Electrochemical reduction of G3-factor endoperoxide ...
|Title||Electrochemical reduction of G3-factor endoperoxide and its methyl ether: Evidence for a competition between concerted and stepwise dissociative electron transfer|
|Author(s)||F. Najjar, C. Andre-Barres, M. Baltas, C. Lacaze-Dufaure, D. C. Magri, M. S. Workentin, T. Tzedakis|
|Journal||Chemistry - A European Journal|
|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.|
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