Cathode generation of thiolate anions and the correlation between their oxidationE 1/2 and nucleophilic reactivity

Cathode reduction of a series of aliphatic, aromatic, and heteroaromatic thiols on a rotating disk Pt electrode in abs. MeCN against the background of 0.1N Bu₄NClO₄ was investigated. It was found that this process results in the formation of the corresponding thiolate anions whose oxidation half-wave potentials are linearly correlated with their nucleophilicity in theS_N 2 reaction.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2539–2544, November, 1992.