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Volume 148, 2011
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Proton-coupled electron transfers in biomimetic water bound metal complexes. The electrochemical approach

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Abstract

Water-bound metal (M) complexes play a central role in the catalytic centers of natural systems such as Photosystem II (PSII), superoxide dismutase, cytochrome c oxidase and others. In these systems, electron transfer reactions involving the metal center are coupled to proton transfers. Besides its fundamental interest, comprehension of these reactions and of possible bio-inspired catalytic devices is an additional motivation for studying the coupling between proton and electron transfer (proton-coupled electron transfers, PCET), starting with an aqua-MII/hydroxo-MIII couple, and going to higher oxidation degrees as in the case of PSII (hydroxo-MIII/oxo-MIV couple). Factors that determine the occurrence of the stepwise and concerted pathways are recalled from the illustrating example of a recently described mononuclear osmium complex, thus opening perspectives for further studies of the biomimicking complex. PCET in a mononuclear aqua/hydroxo manganese couple was then studied using the electrochemical approach.

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Submitted
15 Mar 2010
Accepted
28 Apr 2010
First published
03 Sep 2010

Faraday Discuss., 2011,148, 83-95
Article type
Paper

Proton-coupled electron transfers in biomimetic water bound metal complexes. The electrochemical approach

E. Anxolabéhère-Mallart, C. Costentin, C. Policar, M. Robert, J. Savéant and A. Teillout, Faraday Discuss., 2011, 148, 83
DOI: 10.1039/C004276E

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