title: A nickel phosphine complex as a fast and efficient hydrogen production catalyst.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, Arizona State University , Tempe, Arizona 85287, United States.
authors.forename: Lu
authors.initials: L
authors.lastname: Gan
authors.forename: Thomas L
authors.initials: TL
authors.lastname: Groy
authors.forename: Pilarisetty
authors.initials: P
authors.lastname: Tarakeshwar
authors.forename: Shobeir K S
authors.initials: SK
authors.lastname: Mazinani
authors.forename: Jason
authors.initials: J
authors.lastname: Shearer
authors.forename: Vladimiro
authors.initials: V
authors.lastname: Mujica
authors.forename: Anne K
authors.initials: AK
authors.lastname: Jones
mesh_terms: D002384:Catalysis; D055664:Electrochemical Techniques; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D009942:Organometallic Compounds; D010720:Phosphines; D009532:Nickel; D006859:Hydrogen; C044646:phosphine