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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 697870.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Identification of a spin-coupled Mo(III) in the nitrogenase iron-molybdenum cofactor
Authors:Bjornsson, Ragnar; Lima, Frederico A.; Spatzal, Thomas; Weyhermüller, Thomas; Glatzel, Pieter; Bill, Eckhard; Einsle, Oliver; Neese, Frank; DeBeer, Serena
Date of Publication (YYYY-MM-DD):2014
Title of Journal:Chemical Science
Journal Abbrev.:Chem.Sci.
Issue / Number:8
Start Page:3096
End Page:3103
Review Status:Internal review
Audience:Experts Only
Abstract / Description:Nitrogenase is a complex enzyme that catalyzes the formation of ammonia utilizing a MoFe7S9C cluster. The presence of a central carbon atom was recently revealed, finally completing the atomic level description of the active site. However, important prerequisites for understanding the mechanism - the total charge, metal oxidation states and electronic structure are unknown. Herein we present high-energy resolution fluorescence detected Mo K-edge X-ray absorption spectroscopy of nitrogenase. Comparison to FeMo model complexes of known oxidation state indicates that the Mo in the FeMo cofactor of nitrogenase is best described as Mo(III), in contrast to the universally accepted Mo(IV) assignment. The oxidation state assignment is supported by theoretical calculations, which reveal the presence of an unusual spin-coupled Mo(III) site. Although so far Mo(III) was not reported to occur in biology the suggestion raises interesting parallels with the known homogenous Mo catalysts for N-2 reduction, where a Mo(III) compound is the N-2-binding species. It also requires a reassignment of the Fe oxidation states in the cofactor.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Spatzal, T.; Einsle, O.]Univ Freiburg, Inst Biochem, D-79104 Freiburg, Germany
[Glatzel, P.;]European Synchrotron Radiat Facil, F-38043
Identifiers:ISI:000338652900018 [ID No:1]
ISSN:2041-6520 [ID No:2]
DOI:10.1039/C4SC00337C [ID No:3]
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