3,5,-trithiane (TT) with the metal halide results in AuCI,.(TT).*~~ The structures of [AuR,(dppm)]ClO and [C1Au(dppm)Au(dppm)AuCl][AuClR3][R = C6FS; dppm = bis(diphenylphosphino)methane] have been reported the cation of the latter shows short Au-..Au contacts (ca.3.1 The He' and He" photoelectron spectra of three Au"' complexes [AuMe3L] (L = PMe3 PMe,Fh and PMePh,) have been recorded in the gas phase.298 Treatment of [Me,N][AuCl,] with di- organomercury derivatives R2Hg in which R is an ortho-nitroaryl group (R = o-O2NC6H4 or 2-Me,6-02NC6H3) gives anionic Au'" complexes of the type cis- Me4N[AuR2Cl,J. Mixed Valence Chemistry. Au'-Au" and Au'- Au"' oxidation in ylide complexes with chlorinating agents has been studied300" and a new route for the synthesis of Au' and Au" I pentafluorophenyl(y1ide) complexes rep~rted.~"' Biological Gold.Differences between the structure of the anti-arthritic Au drug Myocrisin in the solid state and in solution have been studied.301 Kinetic studies of dealkylation of ethylcobalamim by tetrachloroaurate have been reported.302 2 Zinc Cadmium and Mercury A useful review of zinc and cadmium has appeared recently.303 Zinc.-A neutron structural study of the successive phase-transitions at 60 100,235 and 300 "C in Rb2ZnC1, has provided evidence that the ZnC1 group undergoes a large libration motion304 and the structure of (NH,),ZnCl has been re-investigated to allow for twinning.304b The structures of [(C,3H27)NH3]2ZnC14 and 29 1 A. Finch P. N. Gates T. H. Page and K. B. Dillon 1.Chem. SOC.,Dalton Trans. 1983 1837. 292 H. Isci and W. R. Mason Inorg.Chem. 1983 22 2266. 293 A. Peloso J. Chem. SOC. Dalton Trans. 1983 1285. 294 R. Ettore J. Chem. Soc. Dalton Trans. 1983 2329. 295 J. A. Davies and J. F. Liebman J. Chem. SOC.,Dalton Trans. 1983 1793. 296 S. R. Wade and G. R. Willey Inorg. Chim. Acta 1983 72 201. 297 R. Ush A. Laguna M. Laguna E. Fernandez M. D. Villacampa P. G. Jones and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1983 1679. 298 G. M. Bancroft T. C. S. Chan and R. J. Puddephatt Inorg. Chem. 1983 22 2133. 299 J. Vicente M. T. Chicote A. Arcas M. Artigao and R. Jimenez J. Organomet. Chem. 1983 247 123. 300 (a) H. Schmidbaur and P. Jandik Inorg. Chim. Acta 1983,74,97; (b) R. Uson A. Laguna M. Laguna and A. Usbn Inorg. Chim. Acta 1983,73 63. 30 I M. C. Grootveld and P.J. Sadler 1.Znorg. Biochem. 1983 19 51. 302 Y.-T. Fanchiang Inorg. Chem. 1983 22 1693. 303 E. C. Constable Coord. Chern. Rev. 1983 52 1. 304 (a) M. Quilichini and J. Pannetier Acta Crystallogr. 1983 B39 657; (b) H. van Koningsveld Acta Ciystallogr. 1983 C39. 15. 296 J. Silver [C4H6N30]2[ZnC14] have been reported.305 The synthesis and thermochemistry of adducts of Zn Cd and Hg halides with N,N-dimethylformamide have been repor- ted306 and the formation of ZnXn2-" (X- = Br- I- or NCS-) complexes in methanol studied.307 The complexes Zn(py~)~X~ and Zn(pyz)X (pyz = pyrazine; Z = C1 or Br) were doped with Mn" ions and studied by e.~.r.~O~ and the mixed ligand complexes of ZnC1 and substituted pyridines in~estigated.~" The syntheses of M(AH)2C12 (M = Zn or Cd; AH2 = l-methyl-4,4-dimercaptopiperidine) are described the AH2 group binds to Zn and Cd via one sulph~r.~" Extracts with tri-n-octylammonium chloro-complexes of Zn" of various compositions have been studied.,' Structural and spectroscopic characterization of a series of d lo metal(I1) compounds of the type [M(dmpd)X,] (M = Zn" Cd" or Hg"; dmpd = 2,2-dimethylpropane-1,3-diamine; X = C1 Br or I) have been de~cribed.