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

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