Development of Functional Metal Complexes Having Active Oxygen Species Controlled by Coordination Sphere

该项目的目的是开发具有活性氧物种的金属络合物。为了合成这类配合物，我们开发了新的配位环境，在这个环境中，第一和第二配位球可以协同工作。酪氨酸酶和甲烷单加氧酶功能模型(μ-η^2：η^2-Peroxo)Cu(II)_2的合成：我们成功地合成了(μ-η^2：η^2-Peroxo)Cu(II)_2配合物[Cu2(O_2)(H-L)]^&lt；(氧基-H-1)，其中H-L=1，3-双[双(6-methyl-2-pyridylmethyl)aminomethyl]benzene，]，它不仅可以进行H-L间木基连接体的羟基化反应，还可以通过过氧化氢与C=C键的亲电加成反应进行苯乙烯的环氧化反应。此外，oxy-H-1还可以通过H原子的抽提氧化具有75-92kcal摩尔分子解离能(BDE)的各种脂肪族C-H键。二阶氧化速率常数logk与BDE之间存在线性相关关系。甲苯单加氧酶功能模型(μ-Peroxo)二铁(III)配合物的合成：我们成功地合成了两类过氧二铁(III)配合物：[Fe_2(LPh_4)(RCO_2)(O_2)]^&lt；(R=Ph_3C(氧基-L)和Ph(氧基-2))，前者导致LPh_4的苯基的区域选择性羟基化，后者表现出可逆的脱氧作用(LPh_4=N，N，N‘，N’-tetrakis[(1-methyl-2-phenyl-4-imidazolyl)methyl]-1，3-diamino-2-propanolate).这是第一个能够进行芳烃羟基化的过氧二铁(III)络合物的例子。这些反应分别模拟甲苯单加氧酶和氯氰菊酯的反应性。

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.