Kinetic analysis of a slow electron transfer coupled with a father—son reaction

Abstract

The electrode reaction mechanism involving interaction of the products of a slow, rate-determining electron transfer with the parent molecule (father—son reaction) has been examined theoretically under the conditions of cyclic voltammetry. The kinetic analysis indicates how to determine the correct values of the kinetic parameters for both the heterogeneous charge transfer and the homogeneous chemical step. The irreversible cathodic reaction of diphenylmethylphenylsulphide in anhydrous DMF provides a good example of this mechanism, since the diphenylmethyl carbanion resulting from the irreversible two-electron reduction undergoes proton transfer from the parent molecule (self-protonation mechanism).