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标题：Concerted heavy-atom bond cleavage and proton and electron transfers illustrated by proton-assisted reductive cleavage of an O–O bond
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作者：Cyrille Costentin ; Viviane Hajj ; Marc Robert 等
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2011
卷号：108
期号：21
页码：8559-8564
DOI：10.1073/pnas.1104952108
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Electron transfer may be concerted with proton transfer. It may also be concerted with the cleavage of a bond between heavy atoms. All three events may also be concerted. A model is presented to analyze the kinetics of these all-concerted reactions for homogeneous or electrochemical reduction or oxidation processes. It allows the estimation of the kinetic advantage that derives from the increase of the bond-breaking driving force resulting from the concerted proton transfer. Application of the model to the electrochemical reductive cleavage of the O-O bond of an organic peroxide in the presence of a proximal acid group illustrates the applicability of the model and provides an example demonstrating that electron transfer, heavy-atom bond breaking, and proton transfer may be all concerted. Such analyses are expected to be useful for the invention, analysis, and optimization of reactions involved in contemporary energy challenges as well as for the comprehension of major biochemical processes, a number of which involve electron and proton transfer together with cleavage of bonds between heavy atoms.
关键词：electrochemistry ; proton-coupled electron transfer ; dissociative electron transfer