A [4Fe−4S] Cluster Dimer Bridged by Bis(2,2′:6′,2″-terpyridine-4′-thiolato)iron(II)

Geer, Erwin P. L. van der; Koten, Gerard van; Gebbink, Robertus J. M. Klein; Hessen, Bart

doi:10.1021/ic702062q

Cited by 15 publications

(27 citation statements)

References 56 publications

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“…This proton is bound to the ring at a position which receives delocalized positive spin density from the cluster-bound sulfur atom, and it is also the hydrogen atom closest to the cluster. Interestingly, a 1 H NMR signal was never observed for the analogous H2 protons of TriSH 3 after coordination to [4Fe-4S] clusters [6,7].…”

Section: H Nmr Analysismentioning

confidence: 99%

“…for C 9 H 9 NS: C, 66. To a mixture of (n-Bu 4 N) 2 [Fe 4 S 4 (S-t-Bu) 4 ] [12] (0.100 g, 0.0838 mmol) and indole-3-thiol [7,9] (63 mg, 0.42 mmol) was added DMF (7 mL). The mixture was stirred overnight to yield a dark violet solution, which was concentrated in vacuo.…”

Section: -Methylindole-3-thiol (2b)mentioning

confidence: 99%

“…In order to test the general applicability of our synthetic approach to [4Fe-4S] clusters with alkyl-and aryl-substituted indole-3-thiolate ligands, we synthesized a series of five indole-3-thiols with varying N-substituents (Scheme 1). Unsubstituted indole-3-thiol 2a [7,9] and its methyl- [13] and benzyl-substituted [6] analogs 2b and 2e have been prepared previously by Harris's method, although synthetic details for 2b and 2e were not reported. Two alkyl-substituted indole-3-thiols with longer aliphatic substituents (2c = pentyl, 2d = decyl) were prepared analogously from the known compounds 1-pentylindole [14] and 1-decylindole [15].…”

Section: -Methylindole-3-thiol (2b)mentioning

confidence: 99%

“…Of these alternatives, the TriSH 3 ligand (Chart 1), reported by Pohl and co-workers in 1997, is arguably the most promising [6]. Not only is TriSH 3 the only alternative to L(SH) 3 for which 1:1 reaction stoichiometry with [4Fe-4S] clusters has been proven crystallographically, [6] but our recent optimization of the synthesis of TriSH 3 has also rendered its preparation both convenient and high-yielding [7].…”

Section: Introductionmentioning

confidence: 99%

“…The thiouronium salt was subsequently hydrolyzed to indole-3-thiol, a thiol that is aromatic but not nearly as acidic as thiophenol [9]. Indole-3-thiol can then be further derivatized to form TriSH 3 [6,7].…”

Section: Introductionmentioning

confidence: 99%

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N-Substituted indole-3-thiolate [4Fe–4S] clusters with a unique and tunable combination of spectral and redox properties

Geer

Koten

et al. 2008

Inorganica Chimica Acta

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A series of N-substituted indole-3-thiols, synthesized by sequential alkylation, thiouronium salt formation, and hydrolysis, are used to generate a novel family of [4Fe-4S] clusters. The redox transitions of the clusters deviate from those of other [4Fe-4S] cluster families, with half-wave potentials lying in a range midway between those of [4Fe-4S] clusters bound by aliphatic thiolate ligands and those bound by thiophenolate-based ligands. In UV-vis spectroscopy, the new cluster family shows absorption maxima that are among the most redshifted reported thus far in [4Fe-4S] cluster chemistry. The indole-3-thiolate ligand thus leads to a highly specific and uncommon combination of [4Fe-4S] cluster properties, which can be fine-tuned by facile derivatization at the indole nitrogen atom.

