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Preparation of the Hydrosulfido-Bridged Diruthenium Complex [(η5-C5Me5)RuCl(μ-SH)2Ru(η5-C5Me5)Cl] and Its Transformation into a Cubane-Type Tetraruthenium Sulfido Cluster or Triangular Heterometallic RhRu2 Sulfido Cluster

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journal contribution
posted on 1996-07-23, 00:00 authored by Kohjiro Hashizume, Yasushi Mizobe, Masanobu Hidai
The hydrosulfido-bridged diruthenium complex [Cp*RuCl(μ-SH)2RuCp*Cl] (4; Cp* = η5-C5Me5) was obtained by the reaction of either [(Cp*Ru)43-Cl)4] (1) or [Cp*RuCl(μ-Cl)2RuCp*Cl] with excess H2S gas, while the reactions of 1 with thiols resulted in the formation of the thiolato-bridged diruthenium complexes [Cp*RuCl(μ-SR)2RuCp*Cl] (R = Et (5a), C6H4Me-p). When a solution of 4 in toluene was heated at reflux, the cubane-type tetraruthenium sulfido cluster [(Cp*Ru)43-S)4]Cl2 (6) was produced. On the other hand, treatment of 4 with 2 molar equiv of [RhCl(PPh3)3] in THF at room temperature afforded the triangular heterometallic sulfido cluster [(Cp*Ru)22-H)(μ3-S)2RhCl2(PPh3)] (10). X-ray analyses have been undertaken to determine the detailed structures for 4, 5a, 6, and 10.

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