~" The structures of the substituted benzylideneamine complexes [ZnBr,(C,,H 18N2)] and [ZnBr2(C13H20N2)] contain tetrahedral Zn bonding to two Br and two N Approximately octahedral Zn is found in [Zn(en),]C1,.2H203'3 and in [Zn(C4HR02)zC12] each Zn atom is in a distorted trig~nal-bipyramid.~'~ NaZn20H(S03) has been ~repared.~ In Zn(PO,), ZnO octahedra are arranged Is in and Zn2P40 I2.8H20 contains two octahedrally co-ordinated Zn atoms.316b Single crystals of KZnP,O have been grown from the ZnP03F-2.5H,0 contains both octahedral and tetrahedral Zn.316d Zn and Hg dis- solve electrolytically in the mixed non-aqueous solvents SO2-dimethylsulphoxide -dimethylformamide -acetonitrile -acetone or -nitrobenzene.I' [MFeCO,] com-plexes (M = Zn Cd or Hg) undergo mild stepwise reduction to give first the kinetically stable [M(Fe(C0),),l2- and subsequently [Fe2(C0)8]2-.317 The interaction of CO with the (1070) ZnO surface has been studied and discussed in the light of the mechanism of methanol synthesis on Zn0.318 Single crystal growth of Zn,0(B02)6 has been rep~rted.~ ZnPt306 contains Zn in a six-co-ordinate environment.320 {Zn[S(NS0)2]2}(AsF6)2.2S02is a 2D-network through 0 atoms.32I The He(1) photo- electron spectra of acetylacetone (HAA) and its Zn"(AA) complex have been mea~ured.'~~" Zn(AA)2 reacts with C2N2 in C2H4C12 or CH2C12 under ambient 305 (a) F.J. Zuhiga and G. Chapius Acta Crystallogr. 1983 839 620; (b) P. E. Bourne and M. R. Taylor Acta Crystallogr. 1983 C39 430. 306 0. A. de Oliveira A. P. Chagas and C. Airoldi Inorg. Chem. 1983 22 136. 307 H. Doe A. Shibagaki and T. Kitagawa Inorg. Chem. 1983 22 1639. 308 R. B. Birdy and M. Goodgame J. Chem. Soc. Dalton Trans. 1983 1469. 309 K. Sawada T. Sakaguchi and T. Suzuki J. Chem. Soc. Dalton Trans. 1983 447. 310 H. Barrera and F.Teixidor Polyhedron 1983 2 1165. 311 F. Cariati G. Ciani L. Menabue G. C. Pellacani G. Rassu and A. Sironi Inorg. Chem. 1983,22 1897. 312 R. Bartnik S. Lesniak A. Laurent R. Faure and H. Loiseleur Acta Crystallogr. 1983 C39 1034. 313 C. Muralikrishna C. Mahadevan S. Sastry M. Seshasayee and S. Subramanian Acta Crystallogr. 1983 C39 1630. 314 A. Boardman R. W. H. Small and 1. J. Worral Acta Crystallogr. 1983 C39 1005. 315 H. D. Lutz W. Eckers W. Buchmeier and B. Engelen 2. Anorg. Allg. Chem. 1983 499 99. 316 (a) M. T. Averbuch-Pouchot A. D. et M. Bagieu-Beucher Acta Crystallogr. 1983 C39 25; (b) M. T. Averbuch-Pouchot 2. Anorg. Allg. Chem. 1983 503 231 ;(c) L. Bohatjl and J. Liebertz Z. Kristallogr. 1983 163 251; (d) J. Durand A.Larbot L. Cot M. Duprat and F. Dabosi Z. Anorg. Allg. Chem. 1983 504 163. 317 B. A. Sosinsky R. G. Shong B. J. Fitzgerald N. Norem and C. O'Rourke Inorg. Chem. 1983,22,3124. 318 K. L. D'Amico F. R. McFeely and E. I. Solomon J. Am. Chem. SOC.,1983 105 6380. 319 L. BohatL S. Houssuhl J. Liebertz and S. Stahr 2. Kristallogr. 1983 161 157. 320 K. B. Schwartz J. B. Parise C. T. Prewitt and R. D. Shannon Acta Crystullogr. 1983 B39 217. 32 I H. W. Roesky M. Thomas J. W. Bats and H. Fuess Inorg. Chem. 1983 22. 2342. Cu Ag Au; Zn Cd Hg 297 conditions undergoing cyanation of the organometallic ring.322 Zn" triflate com- pounds containing aminopropanol isomers have been prepared.'*'' Zinc(r1) fumerate tetrahydrate contains a Zn atom surrounded by six 0 atoms.323 Di-t- butylcatecholato and semiquinonato zinc(r1) complexes have been characterized by cyclic vo1tammet1-y.~~~ and bis[l,3-bis(2- Di-aqua(4-oxoheptanedioato)zinc(11)~~~" hydroxypheny1)-1,3-propanedionato]bis(ethanol)zinc(11)~~~ contain distorted ZnO polyhedra.[M(OS,N,),][AsF,] (M = Zn or Cd) have M atoms co-ordinated by six five-membered heterocyclic ligand~.