Model study of CO inhibition of [NiFe]hydrogenase

Inorg Chem. 2011 Sep 19;50(18):8902-6. doi: 10.1021/ic200965t. Epub 2011 Aug 19.

Abstract

We propose a modified mechanism for the inhibition of [NiFe]hydrogenase ([NiFe]H(2)ase) by CO. We present a model study, using a NiRu H(2)ase mimic, that demonstrates that (i) CO completely inhibits the catalytic cycle of the model compound, (ii) CO prefers to coordinate to the Ru(II) center rather than taking an axial position on the Ni(II) center, and (iii) CO is unable to displace a hydrido ligand from the NiRu center. We combine these studies with a reevaluation of previous studies to propose that, under normal circumstances, CO inhibits [NiFe]H(2)ase by complexing to the Fe(II) center.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biomimetic Materials / chemistry
  • Biomimetic Materials / metabolism*
  • Carbon Monoxide / metabolism*
  • Hydrogenase / antagonists & inhibitors*
  • Hydrogenase / metabolism*
  • Models, Biological
  • Models, Molecular
  • Nickel / chemistry
  • Nickel / metabolism*
  • Ruthenium Compounds / chemistry
  • Ruthenium Compounds / metabolism*

Substances

  • Ruthenium Compounds
  • Nickel
  • Carbon Monoxide
  • nickel-iron hydrogenase
  • Hydrogenase