Cobalt(II) and nickel(II) thiolates, M(SR)2, can be prepared in high yield by the electrochemical oxidation of a metal anode in an acetonitrile or acetone solution of RSH (R = C6H5, o-CH3C6H4, 2-C10H7, 2,3,4,5-C6F4H; not all combinations). When 2,2-bipyridine or 1,10-phenanthroline (=L) is added to the electrolyte phase, the products are the adducts M(SR)2L2. In the case of Co(SC6H5)2(phen)2, aerial oxidation leads to the formation of the cobalt(III) cation [Co(SC6H5)2(phen)2]+, isolated as the perchlorate salt. X-ray crystallographic analysis showed that this cation has a cis-CoS2(N2)2 kernel.

Thispaper is dedicated to Professor Douglas E. Ryarz on the occasior~ of his 65th birthday CORRADO GELOSO, RAJESH KUMAR, JAIME ROMERO LOPEZ-GRADO, and DENNIS G. TUCK. Can. J. Chem. 65, 928 (1987).Dialkyldithiocarbamate derivatives (R,NCS~),,M of a number of metals (M = Fe, Co, Ni, Cu, Ag, Zn, Cd, In, T1) have been synthesised in good yield by electrochemical oxidation of appropriate sacrificial anodes in non-aqueous solutions of either the corresponding tetraalkylthiuram disulphide (RzNCS2)2 (R = Me, Et) or a mixture of carbon disulphide plus the secondary amine R2NH (R = Et, i-Pr; R2NH = piperidine). Similar experiments with solutions of (EtO),P(S)SH (= HL) gave ML, derivatives (M = Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, T1) while in the presence of HL + 1 ,lo-phenanthroline, ML,, .phen derivatives were obtained for M = V, Mn, Fe, Co, Zn, and Ga.CORRADO GELOSO, RAJESH KUMAR, JAIME ROMERO LOPEZ-GRADO et DENNIS G. TUCK. Can. J. Chem. 65, 928 (1987).On a synthCtisC avec de bons rendements les derives dialkyldithiocarbamates (R2NCS2),,M d'un certain nombre de metau (M = Fe, Co, Ni, Cu, Ag, Zn, Cd, In, T1) en mettant en jeu l'oxydation Clectrochimique d'anodes sacrifices appropriees dans des solutions non-aqueuses soit des disulfures de tCtraalkylthiurames correspondants (R2NCS2)2 (R = Me, Et) soit d'un melange de disulfure de carbone plus l'amine secondaire R2NH (R = Et, i-Pr; RzNH = piperidhe). Des experiences semblables avec des solutions de (EtO)?P(S)SH (= HL) conduisent aux derives ML,, (M = Fe, Co, Ni, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, T1) alors que, en presence de HL + phenanthroline-l,10, on obtient des derives ML,, .phen (M = V, Mn, Fe, Co, Zn et Ga).[Traduit par la revue]