Diversity of mechanism in the electrochemical study of different electrophiles in the presence of some thiol nucleophiles: thermodynamic and mechanistic study

Electrochemical oxidation of different electrophiles in the presence of p-toluenesulfinic acid and 2-mercaptobenzoxazole as thiol nucleophiles was studied. Mechanistic study of the electrochemical reactions indicates that the electrochemical oxidation of some electrophiles in the presence of the thiol groups have different mechanisms. But some other electrophiles in the presence of both thiol nucleophiles have the same mechanism. To explain the reason for this difference, the computational study was used. Thermodynamic investigation shows that when ∆Gtot of the electrochemical oxidation of products are less than that of initial species, the electrochemically produced species can be oxidized during controlled-potential coulometry.