Cluster synthesis was carried out by the reactions of [Cp′2Fe2S4] (Cp′=C5Me5, 1,3-C5H3(SiMe3)2) with some transition-metal complexes. The reaction of [Cp*2Fe2S4] (Cp*=C5Me5) with [M(CO)3(MeCN)3] or [M(CO)6] (M=Mo, W) resulted in the formation of tetranuclear tetrathiometalate clusters [(Cp*Fe(CO))2(M(μ3-S)2(μ-S) 2) (M(CO)4)]. In the reaction, redistribution of S and CO ligands took place between iron and tungsten atoms without losing them. The reaction of [Cp*2Fe2S4] with [Cp*Ru(MeCN)3](PF6) gave a tetranuclear cluster [Cp*4Fe2Ru2S4](PF 6)2. In contrast, when [CpS22Fe2S4] containing a bulky Cp derivative (CpS2=1,3-C5H3(SiMe3)2) was used in place of [Cp*2Fe2S4], a trinuclear cluster [(CpS2Fe)2(Cp*Ru)S4](PF6) was obtained. In the cluster, two disulfido ligands bridged over two iron atoms and one ruthenium atom in μ3-η1:η2:η2 and μ3-η1:η1:η2 fashion.
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