~~ [NMe4][Zn{S2P(OC6H,Me-p),l and [NEt,][Zn(S,PPh,),] both have slightly distorted tetrahedral geometries in which one S2PR2 ligand is bidentate and the other two are ~nidentate.,~' The Zn-tartarate- thiocyanate system has been investigated p~laragraphically.~~~ Complex for-mation equilibria between 2-amino-2(hydroxymethyl)propane-I ,3-diol and 1,1,1-tris(N-methylaminomethy1)ethane with Zn have been re~0rted.l~~ Dimeric methyl(dipheny1amino)zinc contains a Zn2N ring.329 Dinitrobis(pyridine)zinc(Ir) and bis(2-methylpyridine)dinitritozinc(11) have similar geometries with the amine ligands occupying cis-co-ordination sites.330 Zinc(I1) compounds of substituted imidozole ligands or benzotriazole and related ligands have been reported.'55a Zinc(rr) complexes with some bidentate ligands involving the pseudo-imidazole functional groups imidazoline benzimidazole and benzothiazole have also been de~cribed.'~~ Reactions of 2-(2-thienyl)benzothiazolinewith Zn Cd and Hg" have been reported.331 [EtZn( Et)(t-Bu)NC(H)=C(Me)6] contains a four membered Zn,02 ring.,, Ion pairing and optical activity in diastereomeric Zn"-phen S-valinate systems has been studied.333 The zinc complexes of 2-acetyl and 2-benzoylpyridine hydrazones have been characteri~ed~,~ and the Zn" Cd" and Hg" complexes of 4,6-dimethylpyrimidine-2(1 H)-one examined.335 Diamminebis( 2-sulphanil- amidopyrimidinato)zinc(11) contains Zn in a distorted tetrahedral N ~o-ordination,~~ while dichloro(terpyridyl-2:2',6':2")zinc(I I) contains pentaco-ordin- ated Zn atoms.337 Bis( N-(2-pyrrolylmethylene)-t-butylamino]zinc(11)has Zn in an elongated tetrahedral site.,,' Complexes of NN'-ethylenebis(salicy1ideneimine)with Zn Cd and Hg" have been ~haracterized.~,' The radical complex [(PhZn)L(ZnPh)]+ 322 B.Corain M. Basato A. Marcomini and H. F. Klein Inorg. Chim. Acta 1983 74 1. 323 M. P. Gupta R. D. Sahu and P.R. Maulik Z. Kristallogr. 1983 163 151. 3 24 M. E. Bodini G. Copia R. Robinson and D. T. Sawyer Znorg. Chem. 1983 22 126. 325 (a) A. Karipides Acta Crystallogr. 1983 C39 1541; (b) X. Solans M. Font-Altaba J. L. Brianso A. Llobet F. Teixidor and J. Casab6 Acta Crystallogr. 1983 C39 1512. 326 H. W. Roesky M. Thomas J. W. Bats and H. Fuess J. Chem. SOC.,Dalton Trans. 1983 1891. 327 J. A. McCleverty R. S. Z. Kowalski N. A. Bailey R. Mulvaney and D. A. O'Cleirigh J. Chem. Soc. Dalton Trans. 1983 627. 328 Km. Krishna and S. K. Jha Polyhedron 1983 2 669. 329 N. A. Bell H. M. M. Shearer and C. B. Spencer Acta Crystallogr. 1983 C39 1182. 330 M. A. Hitchman R. Thomas B. W. Skelton and A. H. White J. Chem. SOC. Dalton Trans. 1983 2273. 33 I L.F. Capitkn-Vallvey and P. Espinosa Polyhedron 1983 11 1147. 332 M. R. P. van Wet J. T. B. H. Jastrzebski G. van Koten K. Vrieze and A. L. Spek J. Organomet. Chem. 1983 251 C17. 333 A. Deciniti and G. Larrazabal Polyhedron 1983 2 1075. 334 D. Demertzi and D. Nicholls Znorg. Chim. Acta 1983 73 37. 335 R. Battistuzzi and G. Peyronel Polyhedron 1983 2 47 I. 336 N. C. Baenziger S. L. Modak and C. L. Fox jun. Acra Crystallogr. 1983 C39 1620. 337 M. Vlasse T. Rojo and D. Beltran-Porter Acta Ctystallogr. 1983 C39 560. 338 J. A. Kanters A. L. Spek R. Postma C. C. van Stein and G. van Koten Acta Crystallogr. 1983 C39 999. 339 H. A. Tajmir-Riahi Po/vhedron 1983 2 723. 298 J. Silver (L = 4,4' bipyridine) has been studied by e.s.r.and [Zn( Me,tren)dmf12' by H n.m.r. ~pectroscopy.