期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 13, 期 4, 页码 1174-1179出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200600445
关键词
electrochemistry; electron transfer; endoperoxide; radical ions
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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