Publication 687

Proc. Nat. Acad. Sci. USA. 108 (21),8559-8564, 2011 DOI:10.1073/pnas.1104952108
Concerted heavy-atom bond cleavage and proton and electron tranfers illustrated by proton-assisted reductive cleavage of an O-O bond

Laboratoire d’Electrochimie Moléculaire, UMR CNRS 7591, Université Paris Diderot, 15 rue Jean-Antoine de Baïf, 75205 Paris Cedex 13, France

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 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.