TY  - JOUR
AU  - Basak, Yudhajeet
AU  - Lorent, Christian
AU  - Jeoung, Jae-Hun
AU  - Zebger, Ingo
AU  - Dobbek, Holger
TI  - Metalloradical-driven enzymatic CO<sub>2</sub> reduction by a dynamic Ni–Fe cluster
JO  - Nature catalysis
VL  - 8
IS  - 8
SN  - 2520-1158
CY  - [London]
PB  - Macmillan Publishers Limited, part of Springer Nature
M1  - PUBDB-2025-04025
SP  - 794 - 803
PY  - 2025
N1  - 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.). 
AB  - Carbon monoxide dehydrogenases (CODHs) selectively catalyse the reversible reduction of CO<sub>2</sub> 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<sub>2</sub> 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<sub>2</sub> activation. The Fe(II) ion switches between two positions, the one preceding CO<sub>2</sub> activation is close to Ni(I) with a potential Ni(I)–Fe(II) interaction and the other binds the substrates CO<sub>2</sub> and water. We demonstrate how the Ni–Fe cluster creates an efficient CO<sub>2</sub> reduction catalyst and provides a blueprint for the design of novel catalysts based on abundant transition metals. 
LB  - PUB:(DE-HGF)16
DO  - DOI:10.1038/s41929-025-01388-5
UR  - https://bib-pubdb1.desy.de/record/638307
ER  -