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Chem Asian J. 2012 May;7(5):920-9. doi: 10.1002/asia.201200039. Epub 2012 Apr 5.

Tridentate thiolate ligands: application to the synthesis of the site-differentiated [4Fe-4S] cluster having a hydrosulfide ligand at the unique iron center.

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  • 1Research Center for Materials Science and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.


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.

Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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