A Nickel(II)–Sulfur‐Based Radical‐Ligand Complex as a Functional Model of Hydrogenase

Better than nature! A nickel(II) dithiolene complex [NiII(L2−)(L−.)][PPh4] (1; see figure; L=1,2-dicarbomethoxyethylene dithiolate) electrocatalyzes hydrogen evolution at the lowest achievable reduction potential (, −0.69 V) in CH3CN and also in aqueous medium (, −0.71 V) to date. Compound 1 shows strikingly similar EPR and reduction potential values to those observed with native Ni-containing hydrogenases.