Computational Study of Anomalous Reduction Potentials for Hydrogen Evolution Catalyzed by Cobalt Dithiolene Complexes

The design of efficient hydrogen-evolving catalysts based on earth-abundant materials is important for developing alternative renewable energy sources. A series of four hydrogen-evolving cobalt dithiolene complexes in acetonitrile–water solvent is studied with computational methods. Co­(mnt)₂ (mnt = maleonitrile-2,3-dithiolate) has been shown experimentally to be the least active electrocatalyst (i.e., to produce H₂ at the most negative potential) in this series, even though it has the most strongly electron-withdrawing substituents and the least negative Co^III/II reduction potential. The calculations provide an explanation for this anomalous behavior in terms of protonation of the sulfur atoms on the dithiolene ligands after the initial Co^III/II reduction. One fewer sulfur atom is protonated in the Co^II(mnt)₂ complex than in the other three complexes in the series. As a result, the subsequent Co^II/I reduction step occurs at the most negative potential for Co­(mnt)₂. According to the proposed mechanism, the resulting Co^I complex undergoes intramolecular proton transfer to form a catalytically active Co^III-hydride that can further react to produce H₂. Understanding the impact of ligand protonation on electrocatalytic activity is important for designing more effective electrocatalysts for solar devices.