~~' Stability constants of Zn" with 9-substituted purines have been deterrnined14'" and the extraction kinetics of zinc with alkyl-substituted dithizones Mucrocylic Complexes. Electrodes coated with poly(viny1pyridine)-co-ordinatedZn"-tetraphenylporphine (ZnTPP) have been investigated.343 Equilibrium constants have been measured for the reversible complexation of ZnTPP with poly(4-~inylpyridine) both in solution and in a system in which the polymer had been adsorbed onto fused A full pH-study of the incorporation of Zn" into uroporphyrin (I) has been reported.344 Excited-state Zn" porphyrin-quinone interactions at 10 A separation have been investigated345 and the photoredox behaviour of Zn"-porphyrins in vesiculal assemblies The synthesis of a decadendate dinucleating ligand and its aqueous equilibria with Zn" has been described"4g Zinc(1r)-sapphyrin (pentapyrrolic macrocycles) chemistry has been reported346 and the thermodynamic stabilities of Zn and Cd" complexes of a series of 0,N3-donor macrocycles Size- and structure-controlled stabilities of polyaza-crown ether complexes with Zn2' ions have been investigated as have the Zn" complexing properties of 1 -oxa-4,7,11 -triazacyclotridecane.'s2 The redox properties of (CN)&Zn a new phthalocyanine charge-transfer complex have been The synthesis of two dibenzo-3,2,3-tetramines and their Zn and Cd" complexes have been The reactions of superoxide ion with Zn and Cd" porphyrins have been studied.351 Biological Zinc.Zinc citrate contains isolated Zn" ions octahedrally co-ordinated to two equivalent ~itrates.~~~ Zinc(11) complexes of N-(2-pyridylmethy1idene)amino acids have been studied as model vitamin B6 systems.l5' Complex formation of Zn Cd and Hg with D-penicillamine has been studied using pH tit ration^.^^^ The Zn" and Co" metal ion effects on target sites of modification in metallocarboxypeptidase B have been investigated.354 X-Ray absorption spectra of native (Zn) and Co-reconstituted bovine carbonic anhydrase (CA) have been and the bicar- 340 W. Kaim J. Organomet. Chem. 1983 241 157. 34I S. F. Lincoln A. M. Hounslow and J. H. Coates Inorg. Chim. Acta 1983 77 L7. 342 H. Watarai and H. Freiser J. Am. Chem. Soc, 1983 105,189.343 (a) H. Kido and C. H.Langford J. Chem. Soc, Dalton Trans. 1983 350; (b) D. S. Becker and R. G. Hayes Znorg. Chem. 1983 22 3050. 344 A. Shamin and P. Hambright Inorg. Chem. 1983 22 694. 345 (a) J. S. Lindsey D. C. Mauzerall and H. Linschitz J. Am. Chem. Soc. 1983 105 6528; (b) K. Hurst L. Y. C. Lec and M. Gratzel J. Am. Chem. Soc. 1983 105 7048. 346 V. J. Bauer D. L. J. Clive D. Dolphin J. B. Paine 111 F. L. Harris M. M. King J. Loder S.-W. C. Wang and R.B. Woodward J. Am. Chem. Soc. 1983 105 6429. 347 K. R. Adam K. P. Dancey B. A. Harrison A. J. Leong L. F. Lindoy M. McPartlin and P. A. Tasker J. Chem. SOC., Dalton Trans. 1983 1351. 348 A. Girandeau A. Louati M. Gross J. J. Andre J. Simon C. H. Su and K. M. Kadish J. Am.Chem. Soc. 1983 105 2917. 349 C. W. G. Ansell M. McPartlin P. A. Tasker and A. Thambythurai Polyhedron 1983 2 83. 350 C. W. G. Ansell K. P. Dancey M. McPartlin P. A. Tasker and L. F. Lindoy J. Chem. SOC.,Dalton Trans. 1983 1789. 35' T. Ozawa and A. Hanaki Inorg. Chim. Acta 1983 80 33. 352 R. Swanson W. H. Ilsley and A. G. Stanislowski J. Inorg. Biochern. 1983 18 187. 353 R. Strand W. Lund and J. Aaseth J. Inorg. Biochem. 1983 19 301. 354 N.Zisapel T.Blank and M. Sokolovsky 1.Inorg. Biochern. 1983 18 253. 355 (a) V. Yachandra L. Powers and T. G. Sprio J. Am. Chem. Soc. 1983 105 6596; (6) Y. Pocker and T. L. Deits J. Am. Chem. SOC.,1983 105. 