| Budget Amount *help |
¥15,700,000 (Direct Cost: ¥15,700,000)
Fiscal Year 2006: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2005: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2004: ¥8,500,000 (Direct Cost: ¥8,500,000)
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| Research Abstract |
The purpose of this project is the development of the peroxo-dicopper(II) and diiron(III) complexes as functional models for tyrosinase and toluene monooxygenase.
We have succeeded in synthesis of (μη^2:η^2-peroxo)Cu(II)_2 complexes, [Cu_2(O_2)(R-L)]^<2+> (oxy-R-1: R = H, MeO, t-Bu, and NO_2), where R-L = 1,3-Bis[bis(6-methyl-2pyridylmethyl)aminomethy1]-5-R-benzene, which can perform not only hydroxylation of the m-xylyl linker of R-L, but also epoxidation of styrene via an electrophilic addition of the peroxide to the C=C bond, the latter of which is the first example of the epoxidation of styrene by a discrete (μη^2:η^2-peroxo)Cu(II)_2 species. In addition, oxy-H-1 can oxidize various aliphatic C-H bonds via H-atom abstraction. A linear correlation between log k (the second order rate constants of oxidation) and the bond dissociation energies of the C-H bonds was observed. The results provide new insights into the reactivity of (μη^2:η^2 peroxo) Cu(II)_2 complexes.
(μ-Peroxo)diiron(III) Complex: A Functional Model for Toluene Monooxygenase. We have succeeded in synthesis of two types of peroxodiiron(III) complexes, [Fe2(L^<Ph4>)(RCO_2)(O_2)]^<2+> (R = Ph_3C (oxy-1) and Ph (oxy-2)), the former leads to regioselective hydroxylation of a phenyl group of L^<Ph4> and the latter exhibits reversible deoxygenation (L^<Ph4> = N, N, N',N'-tetrakis[(1-methyl-2-pheny1-4-imidazolyl)methy1]-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. They provide new insights into the reactivity of the peroxodiiron(III) complexes having a nitrogen-rich coordination environment like alkane arhydroxylase and hemerythrin.
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