| Project/Area Number |
04453044
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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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 | Tokyo Institute of Technology |
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Principal Investigator |
KITAJIMA Nobumasa Tokyo Institute of Technology, Research Laboratory of Resources Utilization, Associate Professor, 資源化学研究所, 助教授 (20177843)
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| Co-Investigator(Kenkyū-buntansha) |
穐田 宗隆 東京工業大学, 資源化学研究所, 助手 (50167839)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1993: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1992: ¥4,300,000 (Direct Cost: ¥4,300,000)
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| Keywords | Dioxygen Complex / Peroxide / Dinuclear Metal Complex / Enzyme Model / Hydroxo Dinulear Complex / Pyrazolylborate / Monooxygenase Reation / Transtion Metal Complex / 酸素錯体 / 酸素モデル / 酸素添加反応 / ピラジリルボレート |
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| Research Abstract |
In order to clarify the effects of ligand donors, geometry and central metal on the rectivity of peroxo complexes, a series of transition metal peroxo complexes have been synthesized with a hindered tripodal ligand L = hydrotris(3,5-diisopropyl-1-pyrazolyl)borate. Because of thermal instability of the resulting peroxo complexes, we have focused on strucutural characterization of the products formed by H_2O_2 treatment of bis(mu-hydroxo) complexes LCu(OH)_2CuL,LNi(OH)_2NiL,LCo(OH)_2CoL and LMn(OH)_2MnL.The mu-eta^2 : eta^2-peroxo complex of copper which we reported to be formed by the reaction of H_2O_2 and LCu(OH)_2CuL.The detailed spectral exploration on the electronic structure of this unique peroxo complex has been undertaken. When LNi(OH)_2NiL was treated with H_2O_2 at low temperature and warmed to room temperature, oxidative dehydrogenation of methyl group in L was found to occur. On the other hand, the similar reaction between LCo(OH)_2CoL and H_2O_2 causes hydroxylation of methine CH bond of the isopropyl groups ; the crystal structures of two isolated products have been determined. Finally, the reaction between LMn(OH)_2MnL and H_2O_2 in the presence of pyrazole gave a novel monomeric side-on peroxo complex LMn(O_2)(HPz). Thus, a variety of peroxo complexes have been successfully synthesized and their reactivities have been elucidated.
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