Kinetics and Thermodynamics of CO2 Binding to the Metal Centre Promotes CO2 Reduction Reaction

Herein, we report the design, synthesis, and characterization of a series of manganese terpyridine dicarbonyl derivatives (1-5) each covalently bonded to a proximal amide moiety as a proton relay. By finely tuning the kinetics of binding of CO2 to the metal centre, we improved the turnover frequency (TOF) for the CO2 reduction reaction (CO2RR) from 325 s-1 to 1359 s-1. The performances ranked this series of catalysts among the most promising earth-abundant molecular catalysts for CO2-to-CO conversion.