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Published on: April 10, 2018
Comparative electronic structures of nitrogenase FeMoco and FeVco
Julian A Rees1, Ragnar Bjornsson2, Joanna K Kowalska3
1Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470 Mülheim an der Ruhr, Germany. serena.debeer@cec.mpg.de and Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195-1700, USA. kovacs@chem.washington.edu.
Abstract:
An investigation of the active site cofactors of the molybdenum and vanadium nitrogenases (FeMoco and FeVco) was performed using high-resolution X-ray spectroscopy. Synthetic heterometallic iron-sulfur cluster models and density functional theory calculations complement the study of the MoFe and VFe holoproteins using both non-resonant and resonant X-ray emission spectroscopy. Spectroscopic data show the presence of direct iron-heterometal bonds, which are found to be weaker in FeVco. Furthermore, the interstitial carbide is found to perturb the electronic structures of the cofactors through highly covalent Fe-C bonding. The implications of these conclusions are discussed in light of the differential reactivity of the molybdenum and vanadium nitrogenases towards various substrates. Possible functional roles for both the heterometal and the interstitial carbide are detailed.
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