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Issue 12, 2017
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Synthesis, structural characterization and conversion of dinuclear iron–sulfur clusters containing the disulfide ligand: [Cp*Fe(μ–η22-bdt)(cis-μ–η11-S2)FeCp*], [Cp*Fe(μ-S(C6H4S2))(cis-μ–η11-S2)FeCp*], and [{Cp*Fe(bdt)}2(trans-μ–η11-S2)]

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Abstract

The treatment of [Cp*Fe(μ–η24-bdt)FeCp*] (1, Cp* = η5-C5Me5, bdt = benzene-1,2-dithiolate) with 1/4 equiv. of elemental sulfur (S8) gave a dinuclear iron–sulfur cluster [Cp*Fe(μ–η22-bdt)(cis-μ–η11-S2)FeCp*] (2), which contains a cis-1,2-disulfide ligand. When complex 2 further interacted with 1/8 equiv. of S8, another sulfur atom inserted into an Fe–S bond to give a rare product [Cp*Fe(μ-S(C6H4S2))(cis-μ–η11-S2)FeCp*] (3). Unexpectedly, a trans-1,2 disulfide-bridged diiron complex [{Cp*Fe(bdt)}2(trans-μ–η11-S2)] (4) was isolated from the reaction of complex 1 with 1/2 equiv. of S8, which represents a structural isomer of [2Fe–2S] ferredoxin-type clusters. In addition, cis-1,2-disulfide-bridged complex 3 can slowly convert into trans-1,2-disulfide-bridged complex 4 and the complex [Cp*Fe(μ–η22-S2)(cis-μ–η11-S2)FeCp*] (5) by self-assembly reaction at ambient temperature, which is evidenced by time-dependent 1H NMR spectroscopy.

Graphical abstract: Synthesis, structural characterization and conversion of dinuclear iron–sulfur clusters containing the disulfide ligand: [Cp*Fe(μ–η2:η2-bdt)(cis-μ–η1:η1-S2)FeCp*], [Cp*Fe(μ-S(C6H4S2))(cis-μ–η1:η1-S2)FeCp*], and [{Cp*Fe(bdt)}2(trans-μ–η1:η1-S2)]

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Publication details

The article was received on 06 Feb 2017, accepted on 23 Feb 2017 and first published on 24 Feb 2017


Article type: Communication
DOI: 10.1039/C7DT00450H
Citation: Dalton Trans., 2017,46, 3820-3824
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    Synthesis, structural characterization and conversion of dinuclear iron–sulfur clusters containing the disulfide ligand: [Cp*Fe(μ–η22-bdt)(cis-μ–η11-S2)FeCp*], [Cp*Fe(μ-S(C6H4S2))(cis-μ–η11-S2)FeCp*], and [{Cp*Fe(bdt)}2(trans-μ–η11-S2)]

    X. Ji, P. Tong, D. Yang, B. Wang, J. Zhao, Y. Li and J. Qu, Dalton Trans., 2017, 46, 3820
    DOI: 10.1039/C7DT00450H

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