A nickel(II)-sulfur-based radical-ligand complex as a functional model of hydrogenase

摘要

Better than nature! A nickel(II) dithiolene complex [Ni~(II)(L ~(2-))(L~(-.))][PPh_4] (1; see figure; L=1,2-dicarbomethoxyethylene dithiolate) electrocatalyzes hydrogen evolution at the lowest achievable reduction potential (Ered p, -0.69 V) in CH_3CN and also in aqueous medium (E p, -0.71 V) to date. Compound 1 shows strikingly similar EPR and reduction potential values to those observed with native Ni-containing hydrogenases.