Electronically Modified Cobalt Aminopyridine Complexes Reveal an Orthogonal Axis for Catalytic Optimization for CO Reduction.

The design of effective electrocatalysts for carbon dioxide reduction requires understanding the mechanistic underpinnings governing the binding, reduction, and protonation of CO. A critical aspect to understanding and tuning these factors for optimal catalysis revolves around controlling the electronic environments of the primary and secondary coordination sphere. Herein we report a series of -substituted cobalt aminopyridine macrocyclic catalysts - capable of carrying out the electrochemical reduction of CO to CO. Under catalytic conditions, complexes -, as well as the unsubstituted cobalt aminopyridine complex , exhibit / values ranging from 144 to 781. Complexes and exhibit a pronounced precatalytic wave suggestive of an ECEC mechanism. A Hammett analysis reveals that ligand modifications with electron-donating groups enhance catalysis (ρ < 0), indicative of positive charge buildup in the transition state. This trend also extends to the Co potential, where complexes possessing more negative (Co) reductions exhibit greater / values. The reported modifications offer a synthetic lever to tune catalytic activity, orthogonal to our previous study of the role of pendant hydrogen bond donors.