980. Cu Ag Au; Zn Cd Hg 299 bonate proton in CA catalysis has been studied.3cch A quarternary Zn complex involving pyridoxamine glycine and ethylenediamine has been described.'06L1 Hexa- aqua-zinc(I 1)bis(2,6-dihydroxybenzoate)dihydrate has been reported as a humic-like model.") Tetrakis(3,5 -di -t -bu ty1-4- hydro xyphe n yI )porp h yri n and its Zn I ' derivative have been studied as models for per~xidases.~~~ The pH dependency of the kinetics of Zn carboxypeptidase-catalysed enolization of a substituted propionic acid has been determined.357 67Zn N.m.r.studies of aqueous Zn*+ Zn2'-insulin complexes and other Zn7+ ligand complexes have been reported. Cadmium.-The structures of many polytypes of Cdl? have been Cd&aCI,.8.5H20 crystals show a persistent occurrence of twinning by pseudosym- met~y.~~" [CdCI,(C,H,(OH)2)]7.C2H4(OH)2contains Cd(C2H,02)CI,,2 octahedra with two edges (CI double bridges) in common which form endless chains.36' 2-amino-4,5-dihydro-3H -1,3-thiazolium trichlorocadmate( I I) is polymeric in struc- ture and consists of ATH+ and CdCI,- anions.The Cd atoms are octahedrally co-ordinated and linked into infinite chains by double CI catena-Di-p-chloro-iodo(I H '-S-methylisothiocarbonohydrazidium-N)cadmium( I I) contains Cd in slightly distorted octahedral co-ordination.'" CdPt'O contains edged-shared PtO octahedra in chains and columnar stacks of planar PtO groups.364 In Cd,Na(VO& CdO octahedra form infinite edge-sharing chains linked by corner- sharing VO and Cd/ NaO tetrahedra.jb5 Cd(SCH2C02Et) contains [Cd(p-SCH2C02Et)2] linear chains along which Cd atoms tetrahedral CdS, and dodecahedra1 CdS,O co-ordinations altenate.365 The growth of mixed crystals of CdS,-,Se has been described.367 Spectra have been reported for the surface- adsorbed free radical anion of methylviologan (MV+') formed from MV' by electron transfer from colloidal CdS particles following photoexcitation by continuous wave Raman lasers.3h8 KCd(N3)?.H20 and K2Cd(N,) both contain Cd surrounded by six azide groups.3hy Cd-thiocyanate-thioacetamide and Cd-thioacetamide-nicotinamide systems have been studied and many mixed complexes detected.37" I13 Cd n.m.r. studies and crystal structure determinations of bis( p-o-hydroxyben- zoato)bis(o-hydroxybenzoat0)tetra-aquodicadmium(I I) and tris(pyridine)bis(o-hydroxybenzoato)cadmium(lr) confirm pentagonal-bipyramidal seven-co-ordinate Cd" .37' An approximately tetrahedral CdS moiety has been found in tetrakis(N,N'-dimethylthiourea-S)-cadmium( 11) nitrate."2 In Cd( NCS)2( 1,2,4-tria~oIe)~ the Cd2+ 356 T.G. Taylor K. B. Nolan and R. Hildreth J. Am. C'hem. Soc. 1983 105 6149. 757 T. E. Spratt T. Sugimoto and E. T. Kaiser J. Am. Chem. Soc. 1983 105 3679. 358 (a)T. Shimizu and M. Hatano Inorg. C'him. Acfa 1983 76 L177; (b) M. Kodaka T. Shimizu and M. Hatano Inorg. C'him.Acrn. 1983 78 L55. 359 (a) B. Palosz Acra ('rysrallogr. 1983 C39 1160; (b) S. K. Chaudhary G. K. Chadhu and G. C. Trigunayat Acra Crystallogr. 1983 C39 675. 360 H. Leligny and J. C. Monier Acra Crystallogr. 1983 839 427. 36 I F. A. Schroder J. W. Bats H. Fuess and E. J. Zehnder Z.Anorg. Allg. Chem. 1983 499 181. 362 M. Kubiak T. Glowiak and H. Kozlowski Acra Cryrfallogr. 1983 C39 1937. 36? F. Bigoli M. Lanfranchi E. Leporati and M. A. Pellinghelli Acta Crystallogr. 1983 C39 1333. 364 C. T. Prewitt K. B. Schwartz and R. D. Shannon ACIUCrysfallogr. 1983 C39 519. 365 S. C. Abrahams P. Marsh and J. Ravez Acra Crysfallogr. 1983 C39 680. 366 I. G. Dance M. L. Scudder and R. Secomb Inorg. Chem. 1983 22 1794. 367 B. A. Kazennov and V. F. Chernysheva Soc. fhys. Cry~fallogr.,1983 28 242. 36X K. Metcalfe and R. E. Hester J. ('hem. Soc. C'hem. Commun. 1983 133. 