Syntheses of Chalcogenklo-Bridged Transition Metal Clusters

1.本文报道了以M（μ-EB）_2M（E=S，Se）为核的Ir，Rh和Ru的硫氢桥联和硒氢桥联双核配合物的合成，并通过二聚反应或与过渡金属化合物及主族金属化合物反应合成了多种硫族桥联的金属簇合物。所产生的尘埃的核数从3到7不等。还制备了三核硫硫醇合Ir [（Cp^*Ir）_3（_<μ3>-S）（_<μ2>-SH）_3]Cl簇合物，并发现该簇合物通过引入一定的M片段可转化为一系列立方烷型Ir_3MS_4簇合物.含MS（μ-S）_2MS核的Mo、W和Re的硫桥联双核配合物被转化为各种不完全立方烷型和立方烷型混合金属硫簇。应注意的是，三金属立方烷可通过逐步添加两种不同的金属源而容易地从Re前体获得。合成了含氧配体（M=Ir，Rh）的混合金属立方烷型Mo_2M_2S_4簇合物，发现其在质子源和还原剂存在下催化甲基苯肼的N-N键断裂反应。作为固氮酶模型反应中间阶段的肼基簇也被分离和充分表征.制备了硫代和硫醇基桥联的In和Ir_2Ru簇合物，并研究了它们对CO、异氰化物和炔等小分子的反应性。对于前者Ir 3催化剂，其催化末端炔的高度立体选择性环三聚的能力已被证明。

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.