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。古巴类型簇[CP_4FE_4E_4] _n（e = s and se，cp = cyclopentadienyl）。发现标题簇从n = 0到1+，2+ 3+和4+的电化学氧化。确定了MECN的晶体结构fo [CP_4FE_4SE_4]（PF_6）_3・MECN.2。簇和含有取代环戊烯基的群集。 [（ ^5-（ME_3SI））C_5H_4）_2FE_2（CO）_4]对S_8的反应比Dinuclear的反应给出了更高的复合物（簇）。另一方面，[（ ^5-（ME_3SI）_2C_5H_3）_2FE_2（CO）_4]与S_8的反应提供了一个双核综合体[（ ^5-（me_3 si）_2C_5H_3）_2fe_2s_2s_4]（d5Wave_4]（d5wave_）（d5wave_）（d5wave_）（主要产品）。确定了__波和相关复合物的X射线晶体柱。3。含有三甲基桥的双Bis（氯甲基环戊二烯）（CP_2^<（3）>）[CP_2^<（3）> Fe_2（CO）_4]（），[CP_2 _2 _2 _2 _2 _ <（3）> Fe]> Fe]（Fe]> Fe]（））和相关复合物。确定了两种氧化物产物的X射线晶体结构。4。甲硅烷基桥梁的可核综合体和簇。准备了新颖的标题化合物。其中，有[CP_2FE_2（CO）_3（<mu> -sihbu^t）]。 [Cu（B _ <> H_4（PME_3）_2）_ <>] i的合成。制备标题复合体并在结构上表征。这是含有硼烷的阳离子铜配合物的第一个例子。6。 w _ <> cl_9^<3->的电子传输反应与[Cox（NH_3）_5]。标题反应进行了动力学研究。在某种情况下，这些反应遵守了零级率定律。提出了针对反应的合理机制。