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Laboratoire d'Electrochimie Moleculaire, LEM, Paris

UMR CNRS - Université Paris Diderot - Paris France

Master Frontiers in Chemistry | UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Université de Paris Master Chimie Sorbonne Paris Cité UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie
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Université Paris Diderot
Université de Paris CNRS, Centre National de la Recherche Scientifique

Le LEM - Publications: Abstracts

Publication 871

Angew. Chem. Int. Ed., 58 (7), 2125-2128, 2019


Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effects


Jean-Michel Savéant

Laboratoire d’Electrochimie Moléculaire, Unité Mixte de Recherche Université − CNRS No. 7591, Bâtiment Lavoisier, Université Paris Diderot, Sorbonne Paris Cité, 15 rue Jean de Baïf, 75205 Paris Cedex 13, France

Homogeneous catalysis of electrochemical reactions, related to contemporary energy challenges, often involves proton-coupled electron transfer sequences. The idea rapidly emerged that installing the proton donor (for reductions, or acceptor for oxidations) inside the catalyst molecule should be beneficial in terms of efficiency, as it would then be closer to the nerve center of the process (usually the metal in the case of transition metal complex catalysts). If this proton relay has indeed done the job, it has lost its proton at the end of each catalytic loop, and must therefore be reprotonated (for reductions, or deprotonated for oxidations) from acid (or base) from the solution before a new catalytic loop can start. The impression may thus be that there is a zero-sum game. The conditions under which this is not the case may entail, in contrast, a considerable boosting of catalysis. This will also allow explain why the proton is such a specifically appropriate agent for this task.

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