Computational Design of Cobalt Catalysts for Hydrogenation of Carbon Dioxide and Dehydrogenation of Formic Acid

Abstract

A series of cobalt complexes with acylmethylpyridinol and aliphatic PNP pincer ligands are proposed based on the active site structure of [Fe]-hydrogenase. Density functional theory calculations indicate that the total free energy barriers of the hydrogenation of CO₂ and dehydrogenation of formic acid catalyzed by these Co complexes are as low as 23.1 kcal/mol in water. The acylmethylpyridinol ligand plays a significant role in the cleavage of H₂ by forming a strong Co-H^δ-···H^δ+-O dihydrogen bond in a fashion of frustrated Lewis pairs.