Development of the Rational Synthetic Routes towards Trinuclear and Cubane-type Tetranuclear Mixed-metal Sulfido Clusters Containing Noble Metals

Tomotake IKADA, Yasushi MIZOBE,* Shigeki KUWATA† and Masanobu HIDAI*,††

Institute of Industrial Science, The University of Tokyo; Komaba, Meguro-ku, Tokyo 153-8505 Japan
† Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo; Hongo, Bunkyo-ku, Tokyo 113-8656 Japan
†† Department of Materials Science and Technology, Faculty of Industrial Science and Technology, Science University of Tokyo; Noda-shi 278-8510 Japan

Dimolybdenum and ditungsten complexes containing terminal and bridging sulfido ligands [M2S2 (μ2-S)2 (S2CNEt2)2] (M=Mo, W) react with a range of noble-metal complexes to afford a series of trinuclear and cubane-type tetranuclear mixed-metal clusters, whereby the core structure of the produced clusters, which is either [M' (μ2 -S) 2M2 (μ2-S)2], [M' (μ3-S) (μ2-S)3M2], or [M'2M2 (μ3-S) 4] (M'=Pd, Pt, Rh, Ir, or Ru), sharply depends upon the choice of the combination M/M' as well as the nature of the ligands bound to the noble metal incorporated into the cluster. Detailed structures of the new clusters obtained in this study have been determined by the single-crystal X-ray analyses for [Pt (PPh3) (μ2-S)2 {W (S2CNEt2) }2 (μ2-S)2], [{Pd (PPh3) }2 {Mo (S2CNEt2) }2 (μ3-S)4], [Ir (PPh3)2 (μ3-S) (μ2-S)3 {W (S2CNEt2 ) }2 (μ2-Cl) ], [{Rh (cod) }2 {MoCl (S2CNEt2) }2 (μ3-S)4] (cod=1,5-cyclooctadiene), and [ (Cp*Ru)2 {MoCl (S2CNEt2) }2 (μ3-S)4] (Cp*=η5-C5Me5).


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