Electrochemical Reduction of Thiophosgene in Acetonitrile

Thiophosgene is reduced at solid electrodes in acetonitrile solutions to a mixture of products which includes an insoluble primarily carbon sulfur polymer and a soluble chlorine-rich oligomeric anion. The solid product, which precipitates from the electrolysis solution and on the electrode during electrolyses, has spectral properties quite similar to those of the polymer which is realized from monomeric arbon sulfide in gas-phase reactions. The synthetic utility of this reduction process is discussed. Cyclic voltammograms show one main reduction wave for thiophosgene in acetonitrile. This wave exhibits passivation behavior at several types of solid electrodes on repeat cycles. The release of chloride ions during this reduction process is detected voltammetrically. Various experiments designed to circumvent the passivation phenomena re described. Coulometric experiments, in which reticulated vitreous carbon (RVC) electrodes are used to reduce thiophosgene at potentials beyond the main reduction wave, yield an n-value of about 1.0. The electrochemical reduction of carbon disulfide in nonaqueous olvents leads to a var iety of anionic or-ganosulfur species, including CS3 s- (1) electrochemica