title: 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 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.
authors.affiliation: Laboratoire de Synthèse et Physicochimie de Molécules d'Intérêt, Biologique, CNRS UMR 5068 Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, France.
authors.forename: Fadia
authors.initials: F
authors.lastname: Najjar
authors.forename: Christiane
authors.initials: C
authors.lastname: André-Barrès
authors.forename: Michel
authors.initials: M
authors.lastname: Baltas
authors.forename: Corinne
authors.initials: C
authors.lastname: Lacaze-Dufaure
authors.forename: David C
authors.initials: DC
authors.lastname: Magri
authors.forename: Mark S
authors.initials: MS
authors.lastname: Workentin
authors.forename: Théodore
authors.initials: T
authors.lastname: Tzédakis