Development of Functional Metal Complexes Having Active Oxygen Species Controlled by Coordination Sphere
配位球控制活性氧的功能金属配合物的开发
基本信息
- 批准号:16074206
- 负责人:
- 金额:$ 7.36万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research on Priority Areas
- 财政年份:2004
- 资助国家:日本
- 起止时间:2004 至 2007
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
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.
本项目的目的是开发具有活性氧的金属络合物。为了合成这样的配合物,我们开发了新的配位环境,其中第一和第二配位球可以协同工作。(μ-η^2:η^2-过氧)Cu(II)_2配合物的合成:我们成功地合成了(μ-η^2:η^2-过氧)Cu(II)_2配合物[Cu_2(O_2)(H-L)]^<2+>(oxy-H-1),其中H-L = 1,3-bis [bis(6-methyl-2-pyridylmethyl)aminomethyl]benzene,它不仅可以羟基化H-L的间二甲苯基连接基团,而且可以通过过氧化物亲电加成到C=C键上来环氧化苯乙烯。此外,氧-H-1可以通过H原子夺取氧化具有键离解能(BDE)75 - 92 kcal mol/L的各种脂肪族C-H键<-1>。氧化二级速率常数log k与BDE呈线性相关.合成(μ-过氧)二铁(III)复合物作为甲苯单加氧酶的功能模型:我们成功地合成了两种过氧二铁配合物[Fe_2(LPh_4)(RCO_2)(O_2)]^<2+>(R = Ph_3C(氧基-1)和Ph(氧基-2)),前者导致LPh 4的苯基的区域选择性羟基化,而后者表现出可逆脱氧(LPh 4 = N,N,N ',N'-四[(1-甲基-2-苯基-4-咪唑基)甲基]-1,3-二氨基-2-丙醇盐)。这是能够进行芳烃羟基化的过氧二铁(III)络合物的第一个实例。反应分别模拟甲苯单加氧酶和血红蛋白反应性。
项目成果
期刊论文数量(80)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Reversible Dioxygen Binding vs Arene Hydroxylation Mediated by Peroxo-diiron(III)Complexes
可逆双氧结合与过氧化二铁 (III) 配合物介导的芳烃羟基化
- DOI:
- 发表时间:2007
- 期刊:
- 影响因子:0
- 作者:Malaviarachchi. S. P. K.;Makishima;A.;Tanimoto. M.;Kuritani. T.;Nakamura E.;秋山隆彦;M.Suzuki
- 通讯作者:M.Suzuki
Structural and Spectroscopic Characterization of (μ-Hydroxo or μ-oxo)(μ-Peroxo)diiron(III) Complexes : Models for Peroxo Intermediates of Non-Heme Diiron Proteins
(μ-Hydroxo 或 μ-oxo)(μ-Peroxo)diiron(III) 配合物的结构和光谱表征:非血红素二铁蛋白的 Peroxo 中间体模型
- DOI:
- 发表时间:2005
- 期刊:
- 影响因子:0
- 作者:X.Zhang;H.Furutachi;S.Fujinami;S.Nagatomo;Y.Maeda;Y.Watanabe;T.Kitagawa;M.Suzuki
- 通讯作者:M.Suzuki
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SUZUKI Masatatsu其他文献
SUZUKI Masatatsu的其他文献
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{{ truncateString('SUZUKI Masatatsu', 18)}}的其他基金
Syntheses of Dimetal Complexes Capable of Oxidizing Alkanes and Arenes
能够氧化烷烃和芳烃的双金属配合物的合成
- 批准号:
22350027 - 财政年份:2010
- 资助金额:
$ 7.36万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of metal complexes having active oxygen species by controlling of reaction cavity
通过控制反应腔开发具有活性氧的金属配合物
- 批准号:
19350029 - 财政年份:2007
- 资助金额:
$ 7.36万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of Highly Functionalized Dimetal Complexes
高功能化双金属配合物的开发
- 批准号:
12640536 - 财政年份:2000
- 资助金额:
$ 7.36万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Investigations of dioxygen activation mechanisms by dimetal complexes
双金属配合物双氧活化机制的研究
- 批准号:
11228202 - 财政年份:1999
- 资助金额:
$ 7.36万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Functionalization of Dimetal Complexes by Ligand Design
通过配体设计对双金属配合物进行功能化
- 批准号:
10640540 - 财政年份:1998
- 资助金额:
$ 7.36万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Syntheses and Reactivity of Diiorn-, Dicobalt-, and Dicopper-Dioxygen Complexes
Diiorn-、二钴-和二铜-双氧配合物的合成和反应性
- 批准号:
07454175 - 财政年份:1995
- 资助金额:
$ 7.36万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
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