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A Nickel Phosphine Complex as a Fast and Efficient Hydrogen Production Catalyst

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journal contribution
posted on 28.01.2015 by Lu Gan, Thomas L. Groy, Pilarisetty Tarakeshwar, Shobeir K. S. Mazinani, Jason Shearer, Vladimiro Mujica, Anne K. Jones
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 efficient 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.