Journal Article

PUBDB-2025-04025

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Metalloradical-driven enzymatic CO$_2$ reduction by a dynamic Ni–Fe cluster

Basak, Y. ; Lorent, C. (Corresponding author)Extern* ; Jeoung, J.-H. ; Zebger, I.Extern* ; Dobbek, H. (Corresponding author)

2025
Macmillan Publishers Limited, part of Springer Nature [London]

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Please use a persistent id in citations: doi:10.1038/s41929-025-01388-5  doi:10.3204/PUBDB-2025-04025

Abstract: Carbon monoxide dehydrogenases (CODHs) selectively catalyse the reversible reduction of CO$_2$ to CO and water. The catalytic centre of CODHs contains a unique [NiFe4(OH)(µ3-S)4] cluster whose role in activating and converting CO$_2$ is poorly understood. Here we reveal the structures of all catalytically relevant oxidation states with and without substrates and products bound. We show that the Ni–Fe cluster combines a rigid Fe–S core with a dynamic Ni(I/II)–Fe(II) dyad. The redox-active element is the Ni ion, cycling between square-planar Ni(II) and T-shaped Ni(I) states with metalloradical character, the latter serving as the nucleophile for CO$_2$ activation. The Fe(II) ion switches between two positions, the one preceding CO$_2$ activation is close to Ni(I) with a potential Ni(I)–Fe(II) interaction and the other binds the substrates CO$_2$ and water. We demonstrate how the Ni–Fe cluster creates an efficient CO$_2$ reduction catalyst and provides a blueprint for the design of novel catalysts based on abundant transition metals.

Note: This work was supported by the Deutsche Forschungsgemeinschaft(DFG; grant no. DO785/6-2, H.D.) and Germany’s ExcellenceStrategy (EXC 2008–390540038–UniSysCat, I.Z. and H.D.).

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Contributing Institute(s):

1. EMBL-User (EMBL-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. DFG project G:(GEPRIS)390540038 - EXC 2008: Unifying Systems in Catalysis "UniSysCat" (390540038) (390540038)

Experiment(s):

1. PETRA Beamline P13 (PETRA III)
2. PETRA Beamline P14 (PETRA III)

Appears in the scientific report 2025

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; DEAL Nature ; Essential Science Indicators ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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