| Project/Area Number |
07454175
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 Faculty of Science, Kanazawa University, Professor of Chemistry., 理学部, 教授 (20091390)
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| Co-Investigator(Kenkyū-buntansha) |
FUJINAMI Shuhei Faculty of Science, Kanazawa University, Assistant Professor of Chemistry., 理学部, 助手 (10115272)
UEHARA Akira Faculty of Science, Kanazawa University, Professor of Chemistry., 理学部, 教授 (30019484)
林 宣仁 金沢大学, 理学部, 助手 (10231531)
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| Project Period (FY) |
1995 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥7,600,000 (Direct Cost: ¥7,600,000)
Fiscal Year 1997: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1996: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1995: ¥5,300,000 (Direct Cost: ¥5,300,000)
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| Keywords | Diiron-Dioxygen Complexes / Dicopper-Dioxygen Complexes / Dioxygen Affinity / Crystal Structures / Reversible Oxygenation / Equilibrium / Thermodynamic Parameters / 二核鉄錯体 / 二核鉄酸素錯体の結晶構造 / 生物無機化学 / 非ヘム鉄 / 酸素化 / 酸化反応 / 熱的安定性 / 非ヘムタンパクモデル錯体 / ヘムエリスリンモデル錯体 |
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| Research Abstract |
Diiron-dioxygen and dicopper-dioxygen complexes play an important role in the reversible binding and activation of O_2 in biological and catalytic processes. We developed various diiron (II) and dicopper (I) complexes as functional models for O_2 transport proteins such as Hemerythrin (Fe_2) and hemocyanin (Cu_2) and mono-oxygenase such as methane monooxygenases (Fe_2 or Cu_n).
Diiron Complexes : Only a few structurally and spectroscopically characterized diiron-dioxygen complexes have been reported. In order to synthesize the diiron-dioxygen complexes, it is important to control the ligand environment which is suitable for O_2 binding by two iron ions and stabilizes the mu-peroxo species toward irreversible oxidation. For this purpose, a series of dinucleating ligands with sterically hindered pyridyl and imidazolyl groups has been developed, which has an N_6O donor set with a phenolate or alkoxide bridging group. They form five-coordinate dinuclear [Fe_2 (L) (RCO_2)]^<2+> with an exoge
… More
nous carboxylate bridge, which react with O_2 to form mu-peroxo species. It was found that thermal stability toward irreversible oxidation and dioxygen affinity of those complexes are highly dependent on the stereochemistry and the electron donor ability of dinucleating ligands and bridging carboxylate. Finally we have succeeded in preparation and structural characterization of a cis-mu-1,2-peroxo diiron complex which is the first example of a crystallographically characterized diiron-dioxygen complex that binds O_2 reversibly at ambient temperature.
Dicopper Complexes : A series of copper (I) complexes ([Cu (L)]^+) having tripodal tetradentate ligands ((R_1R_2NCH_2CH_2)_3N : L) was synthesized. Reactivity of those complexes with O_2 was investigated. They form trans-mu-1,2-peroxo species at low temperature. It was found that stereochemistry and thermal stability of dioxygen complexes are highly dependent on the steric bulkiness of substituents (R). We have succeeded in structural characterization of a trans-mu-1,2-peroxo species ([Cu ((BnHNCH_2CH_2)_3N)]_2 (O_2)), where benzyl (Bn) groups form a cavity around Cu^<2+>-O_2^<2->-Cu^<2+> moiety, which stabilizes peroxo species. Less
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