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Revisiting the Mössbauer Isomer Shifts of the FeMoco Cluster of Nitrogenase and the Cofactor Charge

Revisiting the Mössbauer Isomer Shifts of the FeMoco Cluster of Nitrogenase and the Cofactor Charge


Titill: Revisiting the Mössbauer Isomer Shifts of the FeMoco Cluster of Nitrogenase and the Cofactor Charge
Höfundur: Bjornsson, Ragnar   orcid.org/0000-0003-2167-8374
Neese, Frank
DeBeer, Serena
Útgáfa: 2017-01-10
Tungumál: Enska
Umfang: 1470-1477
Háskóli/Stofnun: Háskóli Íslands
University of Iceland
Svið: Verkfræði- og náttúruvísindasvið (HÍ)
School of Engineering and Natural Sciences (UI)
Deild: Raunvísindastofnun (HÍ)
Science Institute (UI)
Raunvísindadeild (HÍ)
Faculty of Physical Sciences (UI)
Birtist í: Inorganic Chemistry;56(3)
ISSN: 0020-1669
1520-510X (eISSN)
DOI: 10.1021/acs.inorgchem.6b02540
Efnisorð: Inorganic Chemistry; FeMo; Ólífræn efnafræði; Efnasambönd
URI: https://hdl.handle.net/20.500.11815/521

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Tilvitnun:

Bjornsson, R., Neese, F., & DeBeer, S. (2017). Revisiting the Mössbauer Isomer Shifts of the FeMoco Cluster of Nitrogenase and the Cofactor Charge. Inorganic Chemistry, 56(3), 1470-1477. doi:10.1021/acs.inorgchem.6b02540

Útdráttur:

Despite decades of research, the structure–activity relationship of nitrogenase is still not understood. Only recently was the full molecular structure of the FeMo cofactor (FeMoco) revealed, but the charge and metal oxidation states of FeMoco have been controversial. With the recent identification of the interstitial atom as a carbide and the more recent revised oxidation-state assignment of the molybdenum atom as Mo(III), here we revisit the Mössbauer properties of FeMoco. By a detailed error analysis of density functional theory-computed isomer shifts and computing isomer shifts relative to the P-cluster, we find that only the charge of [MoFe7S9C]1– fits the experimental data. In view of the recent Mo(III) identification, the charge of [MoFe7S9C]1– corresponds to a formal oxidation-state assignment of Mo(III)3Fe(II)4Fe(III), although due to spin delocalization, the physical oxidation state distribution might also be interpreted as Mo(III)1Fe(II)4Fe(2.5)2Fe(III), according to a localized orbital analysis of the MS = 3/2 broken symmetry solution. These results can be reconciled with the recent spatially resolved anomalous dispersion study by Einsle et al. that suggests the Mo(III)3Fe(II)4Fe(III) distribution, if some spin localization (either through interactions with the protein environment or through vibronic coupling) were to take place.

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Copyright © 2017 American Chemical Society

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