X-ray Magnetic Circular Dichroism Spectroscopy Applied to Nitrogenase and Related Models: Experimental Evidence for a Spin-Coupled Molybdenum(III) Center

Kowalska, Joanna K.; Henthorn, Justin T.; Van Stappen, Casey; Trncik, Christian; Einsle, Oliver; Keavney, David; DeBeer, Serena

doi:10.1002/anie.201901899

Title: X-ray Magnetic Circular Dichroism Spectroscopy Applied to Nitrogenase and Related Models: Experimental Evidence for a Spin-Coupled Molybdenum(III) Center

Journal Article · 22 May 2019 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201901899 · OSTI ID:1605471

^[1]; Henthorn, Justin T. ^[1]; Van Stappen, Casey ^[1]; Trncik, Christian ^[2]; Einsle, Oliver ^[2]; Keavney, David ^[3];

^[1]

Max Planck Institute for Chemical Energy Conversion, Stiftstrasse (Germany). Inorganic Spectroscopy
Albert Ludwigs Univ. of Freiburg (Germany). Inst. for Biochemistry and BIOSS Centre for Biological Signalling Studies
Argonne National Lab. (ANL), Argonne, IL (United States)

Nitrogenase enzymes catalyze the reduction of atmospheric dinitrogen to ammonia utilizing a Mo-7Fe-9S-C active site, the so-called FeMoco cluster. FeMoco and an analogous small-molecule (Et4N)[(Tp)MoFe₃S₄Cl₃] cubane have both been proposed to contain unusual spin-coupled Mo-III sites with an S(Mo)=1/2 non-Hund configuration at the Mo atom. Herein, we present Fe and Mo L₃-edge X-ray magnetic circular dichroism (XMCD) spectroscopy of the (Et₄N)[(Tp)MoFe₃S₄Cl₃] cubane and Fe L_2,3-edge XMCD spectroscopy of the MoFe protein (containing both FeMoco and the 8Fe-7S P-cluster active sites). As the P-clusters of MoFe protein have an S=0 total spin, these are effectively XMCD-silent at low temperature and high magnetic field, allowing for FeMoco to be selectively probed by Fe L_2,3-edge XMCD within the intact MoFe protein. Further, Mo L₃-edge XMCD spectroscopy of the cubane model has provided experimental support for a local S(Mo)=1/2 configuration, demonstrating the power and selectivity of XMCD.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: European Commission - Community Research and Development Information Service (CORDIS) - Seventh Framework Programme (FP7); German Research Foundation (DFG); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1605471

Alternate ID(s):: OSTI ID: 1526781; OSTI ID: 1559977

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 28; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Characterization of Isolated Nitrogenase FeVco Fay, Aaron W.; Blank, Michael A.; Lee, Chi Chung Journal of the American Chemical Society, Vol. 132, Issue 36 https://doi.org/10.1021/ja1019657	journal	September 2010
Nitrogenase FeMoco investigated by spatially resolved anomalous dispersion refinement Spatzal, Thomas; Schlesier, Julia; Burger, Eva-Maria Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10902	journal	March 2016
High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory Lima, Frederico A.; Bjornsson, Ragnar; Weyhermüller, Thomas Physical Chemistry Chemical Physics, Vol. 15, Issue 48 https://doi.org/10.1039/c3cp53133c	journal	January 2013
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Electron Paramagnetic Resonance of Nitrogenase and Nitrogenase Components from Clostridium pasteurianum W5 and Azotobacter vinelandii OP Orme-Johnson, W. H.; Hamilton, W. D.; Jones, T. L. Proceedings of the National Academy of Sciences, Vol. 69, Issue 11 https://doi.org/10.1073/pnas.69.11.3142	journal	November 1972
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X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor Lancaster, K. M.; Roemelt, M.; Ettenhuber, P. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1206445	journal	November 2011
Evidence for Interstitial Carbon in Nitrogenase FeMo Cofactor Spatzal, T.; Aksoyoglu, M.; Zhang, L. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1214025	journal	November 2011

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Spectroscopic X-ray and Mössbauer Characterization of M ₆ and M ₅ Iron(Molybdenum)-Carbonyl Carbide Clusters: High Carbide-Iron Covalency Enhances Local Iron Site Electron Density Despite Cluster Oxidation McGale, Jeremy; Cutsail, George E.; Joseph, Chris Inorganic Chemistry, Vol. 58, Issue 19 https://doi.org/10.1021/acs.inorgchem.9b01870	journal	September 2019
Localized Electronic Structure of Nitrogenase FeMoco Revealed by Selenium K-Edge High Resolution X-ray Absorption Spectroscopy Henthorn, Justin T.; Arias, Renee J.; Koroidov, Sergey Journal of the American Chemical Society, Vol. 141, Issue 34 https://doi.org/10.1021/jacs.9b06988	journal	July 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
FeMo cofactor
X-ray magnetic circular dichroism spectroscopy
nitrogen fixation
nitrogenase
spin coupling

Title: X-ray Magnetic Circular Dichroism Spectroscopy Applied to Nitrogenase and Related Models: Experimental Evidence for a Spin-Coupled Molybdenum(III) Center

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