[Fe <sub>2</sub> (μ-S <sub>2</sub> )(CN) <sub>2</sub> (CO) <sub>4</sub> ] <sup>2–</sup> , [Fe <sub>2</sub> (μ-SH) <sub>2</sub> (CN) <sub>2</sub> (CO) <sub>4</sub> ] <sup>2–</sup> , and [Fe <sub>2</sub> (μ-SH)(μ-SCH <sub>2</sub> NH <sub>2</sub> )(CN)

This paper discusses diiron complexes implicated as intermediates in the biosynthesis of the [2Fe]<sub>H</sub> site of the [FeFe]-hydrogenases. These complexes include [Fe<sub>2</sub>(μ-SH)(μ-SR)(CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> (R = H, CH<sub>2</sub>NH<sub>2</sub> [<b>2</b><sup>H,R</sup>]<sup>2-</sup>), which are available from the new precursor [Fe<sub>2</sub>(μ-S<sub>2</sub>)(CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>1</b>]<sup>2-</sup>). Complex [<b>1</b>]<sup>2-</sup> was prepared by treating Fe<sub>2</sub>(μ-S<sub>2</sub>)(CO)<sub>6</sub> with two equiv of KN(tms)<sub>2</sub>. Access to [<b>2</b><sup>H,R</sup>]<sup>2-</sup> involves the reaction of [<b>1</b>]<sup>2-</sup> with LiBHEt<sub>3</sub> followed by quenching with the equivalent of R<sup>+</sup>. Similarly, access to [Fe<sub>2</sub>(μ-SMe)(μ-SCH<sub>2</sub>NHFmoc)(CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>2</b><sup>Me,CH2NHFmoc</sup>]<sup>2-</sup>) involves treating [<b>1</b>]<sup>2-</sup> with MeLi, followed by quenching with FmocNHCH<sub>2</sub>OAc. As established by <sup>15</sup>N-labeling, deprotection of [<b>2</b><sup>H,CH2NHFmoc</sup>]<sup>2-</sup> gave the azadithiolate [Fe<sub>2</sub>[(μ-SCH<sub>2</sub>)<sup>15</sup>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>4</b><sup>15</sup>N]<sup>2-</sup>) and <sup>15</sup>NH<sub>3</sub>.

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Publication Details

Journal
Inorganic Chemistry
Published
2025-10-17
DOI
https://doi.org/10.1021/acs.inorgchem.5c03496
Citations
1
Primary Topic
Metalloenzymes and iron-sulfur proteins
Type
article
Field-Weighted Citation Impact
0.36
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article

[Fe 2 (μ-S 2 )(CN) 2 (CO) 4 ] 2– , [Fe 2 (μ-SH) 2 (CN) 2 (CO) 4 ] 2– , and [Fe 2 (μ-SH)(μ-SCH 2 NH 2 )(CN)

Thomas B. Rauchfuss, Yu Zhang, Xin Yu, Toby J. Woods
1 citations
Inorganic Chemistry
Metalloenzymes and iron-sulfur proteins
0.36
article

[Fe 2 (μ-S 2 )(CN) 2 (CO) 4 ] 2– , [Fe 2 (μ-SH) 2 (CN) 2 (CO) 4 ] 2– , and [Fe 2 (μ-SH)(μ-SCH 2 NH 2 )(CN)

Thomas B. Rauchfuss, Yu Zhang, Xin Yu, Toby J. Woods
article en
1 citations

Abstract

This paper discusses diiron complexes implicated as intermediates in the biosynthesis of the [2Fe]<sub>H</sub> site of the [FeFe]-hydrogenases. These complexes include [Fe<sub>2</sub>(μ-SH)(μ-SR)(CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> (R = H, CH<sub>2</sub>NH<sub>2</sub> [<b>2</b><sup>H,R</sup>]<sup>2-</sup>), which are available from the new precursor [Fe<sub>2</sub>(μ-S<sub>2</sub>)(CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>1</b>]<sup>2-</sup>). Complex [<b>1</b>]<sup>2-</sup> was prepared by treating Fe<sub>2</sub>(μ-S<sub>2</sub>)(CO)<sub>6</sub> with two equiv of KN(tms)<sub>2</sub>. Access to [<b>2</b><sup>H,R</sup>]<sup>2-</sup> involves the reaction of [<b>1</b>]<sup>2-</sup> with LiBHEt<sub>3</sub> followed by quenching with the equivalent of R<sup>+</sup>. Similarly, access to [Fe<sub>2</sub>(μ-SMe)(μ-SCH<sub>2</sub>NHFmoc)(CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>2</b><sup>Me,CH2NHFmoc</sup>]<sup>2-</sup>) involves treating [<b>1</b>]<sup>2-</sup> with MeLi, followed by quenching with FmocNHCH<sub>2</sub>OAc. As established by <sup>15</sup>N-labeling, deprotection of [<b>2</b><sup>H,CH2NHFmoc</sup>]<sup>2-</sup> gave the azadithiolate [Fe<sub>2</sub>[(μ-SCH<sub>2</sub>)<sup>15</sup>NH](CN)<sub>2</sub>(CO)<sub>4</sub>]<sup>2-</sup> ([<b>4</b><sup>15</sup>N]<sup>2-</sup>) and <sup>15</sup>NH<sub>3</sub>.

Inorganic ChemistryVol. 64(43)
Tufts University (US), University of Illinois System (US), Jiangxi Science and Technology Normal University (CN), Institute of Organic Chemistry (HU)
Openalex Percentile: Top 37%
Metalloenzymes and iron-sulfur proteins
0.36
DOISourceOpenAlex
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