369 W. Clegg H. Krischner A. I. Saracoglu and G. M. Sheldrick Z. Krisrallogr. 1983 161 307. 37(1 V. G. Dongre. Inorg. Chim. Acfa 1983 73 281. 37 I N.G. C'harles E. A. H. Griffith P. C.. Rodesiler. and t.L. Amma. Inorg. ('him.Acta. 1983 22 2717. 372 P. F. Rodesiler. N. G. Charles. E. A. H. Grifith. and C... L. Amma. Am Crvrtallogr. 1983 C39. 1350. 300 J. Silver is octahedrally co-ordinated to two monodentate N-bonded 1,2,4-triazole ligands two thiocyanate N atoms and two thiocyanate S atoms.373 The stereochemistry of [C~~(SC~H~),O]~-, a cage complex related to the Cd- cysteinate aggregates in metallothioneins has been The essential structure is shown (7). A correlation of u.v. c.d. and '13Cd n.m.r. data and a '13Cd n.m.r. characterization of the binding sites in the reconstituted protein has been reported.375 [Cd4(SPh&,12-S Mercury.-A review with 176 references spanning the years 1980-198 1 has appeared.376 Two complexes of thiamine [ThH] with HgC12-[ThH]"[HgCl,]~ and [ThH]2+[HgC14]2-have been prepared the latter contains tetrachloromercurate ions.377 In [NH3(C2H5)]2[HgCl,] there is a two-dimensional [HgC14]2,"- layer made up of HgCl 0~tahedx-a~~' and 1,4-diazabicycl0[2.2.2]octan-1,4-diium HgC14.H20 contains regular HgC142- tetrahedra.379 HgClz has been used in the chemical trans- port of Ti,,02,- phases.380 Correlations between crystal structures and vibrational spectra of complexes HgX2(PR3) (where X = C1 Br or I and R = Ph; R = 1,2,5-triphenylphospholeand X = C1 or Br; R = cyclohexyl Me or Et and X = C1; R = Me and X = Br) have been rep~rted.~'' Reactions of carbonyl complexes (NN)(Ph,P)M(CO) (M = Mo or W; NN = biby or phen) with HgX2 (X = C1 CN or SCN) involve either partial halogen displacement to yield HgX complexes or retention of both halogens to give addu~ts.,'~ In (urea)HgCl each Hg atom is 373 J.G. Haasnoot G. C. M. de Keyzer and G. C. Verschoor Acta Crysrallogr. 1983 C39 1207. 374 K. S. Hagen and R. H. Holm Inorg. Chem. 1983 22 3171. 375 P. A. W. Dean A. Y. C. Law J. A. Szymanska and M. J. Stillman Inorg. Chim. Acta 1983 78 275. 376 E. C. Constable Coord. Chem. Rev. 1983 52 53. 377 N. Hadjihadis A. Yannopoulos and R. Bau Inorg. Chim. Acta 1983 69 109. 378 B. Salah A. Daoud G. Constant J. Jaud and J. Galy Acta Crystallogr. 1983 C39 63. 379 L. Book and T. C. W. Mak Inorg. Chim.Acta 1983 77 L57. 380 F. J. Seiwert and R. Gruen 2.Anorg. Alfg. Chem. 1983 503 151.381 (a) N.A. Bell M. Goldstein T. Jones and 1. W. Nowell Inorg. Chim. Acta 1983 69 155; (b) N. A. Bell T. D. Dee M. Goldstein P. J. McKenna and I. W. Nowell Inorg. Chim. Am 1983 71 135; (c) N. A. Bell M. Goldstein T. Jones and I. W. Nowell Inorg. Chim. Acta 1983 75 21. 3a2 M. P. Pardo and M. Cano. J. Organomet. Chem. 1983 247 293. Cu Ag Au; Zn,Cd Hg 30 1 essentially in the form of a discrete HgC1 molecule.383 U.V. and IH I3C and 19Hg n.m.r. spectra of CH4-,,(HgX) (X = C1 Br I or CN) have been reported.384 The compounds of tetrathiotetracene and tetraselenotetracene with hexabromodimercur- ate dianion contain centrosymmetric (HgzBr6)'- dimers ;385 similar dimers are found in [Mg(OH2)6][Hg,X6] (X = Br or I),385b and in MgHg3C18.6H20.385' Free-radical chain-substitution reactions of alkymercury halides have been discussed386 and force constants of [Hg(CF,),] [Hg(CCl,),] [Hg(CF,)X] (X = C1 Br or I) and [Hg(CCl,)X] (X = C1 or Br) calculated.3s7 In [OHg3CCHO]N03.H20,388 the geometry is defined by a flat Hg30 oxonium pyramid and a Hg3CC tetrahedron.Hg302(N03) is built up of two Hg302 honey- comb nets and of isolated NO3 Ethylphosphinediacetic acid is a new