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

ID: 733839.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Revisiting the Mössbauer Isomer Shifts of the FeMoco Cluster of Nitrogenase and the Cofactor Charge
Authors:Bjornsson, Ragnar; Neese, Frank; DeBeer, Serena
Date of Publication (YYYY-MM-DD):2017
Title of Journal:Inorganic Chemistry
Journal Abbrev.:Inorg.Chem.
Issue / Number:3
Start Page:1470
End Page:1477
Review Status:Internal review
Audience:Experts Only
Abstract / Description: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 Mossbauer 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 M-S = 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.
Comment of the Author/Creator:Date: 2017, FEB 6 2017
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000393630300050 [ID No:1]
ISSN:0020-1669 [ID No:2]
DOI:10.1021/acs.inorgchem.6b02540 [ID No:3]
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