The Cathodic Reduction of SOCI2 in N,N-dimethyl Formamide I. Controlled Potential Coulometry and Rotating Rink-Disk Electrode Voltammetry

Controlled potential coulOmetry and rotating ring-disk electrode voltammetry for the reduction of SOC12 have been performed at glassy carbon electrodes in N,N-dimethyl-formamide (DMF) with tetrabutylammoniumhexafluorophos-phate (TBAPF6) as supporting electrolyte. Coulometry ields a value of two electrons per molecule of SOC12 reduced. Nor-mal pulse voltammetric analysis of product solutions hows two chloride ions form in solution for each molecule of SOC12 added or reduced. The two-electron product of the reduction is reasonably stable in DMF and is oxidized irreversibly in a two-electron process. Rotating ring-disk voltammetry gives no evidence for coupled chemical reactions. There has been a great deal of interest in the mechanism of the reduction of thionyl chloride as a result of its impor-tance to high energy density lithium battery systems (1-16). The reduction process has been examined in neat SOC12 and under conditions where SOC12 is used as a sol-ute in a variety of nonaqueous solvents; this latter area is the one addressed here. Bowden and Dey performed exhaustive lectrolyses o