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Final Stages in the Biosynthesis of the [FeFe]-Hydrogenase Active Site.

Authors :: Yu X
Rao G
Britt RD
Rauchfuss TB
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 May 27; Vol. 63 (22), pp. e202404044. Date of Electronic Publication: 2024 Apr 18.
Publication Year :: 2024
Abstract: The paper aims to elucidate the final stages in the biosynthesis of the [2Fe] <subscript>H</subscript> active site of the [FeFe]-hydrogenases. The recently hypothesized intermediate [Fe <subscript>2</subscript> (SCH <subscript>2</subscript> NH <subscript>2</subscript> ) <subscript>2</subscript> (CN) <subscript>2</subscript> (CO) <subscript>4</subscript> ] <superscript>2-</superscript> ([1] <superscript>2-</superscript> ) was prepared by a multistep route from [Fe <subscript>2</subscript> (S <subscript>2</subscript> )(CN)(CO) <subscript>5</subscript> ] <superscript>-</superscript> . The following synthetic intermediates were characterized in order: [Fe <subscript>2</subscript> (SCH <subscript>2</subscript> NHFmoc) <subscript>2</subscript> (CNBEt <subscript>3</subscript> )(CO) <subscript>5</subscript> ] <superscript>-</superscript> , [Fe <subscript>2</subscript> (SCH <subscript>2</subscript> NHFmoc) <subscript>2</subscript> (CN)-(CO) <subscript>5</subscript> ] <superscript>-</superscript> , and [Fe <subscript>2</subscript> (SCH <subscript>2</subscript> NHFmoc) <subscript>2</subscript> (CN) <subscript>2</subscript> (CO) <subscript>4</subscript> ] <superscript>2-</superscript> , where Fmoc is fluorenylmethoxycarbonyl). Derivatives of these anions include [K(18-crown-6)] <superscript>+</superscript> , PPh <subscript>4</subscript> <superscript>+</superscript> and PPN <superscript>+</superscript> salts as well as the <superscript>13</superscript> CD <subscript>2</subscript> -isotopologues. These Fe <subscript>2</subscript> species exist as a mixture of two isomers attributed to diequatorial (ee) and axial-equatorial (ae) stereochemistry at sulfur. In vitro experiments demonstrate that [1] <superscript>2-</superscript> maturates HydA1 in the presence of HydF and a cocktail of reagents. HydA1 can also be maturated using a highly simplified cocktail, omitting HydF and other proteins. This result is consistent with HydA1 participating in the maturation process and refines the roles of HydF.<br /> (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)