Electrochemical reduction of G3‐factor endoperoxide and its methyl ether : evidence for a competition between concerted and stepwise dissociative electron transfer

Abstract

The reduction of the bicyclic G-factor endoperoxides G3 and G3Me was studied in N,N-dimethylformamide usingcyclic voltammetry and convolution analysis. Electron transfer leads to irreversible cleavage of the O-O bond. Detailed analysis of the voltammetry curves reveals a non-linear dependence on the transfer coefficient indicatinga mechanistic transition from a stepwise mechanism to one with more concerted character with increasingpotential. By usingquantum calculations to estimate the O-O bond dissociation energies, the experimental data was used to evaluate the standard reduction potentials and other pertinent thermochemical information.