Binding of exogenous cyanide reveals new active-site states in [FeFe] hydrogenases

Author:

Martini Maria Alessandra1ORCID,Bikbaev Konstantin2ORCID,Pang Yunjie13,Lorent Christian4ORCID,Wiemann Charlotte45,Breuer Nina1,Zebger Ingo4ORCID,DeBeer Serena1ORCID,Span Ingrid2,Bjornsson Ragnar16ORCID,Birrell James A.17ORCID,Rodríguez-Maciá Patricia8ORCID

Affiliation:

1. Department of Inorganic Spectroscopy, Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470 Mülheim an der Ruhr, Germany

2. Department of Chemistry and Pharmacy, Friedrich Alexander University Erlangen-Nürnberg, Bioinorganic Chemistry, Erlangen, Germany

3. College of Chemistry, Beijing Normal University, 100875, Beijing, China

4. Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany

5. Ruanda-Zentrum und Büro für Afrika-Kooperationen, Universität Koblenz-Landau, Universitätsstraße 1, 56070 Koblenz, Germany

6. Univ. Grenoble Alpes, CNRS, CEA, IRIG, Laboratoire de Chimie et Biologie des Métaux, 17 Rue des Martyrs, F-38054 Grenoble, Cedex, France

7. School of Life Sciences, University of Essex, Colchester, CO4 3SQ, UK

8. Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK

Abstract

Binding of exogenous cyanide to the active site H-cluster in [FeFe] hydrogenase stabilizes new active-site states with an overoxidized diiron cofactor showing how σ-donor/π-acceptor interactions influence the electronic structure of metallocofactors.

Funder

Deutsche Forschungsgemeinschaft

Max-Planck-Gesellschaft

China Scholarship Council

University of Oxford

Publisher

Royal Society of Chemistry (RSC)

Subject

General Chemistry

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