Proton-Coupled Reduction of the Catalytic [4Fe-4S] Cluster in [FeFe]-Hydrogenases

Angewandte Chemie
Moritz SengerSven T Stripp

Abstract

In nature, [FeFe]-hydrogenases catalyze the uptake and release of molecular hydrogen (H2 ) at a unique iron-sulfur cofactor. The absence of an electrochemical overpotential in the H2 release reaction makes [FeFe]-hydrogenases a prime example of efficient biocatalysis. However, the molecular details of hydrogen turnover are not yet fully understood. Herein, we characterize the initial one-electron reduction of [FeFe]-hydrogenases by infrared spectroscopy and electrochemistry and present evidence for proton-coupled electron transport during the formation of the reduced state Hred'. Charge compensation stabilizes the excess electron at the [4Fe-4S] cluster and maintains a conservative configuration of the diiron site. The role of Hred' in hydrogen turnover and possible implications on the catalytic mechanism are discussed. We propose that regulation of the electronic properties in the periphery of metal cofactors is key to orchestrating multielectron processes.

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Citations

Aug 14, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Changguang YaoKuo-Wei Huang
Jul 25, 2019·Proceedings of the National Academy of Sciences of the United States of America·Oliver LampretThomas Happe
Aug 17, 2020·Proceedings of the National Academy of Sciences of the United States of America·Oliver LampretThomas Happe
May 5, 2018·Chemical Communications : Chem Comm·F WittkampU-P Apfel
Jul 11, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Konstantin LaunSven T Stripp
Dec 12, 2020·Chemical Society Reviews·Julian T KleinhausUlf-Peter Apfel
Feb 26, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Konstantin LaunSven T Stripp
Dec 19, 2017·Journal of the American Chemical Society·Nipa ChongdarHideaki Ogata
Oct 4, 2019·Journal of the American Chemical Society·Moritz SengerSven Timo Stripp
Dec 17, 2020·Accounts of Chemical Research·Hulin TaiSven T Stripp
Jul 13, 2018·Accounts of Chemical Research·Michael Haumann, Sven T Stripp
Apr 24, 2019·Journal of the American Chemical Society·Eric S Wiedner
Dec 14, 2018·Journal of the American Chemical Society·Patricia Rodríguez-MaciáOlaf Rüdiger
Oct 21, 2021·Journal of the American Chemical Society·Maria Alessandra MartiniJames A Birrell

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