Syntheses of Chalcogenklo-Bridged Transition Metal Clusters

Chalcogenklo桥过渡金属簇的合成

基本信息

批准号：
14078206
负责人：
MIZOBE Yasushi
金额：
$ 15.87万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

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.

1。在含有M（μ-EB）_2M核心（E = S，SE）的IR，RH和RU的新型Hydrosulfido和Hydroselenido桥接的Dinudear络合物已被分离出来，它们已被提供作为多功能预制的多功能前体，可通过多种多样的跨度briDIdo brided Contrient andition by-Mealo-Mealo-Mealo-Mealo-Mealo-Mealoters组合，并将其用于多样性的组合，并构成多样性的组合，并将其用于多样性的组合，并将其用于多样性的组合，并将其用于多样性的组合，并将其用于多样性的组合。以及主要的金属物种。产生的流浪者的核性从三到七个变化。还准备了IR的三核硫酸硫醇 - 硫醇[（cp^*ir）_3（_<μ3>-s）（_<μ2>-SH）_3] Cl也已准备好，已发现该Cl被发现转换为一系列Cubane型IR_3ms_4 Dusters，由某些M Fragments compand.2。 Mo，W和Re含有MS（μ-S）_2ms核心的硫桥式的Dinudear复合物已转换为多种不完整的古巴型和古巴型混合硫磺硫磺dusters。值得注意的是，通过逐步添加两个不同的金属源，可以从re precursor获得三金属古巴。3。已经制备了混合金属古巴型MO_2M_2S_2S_4带有Oxo配体（M = IR，RH）的Dusters，在存在质子源和还原剂的情况下，已经发现它们可以催化甲基苯基氢氮的N-N键裂解反应。 hidyazido duster作为该氮酶模型反应的中间阶段也已被分离并充分表征。4。已经制备了硫磺和硫醇桥接的硫酸和IR2RU的流浪者，并研究了它们对CO，Isocyanide和Alkynes等小分子的反应。对于以前的IR3 duster，已经证明了其催化高度立体选择性氧化氧化的能力。

项目成果

期刊论文数量（140）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

DFT Calculations of the Cubane-Type Mo_2Ru_2S_4 Clusters. Stability of the Possible Dinitrogen Cluster and the Isolable Acetonitrile Cluster

古巴烷型 Mo_2Ru_2S_4 团簇的 DFT 计算。

DOI：
发表时间：
2006
期刊：
Bull. Chem. Soc. Jpn. 79
影响因子：
0
作者：
P.;M.;Kozlowski;A.Staykov et al.;P.M.Kozlowski et al.;M.S.Seo et al.;K.Yoshizawa et al.;K.Yoshizawa et al.;K.Yoshizawa et al.;K.Yoshizawa et al.;T.Kamachi et al.;Y.Girard et al.;T.Yumura et al.;Y.Shiota et al.;K.Yoshizawa et al.
通讯作者：
K.Yoshizawa et al.

Preparation of Mononuclear and Dinuclear Rh Hydrotris(pyrazolyl)-borato Complexes Containing Arenethiolato Ligands

含芳硫醇配体的单核和双核 Rh 氢化三(吡唑基)-硼酸配合物的制备