Design of a Catalytic Active Site for Electrochemical CO₂ Reduction with Mn(I)-Tricarbonyl Species

The design, synthesis, and assessment of a new manganese-centered catalyst for the electrochemical reduction of CO₂ is described. The reported species, MnBr­(6-(2-hydroxyphenol)-2,2′-bipyridine)­(CO)₃, includes a ligand framework with a phenolic proton in close proximity to the CO₂ binding site, which allows for facile proton-assisted C–O bond cleavage. As a result of this modification, seven times the electrocatalytic current enhancement is observed compared to MnBr­(2,2′-bipyridine)­(CO)₃. Moreover, reduction is possible at only 440 mV of overpotential. Theoretical computations suggest that the entropic contribution to the activation free energy is partially responsible for the increased catalytic activity. Experimental work, including voltammetry and product quantification from controlled potential electrolysis, suggests a key mechanistic role for the phenolic proton in the conversion of CO₂ to CO