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<p>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 [NiFe<sub>4</sub>(OH)(µ<sub>3</sub>-S)<sub>4</sub>] 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.</p><p></p>

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Metalloradical-driven enzymatic CO2 reduction by a dynamic Ni–Fe cluster

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年8月1日

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  • Yudhajeet Basak,
  • Christian Lorent,
  • Jae-Hun Jeoung,
  • Ingo Zebger,
  • Holger Dobbek

摘要

Carbon monoxide dehydrogenases (CODHs) selectively catalyse the reversible reduction of CO2 to CO and water. The catalytic centre of CODHs contains a unique [NiFe4(OH)(µ3-S)4] cluster whose role in activating and converting CO2 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 CO2 activation. The Fe(II) ion switches between two positions, the one preceding CO2 activation is close to Ni(I) with a potential Ni(I)–Fe(II) interaction and the other binds the substrates CO2 and water. We demonstrate how the Ni–Fe cluster creates an efficient CO2 reduction catalyst and provides a blueprint for the design of novel catalysts based on abundant transition metals.