Molecular Catalysis of Electrochemical Reactions: Competition between Reduction of the Substrate and Deactivation of the Catalyst by a Cosubstrate Application to N2O Reduction.

In the context of molecular catalysis of electrochemical reactions, the competition between reduction of the substrate and deactivation of the catalyst by a cosubstrate is investigated. It is a frequent situation because proton donors are ubiquitous cosubstrates in reductive electrochemical reactions and molecular catalysts, either transition metal complexes or organic aromatic molecules, and are often prone to electrohydrogenation. We provide a formal kinetic analysis in the framework of cyclic voltammetry, and we show that the response is governed by two parameters and that the competition does not depend on the scan rate. From this analysis a methodology is proposed to analyze such systems and then illustrated via the study of N2O to N2 electroreduction catalyzed by 4‐cyanopyridine in acetonitrile electrolyte with water as proton donor. Incidentally, new insights into the mechanism of 4‐cyanopyridine radical anion protonation are revealed. [ABSTRACT FROM AUTHOR]