| Project/Area Number |
02403012
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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 | Yamagata University |
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Principal Investigator |
NISHIDA Yuzo Yamagata University Department of Chemistry Professor, 理学部, 教授 (10037244)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥22,000,000 (Direct Cost: ¥22,000,000)
Fiscal Year 1991: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1990: ¥19,000,000 (Direct Cost: ¥19,000,000)
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| Keywords | activation of dioxygen / metal compounds / d-orbital and dioxygen molecule / dー軌道と酸素分子 / dー軌道と酵素反応 |
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| Research Abstract |
There has been much recent interest in the interpretation of the mechanism of activation of molecular dioxygen by metal complexes. Although many reports have been published on this problem, the most important point remains unsolved ; why and how dioxygen molecule reacts with organic compound in the presence of a metal complex catalyst? In this study we have investigated many oxygenation reactions catalyzed by metal ion, and confirmed that some specific d-orbitals are playing a very important role in these reactions.
(1) some oxovanadium(IV) compounds exhibit high SOD-like function (decomposition of superoxide anion), whereas some vanadium(IV) compounds do not. The electrochemical, spectroscopic, and ESR data have revealed that the presence of the d-orbital whose lobes are not completely screened by the ligand system is necessary for the appearance of SOD-like function, and the results observed for the Fe(III) and Mn(II) compounds are also supporting the above discussion.
(2) several binuclear Fe(III) compounds react with hydrogen peroxide to yield a peroxide aduct. In this study we have observed that the reactivity of the peroxide adduct is highly dependent on the compound used ; the peroxide adduct of Fe(III) with H(HPTP) is highly reactive, whereas the activity of the corresponding Fe(III) with H_5 (L-pac) is much lower. The origin for the above fact can be elucidated by the similar discussion developed in (1).
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