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 O--O 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 O--O bond dissociation energies, the experimental data was used to evaluate the standard reduction potentials and other pertinent thermochemical information.
Najjar
Fadia
F
Laboratoire de Synthèse et Physicochimie de Molécules d'Intérêt, Biologique, CNRS UMR 5068 Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, France.
André-Barrès
Christiane
C
Baltas
Michel
M
Lacaze-Dufaure
Corinne
C
Magri
David C
DC
Workentin
Mark S
MS
Tzédakis
Théodore
T