Syntheses of Chalcogenklo-Bridged Transition Metal Clusters

1. 以M(μ-EB)_2M为核心（E=S, Se）的新型氢硫代和氢硒代桥接Ir、Rh和Ru双核配合物被分离出来，通过二聚化或与某些过渡金属化合物及主要基团金属处理，可以作为合成各种硫原代桥接的均金属和杂金属簇的多功能前驱体。所生产的粉尘的核数从3到7不等。本文还制备了Ir [(Cp^*Ir)_3(_<μ3>-S)(_<μ2>-SH)_3]Cl的三核硫代硫代粉尘，发现加入一定量的M片段后，该粉尘可转化为一系列的古巴型Ir_3MS_4粉尘。含有MS(μ-S)_2MS核的Mo、W和Re的硫化桥接二元配合物转化为各种不完全立方型和立方型混合金属硫粉尘。值得注意的是，通过逐步加入两种不同的金属源，可以很容易地从稀土前驱体中得到三金属立方烷。制备了含氧配体（M=Ir, Rh）的混合金属cubane型Mo_2M_2S_4粉尘，在质子源和还原剂存在下催化甲基苯基肼的N-N键裂解反应。作为该模型反应中间阶段的肼粉尘也得到了分离和充分表征。制备了硫代和硫代桥接的In和Ir2Ru粉尘，并研究了它们对CO、异氰化物和炔烃等小分子的反应性。对于前Ir3除尘器，其催化末端炔的高度立体选择性细胞三聚化的能力已被证明。

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.