Syntheses of Chalcogenklo-Bridged Transition Metal Clusters

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1. Novel hydrosulfido-and hydroselenido-bridged dinudear complexes of Ir, Rh, and Ru containing the M(μ-EB)_2M cores (E=S, Se) have been isolated, which have proved to serve as versatile precursors to synthesize a variety of chalcogenido bridged homo-and hetermetallic clusters through dimerizartion or by treatment with certain transition metal compounds as well as main group metal species. The nuclearities of the produced dusters vary from three to seven. Trinuclear sulfido-thiolato duster of Ir [(Cp^*Ir)_3(_<μ3>-S)(_<μ2>-SH)_3]Cl has also been prepared, which has been found to be converted to a series of cubane-type Ir_3MS_4 dusters by incorporating certain M fragments.2. Sulfido-bridged dinudear complexes of Mo, W, and Re containing the MS(μ-S)_2MS cores have been converted to a variety of incomplete cubane-type and cubane-type mixed-metal sulfido dusters. It is to be noted that trimetallic cubanes are readily available from Re precursor by the stepwise addition of two different metal sources.3. Mixed-metal cubane-type Mo_2M_2S_4 dusters with oxo ligand (M=Ir, Rh) have been prepared, which have been found to catalyze the N-N bond cleaving reaction of methylphenylhydrazine in the presence of a proton source and reducing agent. Hydrazido duster as an intermediate stage of this nitrogenase model reaction has also been isolated and fully characterized.4. Sulfido-and thiolato-bridged In and Ir2Ru dusters have been prepared and their reactivities toward small molecules such as CO, isocyanide, and alkynes investigated. For the former Ir3 duster, its ability to catalyze highly stereoselective cydotrimerization of terminal alkyne has been demonstrated.