Structural Characterization of Two CO Molecules Bound to the Nitrogenase Active Site

Buscagan, Trixia M.; Perez, Kathryn A.; Maggiolo, Ailiena O.; Rees, Douglas C.; Spatzal, Thomas

doi:10.1002/anie.202015751

Title: Structural Characterization of Two CO Molecules Bound to the Nitrogenase Active Site

Journal Article · Wed Jan 27 00:00:00 EST 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202015751· OSTI ID:1816336

^[1]; Perez, Kathryn A. ^[2]; Maggiolo, Ailiena O. ^[2];

^[1];

^[2]

California Institute of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering; California Institute of Technology (CalTech), Pasadena, CA (United States). Howard Hughes Medical Inst.
California Institute of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering

As an approach towards unraveling the nitrogenase mechanism, we have studied the binding of CO to the activesite FeMo-cofactor. CO is not only an inhibitor of nitrogenase, but it is also a substrate, undergoing reduction to hydrocarbons (Fischer–Tropsch-type chemistry). The CC bond forming capabilities of nitrogenase suggest that multiple CO or COderived ligands bind to the active site. Herein, we report a crystal structure with two CO ligands coordinated to the FeMo-cofactor of the molybdenum nitrogenase at 1.33 resolution. In addition to the previously observed bridging CO ligand between Fe2 and Fe6 of the FeMo-cofactor, a new ligand binding mode is revealed through a second CO ligand coordinated terminally to Fe6. While the relevance of this state to nitrogenase-catalyzed reactions remains to be established, it highlights the privileged roles for Fe2 and Fe6 in ligand binding, with multiple coordination modes available depending on the ligand and reaction conditions.

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Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER). Biological Systems Science Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1816336

Journal Information:: Angewandte Chemie (International Edition), Vol. 60, Issue 11; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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