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An Approach to Metal Cluster Chemistry

金属簇化学的一种方法

基本信息

批准号：
60430011
负责人：
OGINO Hiroshi
金额：
$ 17.28万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

项目摘要

1. Cubane type clusters [Cp_4Fe_4E_4]_n (E = S and Se, Cp = cyclopentadienyl). the title clusters were found to be oxidized electrochemically from n = 0 to 1+, 2+ 3+, and 4+. The crystal structure fo [Cp_4Fe_4Se_4](PF_6)_3・MeCN was determined.2. Clusters and dinuclear complexes containing substituted cyclopentadienyls. The reaction of [( ^5-(Me_3Si))C_5H_4)_2Fe_2(CO)_4] with S_8 gives higher complexes (clusters) than dinuclear one. On the other hand, the reaction of [( ^5-(Me_3Si)_2C_5H_3)_2Fe_2(CO)_4] with S_8 afforded a dinuclear complex [( ^5-(Me_3 Si)_2C_5H_3)_2Fe_2S_4] (D5wave_) as the main product. The X-ray crystal stucturs of__wave and related complexes were determined.3. Complexes containing trimethylene-bridged bis(permethylcyclopentadienyl) (Cp_2^<(3)>) [Cp_2^<(3)>Fe_2(CO)_4] ( ), [Cp_2_<(3)>Fe] ( ), and related complexes were prepared. The X-ray crystal structures of and thw two-electron oxidation product of were determined.4. Silylene-bridged dinuclear complexes and clusters. Novel title compounds were prepared. Among them, there is [Cp_2Fe_2(CO)_3(<mu>-SiHBu^t)].5. Synthesis of [Cu(B_<>H_4(PMe_3)_2)_<>]I. The title complex was prepared and structurally characterized. This is the first example of cationic Cu complexes containing boranes.6. Electron transfer reactions of W_<>Cl_9^<3-> with [CoX(NH_3)_5]. The title reactions were investigated kinetically. Under some condition, the reactions obeyed zeroth-order rate law. A plausible mechanism was proposed for the reactions.

1.立方烷型团簇[Cp_4Fe_4E_4]_n（E = S和Se，Cp = Fe）。发现标题簇从n = 0电化学氧化为1+、2+、3+和4+。测定了[Cp_4Fe_4Se_4]（PF_6）_3·MeCN的晶体结构.含有取代环戊二烯基的簇合物和双核配合物。[（^5-（Me_3Si））C_5H_4）_2Fe_2（CO）_4]与S_8的反应生成的配合物（簇合物）比双核配合物（簇合物）高。另一方面，[（^5-（Me_3Si）_2C_5H_3）_2Fe_2（CO）_4]与S_8反应，主要产物为双核配合物[（^5-（Me_3Si）_2C_5H_3）_2Fe_2S_4]（D5波）。测定了__波及其配合物的X射线晶体结构.合成了含三亚甲基桥连的双（全甲撑）（Cp_2 ^<（3）>）[Cp_2^<（3）>Fe_2（CO）_4]（）、[Cp_2_<（3）>Fe]（）及相关配合物。并测定了其双电子氧化产物的X射线晶体结构.亚硅桥双核配合物和簇合物。合成了新的标题化合物。其中有[Cp_2Fe_2（CO）_3（<mu>-SiHBu^t）]。[Cu（B_<>H_4（PMe_3）_2）_<>]的合成I.标题配合物的制备和结构表征。这是含硼烷的阳离子Cu络合物的第一个实例。W_<>Cl_9 ~* <3->与[考克斯（NH_3）_5]的电子转移反应对反应进行了动力学研究。在一定条件下，反应服从零级速率定律。提出了一个合理的反应机理。