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Section: H Nmr Analysismentioning

confidence: 99%

Section: -Methylindole-3-thiol (2b)mentioning

confidence: 99%

Section: -Methylindole-3-thiol (2b)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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N-Substituted indole-3-thiolate [4Fe–4S] clusters with a unique and tunable combination of spectral and redox properties

Geer

Koten

et al. 2008

Inorganica Chimica Acta

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Tridentate Thiolate Ligands: Application to the Synthesis of the Site‐Differentiated [4Fe‐4S] Cluster having a Hydrosulfide Ligand at the Unique Iron Center

Terada

Wakimoto

Nakamura

et al. 2012

Chemistry An Asian Journal

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We have designed new trithiols Temp(SH)(3) and Tefp(SH)(3) that can be synthesized conveniently in short steps and are useful for preparation of crystalline [3:1] site-differentiated [4Fe-4S] clusters suitable for X-ray structural analysis. The ethanethiolate clusters (PPh(4))(2)[Fe(4)S(4)(SEt)(TempS(3))] (4a) and (PPh(4))(2)[Fe(4)S(4)(SEt)(TefpS(3))] (4b) were prepared as precursors, and the unique iron sites were then selectively substituted. Upon reaction with H(2)S, (PPh(4))(2)[Fe(4)S(4)(SH)(TempS(3))] (6a) and (PPh(4))(2)[Fe(4)S(4)(SH)(TefpS(3))] (6b), which model the [4Fe-4S] cluster in the β subunit of (R)-2-hydroxyisocaproyl-CoA dehydratase, were synthesized. Clusters 6a and 6b were further converted to the sulfido-bridged double cubanes (PPh(4))(4)[{Fe(4)S(4)(TempS(3))}(2)(μ(2)-S)] (7a) and (PPh(4))(4)[{Fe(4)S(4)(TefpS(3))}(2)(μ(2)-S)] (7b), respectively, via intermolecular condensation with the release of H(2)S. Conversely, addition of H(2)S to 7a,b afforded the hydrosulfide clusters 6a,b. The molecular structures of the clusters reported herein were elucidated by X-ray crystallographic analysis. Their redox properties were investigated by cyclic voltammetry.

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Connecting [4Fe–4S] Clusters and Hemes – Towards Modeling the Active Site of Sulfite Reductase

2013

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In this paper, we present a new design for biologically inspired models for the active site of assimilatory sulfite and nitrite reductases (aSIR and aNIR), which consists of a siroheme that is directly linked to a [4Fe-4S] cubane cluster. The individual components used here to construct this model are a site-differentiated [4Fe-4S] cluster, a bifunctional bridging ligand, and a metalloporphyrin. We have prepared two new site-differentiated clusters, [Fe 4 S 4 (TriS)(SPy)] and [Fe 4 S 4 (TriS)(SEtIm)], which contain pyridine and imidazole linkers for the binding to a metalloporphyrin, and characterized these compounds, using UV/Vis, IR, and 1 H-NMR spectroscopy, cyclic voltammetry (CV), and mass spectrometry. Titration experiments where then performed by using [Zn(TPP)] (TPP 2-= meso-tetraphenylporphyrin dianion) and

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A [4Fe−4S] Cluster Dimer Bridged by Bis(2,2′:6′,2″-terpyridine-4′-thiolato)iron(II)

Abstract: The use of 2,2′:6′,2″-terpyridine-4′-thiol (tpySH) was explored as a bridging ligand for the formation of stable assemblies containing both [4Fe-4S] clusters and single metal ions. Reaction of tpySH (2 equiv

Cited by 15 publications

References 56 publications

N-Substituted indole-3-thiolate [4Fe–4S] clusters with a unique and tunable combination of spectral and redox properties

N-Substituted indole-3-thiolate [4Fe–4S] clusters with a unique and tunable combination of spectral and redox properties

Tridentate Thiolate Ligands: Application to the Synthesis of the Site‐Differentiated [4Fe‐4S] Cluster having a Hydrosulfide Ligand at the Unique Iron Center

Connecting [4Fe–4S] Clusters and Hemes – Towards Modeling the Active Site of Sulfite Reductase

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