A nickel phosphine complex as a fast and efficient hydrogen production catalyst

(Chemical Equation Presented) Here we report the electrocatalytic reduction of protons to hydrogen by a novel S₂P₂ coordinated nickel complex, [Ni(bdt)(dppf)] (bdt = 1,2-benzenedithiolate, dppf = 1,1′-bis(diphenylphosphino)ferrocene). The catalysis is fast and effi cient with a turnover frequency of 1240 s^-1 and an overpotential of only 265 mV for half activity at low acid concentrations. Furthermore, catalysis is possible using a weak acid, and the complex is stable for at least 4 h in acidic solution. Calculations of the system carried out at the density functional level of theory (DFT) are consistent with a mechanism for catalysis in which both protonations take place at the nickel center.