An Approach to Metal Cluster Chemistry

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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.