Nitrogen Binding to the FeMo-Cofactor of Nitrogenase
- 26 November 2003
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (51) , 15772-15778
- https://doi.org/10.1021/ja0367997
Abstract
Density functional calculations are presented to unravel the first steps of nitrogen fixation of nitrogenase. The individual steps leading from the resting state to nitrogen binding at the FeMo-cofactor with a central nitrogen ligand are characterized. The calculations indicate that the Fe-Mo cage opens as dinitrogen binds to the cluster. In the resting state, the central cage is overall neutral. Electrons and protons are transferred in an alternating manner. Upon dinitrogen binding, one protonated sulfur bridge is broken. An axial and a bridged binding mode of dinitrogen have been identified. Adsorption at the Mo site has been investigated but appears to be less favorable than binding at Fe sites.Keywords
This publication has 52 references indexed in Scilit:
- Localization of a Substrate Binding Site on the FeMo-Cofactor in Nitrogenase: Trapping Propargyl Alcohol with an α-70-Substituted MoFe ProteinBiochemistry, 2003
- The Interstitial Atom of the Nitrogenase FeMo-Cofactor: ENDOR and ESEEM Show It Is Not an Exchangeable NitrogenJournal of the American Chemical Society, 2003
- FeMo cofactor of nitrogenase: energetics and local interactions in the protein environmentJBIC Journal of Biological Inorganic Chemistry, 2002
- Reduction of short chain alkynes by a nitrogenase α-70Ala-substituted MoFe proteinBased on the presentation given at Dalton Discussion No. 4, 10–13th January 2002, Kloster Banz, Germany. Research supported by National Institutes of Health Grant R01-GM59087.J. Chem. Soc., Dalton Trans., 2002
- FeMo Cofactor of Nitrogenase: A Density Functional Study of States MN, MOX, MR, and MIJournal of the American Chemical Society, 2001
- New insights into structure-function relationships in nitrogenase: a 1.6 Å resolution X-ray crystallographic study of Klebsiella pneumoniae MoFe-proteinJournal of Molecular Biology, 1999
- Why R-Homocitrate Is Essential to the Reactivity of FeMo-Cofactor of Nitrogenase: Studies on NifV--Extracted FeMo-CofactorJournal of the American Chemical Society, 1998
- Fully Unconstrained Approach to Noncollinear Magnetism: Application to Small Fe ClustersPhysical Review Letters, 1998
- Calculated details of a mechanism for conversion of N2 to NH3 at the FeMo cluster of nitrogenaseChemical Communications, 1997
- Structure−Function Relationships of Alternative NitrogenasesChemical Reviews, 1996