Farouq F. Said

The direct electrochemical synthesis of some thiolates of zinc, cadmium and mercury

Abstract The electrochemical oxidation of anodic Zn, Cd or Hg (M) into acetonitrile solutions of RSH (or R 2 S 2 ) gives the corresponding M(SR) 2 compounds in high yield. The mechanism of the electrochemical reactions is discussed. The insolubility, and the far infrared spectra (500–50 cm −1 ), are compatible with a polymeric structure for M(SR) 2 in the solid state.

The direct electrochemical synthesis and crystal structure of salts of [M4(SC6H5)10]2− anions (M = Zn, Cd)

Abstract The salts [(C2H5)3NH]2[M4(SC6H5)10] (M = Zn, Cd) can be prepared by the electrochemical oxidation of the metal in an acetonitrile solution of triethylamine and benzenethiol. An X-ray crystal structure determination shows that the anion consists of a tetrahedron of metal atoms, each carrying a terminal -SC6H5 ligand, and connected to the three other metal atoms by bridging > SC6H5 groups. The results are compared with those for similar compounds reported in the literature.

Electrochemical preparation and structure of an unusual zinc(II) thiolato anionic cluster

The electrochemical oxidation of anodic zinc into a solution of PhSH + Et3N in CH3CN yields *Et3NH)2[Zn4(SPh)10]. The structure, as determined by X-ray crystallography, shows that the anion is a novel cluster based on a tetrahedral Zn4S10 kernel.

Coordination compounds of indium : XXXVI. The direct electrochemical synthesis of neutral and anionic organoindium halides

Abstract The electrochemical oxidation of indium metal in cells of the type leads to the formation of RInX 2 compounds; if 2,2′-bipyridine is also present, the products are the adducts RInX 2 ·bipy (R = CH 3 , C 2 H 5 , C 6 H 5 , C 6 H 5 CH 2 , C 6 F 5 ; X = Cl, Br, I (not all combinations)). When R′ 4 NX is present instead of bipy, the products are the salts R′ 4 N[RInX 3 ]. The electrochemical oxidation apparently proceeds via the general mechanism discussed previously. Anomalous results with CH 3 I or C 2 H 5 I are discussed in the light of the known solution chemistry of organoindium(III) compounds.

The direct electrochemical synthesis of organometallic halides of zinc and cadmium with substituted phenyl halides

Abstract The electrochemical oxidation of zinc or cadmium into acetonitrile solutions of RC 6 H 4 X (R  CN, NO 2 ; X  Cl, Br, I; not all combinations) gives the corresponding RC 6 H 4 MX compounds, which form stable 1 : 1 adducts with 2,2′-bi-pyridine. The method provides a simple and direct synthesis of these and related compounds.

Co-ordination compounds of indium. Part 35. The direct electrochemical synthesis of adducts of indium(III) halides

Electrochemical oxidation of anodic indium in non-aqueous media containing halogen may yield either the trihalides (Cl, Br, or I) or the adducts of the trihalides with neutral ligands, depending on the solutes present. Details are given for the preparation of adducts with acetonitrile, pyridine, 2,2′-bipyridine, and triphenylphosphine. The structures of the acetonitrile and pyridine adducts are discussed in the light of new spectroscopic results.

The direct electrochemical synthesis of cationic complexes of metal ions

Transition and main group metals can be oxidised electrochemically in cells containing HBF4 in dimethylsulphoxide; the direct products are the [M(dmso)6]n+ salts with BF4 staggered|−, but products such as [M(bipy)3]n+, [M(en)3]n+ and [M(diphos)m]n+ can be obtained by subsequent reaction (M ≠ n = 2,3).

Direct electrochemical synthesis of cationic complexes

The electrochemical oxidation of both transition and main-group metals in the presence of dimethyl sulphoxide (dmso) or acetonitrile plus tetrafluoroboric acid gives rise to salts of the type [ML6][BF4]n[M = V, Cr, Mn, Fe, Co, Ni, Zn, Cd, or In; L = dmso or CH3CN (not all combinations); n= 2 or 3, depending on M]. The electrochemical conditions described give gram quantities of product from 5–25 h electrolyses with simple apparatus.