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

Homogeneous catalysis of electrochemical reactions often involves proton‐coupled electron‐transfer. The conditions that make installing proton relays inside the catalyst molecule lead to a considerable boosting of catalysis instead of being a zero‐sum game are analyzed in detail, showing why the proton is such a uniquely appropriate agent for this task.

Abstract

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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