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

J Am Chem Soc. 2015 Jan 28;137(3):1109-15. doi: 10.1021/ja509779q. Epub 2015 Jan 16.

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Catalysis
  • Electrochemical Techniques
  • Hydrogen / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Nickel / chemistry*
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Phosphines / chemistry*
  • Quantum Theory

Substances

  • Organometallic Compounds
  • Phosphines
  • Nickel
  • Hydrogen
  • phosphine