Evidence for the formation of terminal hydrides by protonation of an asymmetric iron hydrogenase active site mimic

Inorg Chem. 2007 Apr 30;46(9):3426-8. doi: 10.1021/ic0703124. Epub 2007 Mar 31.

Abstract

Treatment of [Fe2(mu-pdt)(CO)6] [pdt=S(CH2)3S] with dppe (Ph2PCH2CH2PPh2) in refluxing toluene affords the asymmetric complex [Fe2(mu-pdt)(CO)4(dppe)] (1). Protonation of 1 with HBF4-Et2O in CH2Cl2 gives at room temperature the mu-hydrido derivative [Fe2(mu-pdt)(CO)4(dppe)(mu-H)](BF4) (2). Monitoring the reaction by 1H, 31P, and 13C NMR at low temperature reveals unambiguously that the process of the protonation of 1 implies terminal hydride intermediates.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Binding Sites
  • Biomimetic Materials / chemistry*
  • Biomimetic Materials / metabolism*
  • Hydrogenase / chemistry*
  • Iron-Sulfur Proteins / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Protons*
  • Stereoisomerism
  • Temperature
  • Water / chemistry

Substances

  • Iron-Sulfur Proteins
  • Protons
  • Water
  • iron hydrogenase
  • Hydrogenase