| Project/Area Number |
12640536
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | KANAZAWA UNIVERSITY |
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Principal Investigator |
SUZUKI Masatatsu KANAZAWA UNIVERSITY, Department of Chemistry, Faculty of Science, Professor of Chemistry, 理学部, 教授 (20091390)
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| Co-Investigator(Kenkyū-buntansha) |
FUJINAMI Schuhei KANAZAWA UNIVERSITY, Department of Chemistry, Faculty of Science, Reserch Associate of Chemistry, 理学部, 助手 (10115272)
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| Project Period (FY) |
2000 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2001: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
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| Keywords | Heterodimital complexes / Magnetism / Ferromagnetic interaction / Crystallography / Didopeer(III)complex / Monooxyganse / Activation of dioxygen / Oxidation reaction / (μ-oxo)(μ-hydroxo)Fe_2(III) / (μ-oxo)(μ-peroxo)Fe_2(III) / (μ-hydroxo)(μ-peroxo)Fe_2(III) / 二核μ-peroxo鉄錯体 / メスバウアースペクトル / 共鳴ラマンスペクトル / 二核非ヘム鉄 |
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| Research Abstract |
The purpose of this research project is development of highly functionalized di-and polynuclear metal complexes by controlling the nature of the coordination environment around metal ions.
Control of Magnetic interaction of heterbdinuclear meatl complexes : A series of heterodinuclear bis(μ-hydroxo)Cr(III)Ni(II) complexes, [(phen)_2Cr(μ-OH)_2Ni(Me_n-tpa)](ClO_4)_3, with sterically bulky tpa (tris(2 pyridylmethyl)amine) derivatives having 6-methyl group(s) (n = 0 - 3) was prepared. Introduction of the 6 methyl group(s) onto the pyridyl group(s) results in systematic elongation of the Ni-N bond distances, leading to the systematic magnetic interaction change from weak antiferromagnetic interaction to relatively strong ferromagnetic interaction. This can be interpreted in terms of lie lowering of the d-orbital energies on the nickel centers, which leads to a decrease of the antiferromagnetic contribution. The present results shows that the magnetic interaction-can be controlled by the d-orbital energies of the. Metal ions by modifying the coordination environments.
Control of dioxygen reactivity of cbppef(I) complexes : A copper(I) complex ([Cu(L)]^+) having a tripodal tetradentate ligand (bis(6-methyl-2-pyridylmethyl)(2-pyridylethyl)amine) reacted with dioxygen at -80℃ to genertate a bis(μ-oxo)dicopper(III) complex whose structure was determined by X-ray crystallography. The bis(μ-oxo)dicopper(III) complex showed a reversible conversion with a precursor copper (I) complex by bubbling N_2 gas at -80 - 55℃ and also showed a monooxygenase activity for the supporting ligand at higher temperature. Such reversible 4 electron reduction and oxidation of between O_2 and O^<2-> is of particular importance for dioxygen activation and water oxidation chemistry.
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