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Organometallic Fe <sub>2</sub> (μ-SH) <sub>2</sub> (CO) <sub>4</sub> (CN) <sub>2</sub> Cluster Allows the Biosynthesis of the [FeFe]-Hydrogenase with Only the HydF Maturase

Yu Zhang, Lizhi Tao, Toby J. Woods, R. David Britt, Thomas B. Rauchfuss

2022Journal of the American Chemical Society35 citationsDOIOpen Access PDF

Abstract

The biosynthesis of the active site of the [FeFe]-hydrogenases (HydA1), the H-cluster, is of interest because these enzymes are highly efficient catalysts for the oxidation and production of H2. The biosynthesis of the [2Fe]H subcluster of the H-cluster proceeds from simple precursors, which are processed by three maturases: HydG, HydE, and HydF. Previous studies established that HydG produces an Fe(CO)2(CN) adduct of cysteine, which is the substrate for HydE. In this work, we show that by using the synthetic cluster [Fe2(μ-SH)2(CN)2(CO)4]2– active HydA1 can be biosynthesized without maturases HydG and HydE.

Topics & Concepts

ChemistryHydrogenaseBiosynthesisCluster (spacecraft)CatalysisAdductActive siteSubstrate (aquarium)EnzymeStereochemistryOrganic chemistryProgramming languageGeologyOceanographyComputer scienceMetalloenzymes and iron-sulfur proteinsElectrocatalysts for Energy ConversionAdvanced battery technologies research