Unravelling the Mechanistic Pathway of the Hydrogen Evolution Reaction Driven by a Cobalt Catalyst

A Co^I complex bearing a redox-active κ-N₃P₂ pentadentate ligand and its activity towards hydrogen evolution reaction is reported in this work. A combination of spectroscopic, electrochemical and computational techniques is employed to characterize the intermediate species, demonstrating an unusual homolytic coupling reaction pathway between two catalyst units.