ligand that is highly selective for soft metals such as Hg.389 c~Mn(C0)~ reacts with excess Hg(OCOCF3) to generate (C0)3MnC,(HgOCOF3),.390 A number of organomercury derivatives of arylazobenzoic acids have been prepared391 and com- plexes of the type C(HgX),) (X = CN- HCO, CH,CO, and CF3C0y) studied by i.r. and Raman spectroscopy.392 Tetramethylammonium tetrakis(4-chloroben- zenethiolato)mercury(rr) contains the [Hg(SC6H4C1)4]2- complex anions.393 The n- and i-propyl mercury selenocyanates have been reacted with thiocyanates of Co" and Ni" to form (SCN),M(NCSeHgR) [M = Co" or Ni"; R = n-propyl or i- pr~pyl].~~~ Zn Cd and Hg complexes of the substituted pyrimidine (dmtp) have been reported; the structures of Cd(NCS)2(dmtp)2(H20)2 and Hg(SCN),(dmtp) have been solved the latter contains Hg in a distorted tetrahedral ~o-ordination.~~' 31P and '99Hg n.m.r.measurements have been reported for cationic Hg ph~sphite,~~~" anionic phosphito-P-Hg complexes,396b and compounds involving (Hg- P) ten-membered rings.396c Hg4(AsF6) contains almost linear Hg,,+ ions and octahedral AsF,- ions.397 Reaction of trifluoromethyl radicals with dimethylmercury generated bis(tri- fluoromethyl)mercury.398Organomercury( 11) derivatives of 2-thiouracil have been 383 K.Lewinski J. Sliwinski and L. Lebioda Inorg. Chern. 1983 22 2339. 384 (a) D. K. Breitinger W. Kress R. Sendelbeck and K. Ishiwada J. Organornet. Chern. 1983 243 245; (6) W. Kress D. K. Breitinger and R. Sendelbeck J. Organornet.Chern. 1983,246 1 ;(c) D. K. Breitinger and W. Kress J. Organornet. Chern. 1983 256 217. 385 (a) R. P. Shibaeva and V. F. Kaminski Sou. Phys. Crystallogr. 1983 28 173; (b) K. Brodersen G. Pezzei and G. Thiele Z. Anorg. Allg. Chern. 1983,502 209; (c) K. Brodersen G. Pezzei and G. Thiele Z. Anorg. Allg. Chern. 1983 499 169. 386 G. A. Russell and H.Tashtoush J. Am. Chern. Soc. 1983 105 1398. 387 J. Mink and P. L. Goggin J. Organornet. Chern. 1983 246 115. 388 (a) D. Grdenic M. Sikirica D. MatkoviC-CalogoviC and A. Nagl J. Organornet. Chern. 1983 253 283 ; (6) H. Behm Acta Crystallogr. 1983 C39 1319. 389 D. Noskova and J. Podlahova Polyhedron 1983 2 349. 390 L. G. Kuzimina A. G. Ginzburg Yu. T. Struchkov and D. N. Kursanov 1.Organornet. Chern. 1983 253 329. 39 I K. K. Sarkar T. K. Chattopadhyay and B. Majee Polyhedron 1983 2 493. 392 J. Mink Z. Meic M. Gal and B. Korpar-Colig J. Organornet. Chern. 1983 256 203. 393 S. Choudhury I. G. Dance P. J. Guerney and A. D. Rae Inorg. Chirn. Acta 1983 70 227. 394 P. P. Singh and V. P. Singh Znorg. Chirn.Acta 1983 71 205. 395 J.Dillen A. T. H. Lenstra J. G. Haasnoot and J. Reedijk Polyhedron 1983 2 195. 396 (a) P.-P. Winkler and P. Peringer Znorg. Chirn. Acta 1983 76 59; (b) P. Peringer and D. Obendorf Znorg. Chirn.Acta 1983,77 L147; (c) P. Peringer and J. Eichbichler J. Organornet. Chern. 1983,241,281. 397 B. D. Cutforth R. J. Gillespie P. Ireland J. F. Sawyer and P. K. Ummat Inorg. Chern. 1983 22 1344. 398 M. Guerra R. L. Armstrong W. J. Bailey jun. and R. J. Lagow J. Organornef. Chern. 1983 254 53. 302 J. Silver reported.399 A 199Hg n.m.r. study of some silylmercury derivatives and selected organomercury compounds has been pre~ented.~~ Reactions of Mo(CO),DAB (DAB = diacetyldihydrazone) and Mo(CO)~-(PPh3)*DAB with HgX (X = C1 I or SCN) have been st~died.