| Project/Area Number |
16074206
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Kanazawa University |
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Principal Investigator |
SUZUKI Masatatsu Kanazawa University, Graduate School of Natural Science and Technology, Division of Material Sciences, Professor (20091390)
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| Co-Investigator(Kenkyū-buntansha) |
FUJINAMI Shuhei , Associate Professor (10115272)
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| Project Period (FY) |
2004 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥11,500,000 (Direct Cost: ¥11,500,000)
Fiscal Year 2007: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2006: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2005: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2004: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | Coordination Sphere / Synthetic Chemistry / Diron(III)-Peroxo Complexes / Dicopper(II)-Peroxo Complexes / Dioxygen Activation / Hydroxylation Reactions / Models for Toluene monooxygenase / Models for Methane monooxygenase / 二核鉄(III)ペルオキソ錯体 / C-H結合の活性化 / アレン水酸化 / 二核鉄(II)ペルオキソ錯体 / チロシナーゼモデル / 銅酸素錯体 / 酸化反応 / エポキシ化 / 金属酵素モデル / エポキシ化反応 / Toluene monoxoygenase / 生物無機化学 |
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| Research Abstract |
The purpose of this project is the development of metal complexes having active-oxygen species. In order to syntheses such complexes, we have developed new coordination environments, where the first and second coordination spheres can cooperatively function.
1. Synthesis of (μ-η^2:η^2-Peroxo)Cu(II)_2 Complexes as Functional Models for Tyrosinase and Methane Monooxygenase: We have succeeded in synthesis of (μ-η^2:η^2-peroxo)Cu(II)_2 complexes, [Cu_2(O_2) (H-L)]^<2+> (oxy-H-1), where H-L = 1, 3-bis [bis (6-methyl-2-pyridylmethyl)aminomethyl]benzene, which can perform not only hydroxylation of the m-xylyl linker of H-L, but also epoxidation of styrene via an electrophilic addition of the peroxide to the C=C bond. In addition, oxy-H-1 can oxidize various aliphatic C-H bonds having the bond dissociation energies (BDE) 75 - 92 kcal mol^<-1> via H-atom abstraction. A linear correlation between log k (the second order rate constants of oxidation) and BDE was observed.
2. Synthesis of (μ-Peroxo)diiron (III) Complex as a Functional Model for Toluene Monooxygenase: We have succeeded in synthesis of two types of peroxodiiron (III) complexes, [Fe_2(LPh4) (RCO_2) (O_2)]^<2+> (R = Ph_3C (oxy-l) and Ph (oxy-2)), the former leads to regioselective hydroxylation of a phenyl group of LPh4 and the latter exhibits reversible deoxygenation (LPh4 = N,N,N',N'-tetrakis[(1-methyl-2-phenyl-4-imidazolyl)methyl]-1,3-diamino-2-propanolate). This is the first example of the peroxodiiron (III) complex which is capable of arene hydroxylation. The reactions mimic toluene monooxygenase and hemerythrin reactivity, respectively.
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