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 th...

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Published in:Chemistry : a European journal 2007-01, Vol.13 (4), p.1174-1179
Main Authors: Najjar, Fadia, André-Barrès, Christiane, Baltas, Michel, Lacaze-Dufaure, Corinne, Magri, David C., Workentin, Mark S., Tzédakis, Théodore
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Language:English
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Chemical Sciences
electrochemistry
electron transfer
endoperoxide
Material chemistry
radical ions
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cited_by cdi_FETCH-LOGICAL-c4555-907ab259a5a5b93d3339b3414aa90b37f65bc47e7d40acd153431f800bae530f3
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description 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. A parabolic shape such as that depicted of the electron transfer coefficient (α) against potential E (see figure) clearly indicates a competition between concerted and stepwise dissociative electron transfer in the electrochemical reduction of G3‐factor endoperoxide and its methyl ether.
doi_str_mv 10.1002/chem.200600445
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subjects Chemical Sciences
electrochemistry
electron transfer
endoperoxide
Material chemistry
radical ions
title Electrochemical Reduction of G3-Factor Endoperoxide and Its Methyl Ether: Evidence for a Competition between Concerted and Stepwise Dissociative Electron Transfer
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