~" Hg(CN)- { truns-Mo(CO),(AsMe2Ph)( q5-C5Hs)} contains an Hg-Mo bond length of 2.65 A which is the shortest yet Reaction of perfluor-n-propyliron tetracarbonyl iodide with mercury compounds yields [C3F7Fe(C0)4]2Hg and C3F7Fe(C0)4HgC3F7.403 The structures of (p-MeHgS),Fe2(NO) and (p-MeHgS)2Fe2(C0)6 have been solved.404 Hg[Ru3(C0),(C2-t-Bu)1 and [(C2-t-Bu)Ru,(CO),HgMo( .I)-C,H,)(CO),] contain Hg-bridged metal clusters in the latter the Hg cation bridges one side of the triangular Ru cluster and also bonds to the Mo atom.405 [{CON(CH,CH,PP~,)~]}~( p-Hgz].thf contains a Co-Hg-Hg-Co linear Trimetallic complexes of [IrC1(SnC13)( HgCl)(CO)(PR),] have been studied by 31P l19Sn and I9,Hg n.m.r.407 Ir-Hg bonds have been found in [(PPh3),(CO)Cl,IrHgR] (R = c6Cl, C2cl3 or C6H3C12) complexes.408 [(C6F,)3Ge]3Hg and (Ph3P),Ni react to give (Ph3P)2Ni[Ge(C6F5)3]HgGe(C6F5)3 which contains a Ge- Ni-Ge chain.409 The complexes [Pd3(C0)3(PEt)3]2Hg and Pd4(CO),(PEt3)4(HgBr)2 have been prepared the latter consists of two Pd3Hg tetrahedra with a common Pd-Pd edge.410 The synthesis of a number of Hg-Pt acetylides of the type (RCEC),Pt( p-dppm)2HgC12 (R = C&Me-p Ph Me or Pr") have been rep~rted.~' I The Rh-catalysed decomposition of hydroxymercurated ethylene to ethanol and acetate has been reported4I2 and reduction and exchange reactions of Hg" phosphine complexes at Hg electrodes in dichloromethane have been studied.413 Biological Mercury.A "N and 199Hg n.m.r. investigation of inosine protonation and diamagnetic Hg2+ (and Zn2') ion complexation supports the notion that the binding of the first equivalent of Hg2+ is site selective (at the N-7 A number of studies of Me"-complexes have appeared,,I5 including complexes with thiol and 399 G.C. Stocco A. Tarnburello and M. A. Girasolo Inorg. Chim.Acta 1983 78 57. 400 M. J. Albright T. F. Schaaf A. K. Hovland. and J. P. Oliver J. Organomet. Chem. 1983. 259. 37. 401 M. Iglesias A. Llorente C. Del Pino and A. Santos J. Organomet. Chem. 1983 256 75. 402 G. Salem B. W. Skelton A. H. White and S. B. Wild J. Chem. Soc. Dalton Trans. 1983 21 17. 403 I. I. Gueros and Yu. L. Yagupolskii J. Organomet. Chem. 1983 247 81. 404 T. C. W. Mak L. Book C. Chieh M. K. Gallagher L. C. Song and D. Seyferth Inorg. Chim. Acta 1983 73 159. 405 S.Errner K. King K. I. Hardcastle E. Rosenberg A. M. Manotti Lanfredi A. Tiripicchio and M. T. Carnellini Inorg. Chem. 1983 22 1339. 406 F. Cecconi G. A. Ghilardi S. Midollini and S. Moneti J. Chem. SOC.,Dalton Trans. 1983 349. 407 M. Kretschrner P. S. Pregosin P. Favre and C. W. Schlaepfer J. Organomet. Chem. 1983 253 17. 408 0. Rossell and M. Seco Inorg. Chim.Actu 1983 74 119. 409 L. S. Isaeva L. N. Morozova V. V. Bashilov P. V. Petrovskii V. 1. Sokolov and 0.A. Reutov J. Orgunomet. Chem. 1983 243 253. 410 (a) E. G. Mednikov N. K. Erernenko V. V. Basilov and V. 1. Sokolov Inorg. Chim.Acta 1983 76 L31; (6) E. G. Mednikov V. V. Basilov V. I. Sokolov Yu. L. Slovokhotov and Yu. T. Struchkov Polyhedron 1983 2 141. 41 I C. R. Landrik D.M. McEwan P. G. Pringle and B. L. Shaw J. Chem. SOC.,Dalton Trans. 1983 2487. 412 J. Cook and P. M. Maitlis J. Chem. Soc. Dalton Trans. 1983,?319. 413 A. M. Bond R.Colton D. Dakternieks K.W. Hank and M. Svestka Inorg. Chem. 1983 22 236. 414 G. W. Buchanan and M. J. Bell Can. J. Chem. 1983,61 2445. 415 (a) A. J. Carty S. F. Malone N. J. Taylor and A. J. Canty J. Inorg. Biochem. 1983 18 291; (6) A. J. Canty A. J. Carty and S. F. Malone J. Inorg. Eiochern. 1983 19 133; (c) A. P. Arnold A. J. Canty P. W. Moors and G. B. Deacon J. Inorg. Biochem. 1983. 19 319. Cu Ag Au; Zn,Cd Hg dithiol antidotes selonates and amino acids. The removal of (MeHg") from its glutathione and haemoglobin complexes in haemolysed erythrocytes has been studied by 'Hn.m.r.D. L. Robenstein R. S. Reid and A. A. Isab J. Inorg. Biochem. 1983 18 241.