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Issue 8, 2017
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Comparative electronic structures of nitrogenase FeMoco and FeVco

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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.

Graphical abstract: Comparative electronic structures of nitrogenase FeMoco and FeVco

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Publication details

The article was received on 12 Jan 2017, accepted on 25 Jan 2017 and first published on 02 Feb 2017


Article type: Paper
DOI: 10.1039/C7DT00128B
Dalton Trans., 2017,46, 2445-2455
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    Comparative electronic structures of nitrogenase FeMoco and FeVco

    J. A. Rees, R. Bjornsson, J. K. Kowalska, F. A. Lima, J. Schlesier, D. Sippel, T. Weyhermüller, O. Einsle, J. A. Kovacs and S. DeBeer, Dalton Trans., 2017, 46, 2445
    DOI: 10.1039/C7DT00128B

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