The direct electrochemical synthesis of dialkyldithiocarbamate and diethyldithiophosphate complexes of main group and transition metals

Abstract

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]

Investigation of Electrochemical Behavior of Some Dithiophosphonates in Acetonitrile on the Platinum and Gold Electrodes

“…The possible reaction steps at the anode and cathode were identified. Geloso et al have investigated the electrochemical oxidation of transition and main group metals in the presence diethyldithiophosphate to synthesize some diethyldithiophosphate complexes [18]. Schischkov et al reported the electrochemical behavior of bis(diphenyldithiophosphine)disulfide and mercuric diphenyldithiophosphinate in ethanol-lithium perchlorate and ethanol-sulfuric acid media by the method of classical polarography and potential controlled electrolysis at a rotating Pt disk electrode [19].…”

The direct electrochemical synthesis of d10 metal ion derivatives of some anionic bidentate oxygen donors

“…The method of preparing these new compounds was essentially the same as those used in our previous papers (1)(2)(3)(4)(5)(6)(7)(8)(9)(10). The solution phase was contained in a 100 mL round-bottomed flask with a Schlenk arm; a metal rod suspended through rubber septum formed the anode of the cell, and a platinum wire was the cathode.…”