| Project/Area Number |
60430011
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | TOHOKU UNIVERSITY |
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Principal Investigator |
OGINO Hiroshi Dept. of Chem., Fac. of Sci., Tohoku Univ.・ Professor, 理学部, 教授 (00004292)
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| Co-Investigator(Kenkyū-buntansha) |
TOBITA Hiromi Dept. of Chem., Fac. of Sci., Tohoku Univ.・ Research Instructor, 理学部, 助手 (30180160)
SHIMURA Makoto Dept. of Chem., Fac. of Sci., Tohoku Univ.・ Research Instructor, 理学部, 助手 (00170994)
KABUTO Chizuko Dept. of Chem., Fac. of Sci., Tohoku Univ.・ Research Instructor, 理学部, 助手 (10089782)
SHIMOI Mamoru Dept. of Chem., Fac. of Sci., Tohoku Univ.・ Associate Professor, 理学部, 助教授 (30092240)
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| Project Period (FY) |
1985 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥27,000,000 (Direct Cost: ¥27,000,000)
Fiscal Year 1987: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1986: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1985: ¥21,000,000 (Direct Cost: ¥21,000,000)
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| Keywords | Metal Clusters / Cubane Type Clusters / Dinuclear Complexes / Trinuclear Clusters / Tetranuclear Clusters / Electron Transfer / Zeroth Order Rare Law / 不均化反応 / 混合金属クラスター / 三核錯体 / 鉄錯体 / コバルト錯体 / ジスルフィド配位子 / 銅錯体 / タングステン錯体 |
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| Research Abstract |
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.
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