Hydrogen Evolution Mediated by Cobalt Diimine‐Dioxime Complexes: Insights into the Role of the Ligand Acid/Base Functionalities.

The benchmarking of the performance for H2 evolution cobalt diimine-dioxime catalysts is provided based on a comprehensive study their catalytic mechanism. latter follows an ECE'CC pathway with intermediate formation Co(II)-hydride and second protonation possibly at basic site ligand, acting as proton relay. This suggests intramolecular coupling between hydride protonated ligand concentration-independent rate-determining step controlling turnover frequency evolution.