Comparative electronic structures of nitrogenase FeMoco and FeVco

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

Standort
Deutsche Nationalbibliothek Frankfurt am Main
Umfang
Online-Ressource
Sprache
Englisch
Anmerkungen
Dalton transactions. 46, 8 (2017), 2445-2455, DOI 10.1039/c7dt00128b, issn: 1477-9234

Schlagwort
Vanadiumnitride
Nitrogenase
Elektronenstruktur

Ereignis
Veröffentlichung
(wo)
Freiburg
(wer)
Universität
(wann)
2018
Urheber
Rees, Julian A.
Bjornsson, Ragnar
Kowalska, Joanna K.
Lima, Frederico A.
Netzer, Julia Clarissa
Sippel, Daniel
Weyhermüller, Thomas
Einsle, Oliver
Kovacs, Julie A.
DeBeer, Serena

DOI
10.1039/c7dt00128b
URN
urn:nbn:de:bsz:25-freidok-150312
Rechteinformation
Kein Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
Letzte Aktualisierung
25.03.2025, 13:49 MEZ

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Entstanden

  • 2018

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