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Stepwise O2 -Induced Rearrangement and Disassembly of the [NiFe4 (OH)(μ3 -S)4 ] Active Site Cluster of CO Dehydrogenase.

Basak Y, Jeoung JH, Domnik L, Dobbek H
Angew Chem Int Ed Engl 62 e202305341 (2023)
Related entries: 8omx, 8omy, 8on1, 8on2, 8on3

Cited: 4 times
EuropePMC logo PMID: 37279092

Abstract

Ni,Fe-containing carbon monoxide dehydrogenases (CODHs) catalyze the reversible reduction of carbon dioxide to carbon monoxide. CODHs are found in anaerobic microorganisms and can rapidly lose their activity when exposed to air. What causes the loss of activity is unclear. In this study, we analyzed the time-dependent structural changes induced by the presence of air on the metal centers of CODH-II. We show that inactivation is a multistep process. In a reversible step, the open coordination site on the Ni ion is blocked by a Ni,Fe-bridging μ-sulfido or chlorido ligand. Blocking this open coordination site with a cyanide ligand stabilizes the cluster against O2 -induced decomposition, indicating that O2 attacks at the Ni ion. In the subsequent irreversible phase, nickel is lost, the Fe ions rearrange and the sulfido ligands disappear. Our data are consistent with a reversible reductive reactivation mechanism to protect CODHs from transient over-oxidation.

Articles citing this publication (4)

  1. Three-Coordinate Nickel and Metal-Metal Interactions in a Heterometallic Iron-Sulfur Cluster. Wilson DWN, Fataftah MS, Mathe Z, Mercado BQ, DeBeer S, Holland PL. J Am Chem Soc 146 4013-4025 (2024)
  2. Bioinspired Binickel Catalyst for Carbon Dioxide Reduction: The Importance of Metal-ligand Cooperation. Xiao Y, Xie F, Zhang HT, Zhang MT. JACS Au 4 1207-1218 (2024)
  3. Electronic isomerism in a heterometallic nickel-iron-sulfur cluster models substrate binding and cyanide inhibition of carbon monoxide dehydrogenase. Lewis LC, Sanabria-Gracia JA, Lee Y, Jenkins AJ, Shafaat HS. Chem Sci 15 5916-5928 (2024)
  4. Inserting Three-Coordinate Nickel into [4Fe-4S] Clusters. Fataftah MS, Wilson DWN, Mathe Z, Gerard TJ, Mercado BQ, DeBeer S, Holland PL. ACS Cent Sci 10 1910-1919 (2024)


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