Laboratoire d'Electrochimie Moléculaire, Unité Mixte de Recherche 7591, Centre National de la Recherche Scientifique, Université Paris Diderot, Sorbonne Paris Cité, 15 Rue Jean-Antoine de Baïf, F-75205 Paris Cedex 13, France.
Proc Natl Acad Sci U S A. 2011 May 24;108(21):8559-64. doi: 10.1073/pnas.1104952108. Epub 2011 May 5.
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.
电子转移可能与质子转移协同发生。它也可能与重原子之间键的断裂协同发生。这三个事件也可能协同发生。本文提出了一个模型来分析均相或电化学还原或氧化过程中所有协同反应的动力学。它允许估计由于协同质子转移导致的键断裂驱动力增加而带来的动力学优势。该模型在存在邻近酸基团的情况下应用于有机过氧化物的 O-O 键的电化学还原断裂，说明了该模型的适用性，并提供了一个示例，证明电子转移、重原子键断裂和质子转移可以协同发生。这些分析预计将有助于发明、分析和优化当代能源挑战中涉及的反应，以及理解许多涉及电子和质子转移以及重原子之间键断裂的主要生化过程。
