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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.古巴烷型簇[Cp_4Fe_4E_4]_n（E = S和Se，Cp =环戊二烯基）。发现标题簇被电化学氧化，从 n = 0 到 1+、2+、3+ 和 4+。确定了[Cp_4Fe_4Se_4](PF_6)_3·MeCN的晶体结构。 2．含有取代环戊二烯基的簇和双核络合物。 [( ^5-(Me_3Si))C_5H_4)_2Fe_2(CO)_4] 与 S_8 的反应产生比双核复合物更高的复合物（簇）。另一方面，[(^5-(Me_3Si)_2C_5H_3)_2Fe_2(CO)_4]与S_8反应得到双核配合物[(^5-(Me_3 Si)_2C_5H_3)_2Fe_2S_4](D5wave_)作为主要产物。测定了__波及相关配合物的X射线晶体结构。 3．制备了含有三亚甲基桥联双(全甲基环戊二烯基)(Cp_2^<(3)>)[Cp_2^<(3)>Fe_2(CO)_4]( )、[Cp_2_<(3)>Fe]( )的配合物以及相关配合物。测定了X射线晶体结构和双电子氧化产物的X射线晶体结构。 4．亚硅基桥联的双核配合物和簇。制备了新的标题化合物。其中，有[Cp_2Fe_2(CO)_3(<mu>-SiHBu^t)].5。 [Cu(B_<>H_4(PMe_3)_2)_<>]I 的合成。制备了标题配合物并进行了结构表征。这是含硼烷的阳离子铜配合物的第一个例子。6． W_<>Cl_9^<3->与[CoX(NH_3)_5]的电子转移反应。对标题反应进行了动力学研究。在一定条件下，反应遵循零级速率定律。提出了该反应的合理机制。