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Synthesis of metal complexes to clarify mechanism of O_2-activation by non-heme metalloproteins

合成金属配合物以阐明非血红素金属蛋白激活 O_2 的机制

基本信息

批准号：
11640572
负责人：
KODERA Masahito
金额：
$ 2.3万
依托单位：
Doshisha University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

Various hexapyridine dinucleating ligands and their dicopper complexes have been synthesized to obtain functional models to mimic the reversible O_2-binding and O_2-activation of type III copper proteins. On the basis of reactions and structures of the copper complexes, it is shown that the reaction of μ-η^2 : η^2-peroxodicopper complex as an active species of the type III proteins is directed by various factors, such as the Cu coordination geometry, the orientation of two Cu ions, the Cu-Cu distance, and the electronic effect of the nitrogen donor ligands. Furthermore, it is suggested that the Cu-Cu distance and the distortion of the Cu coordination geometry may be important in controlling the reversible O_2-binding of the μ-η^2 : η^2-peroxodicopper complex.A thermally stable (μ-1, 2-peroxo) diiron (III) complex [Fe_2 (O_2)(O)(OAc)(L)](CF_3SO_3)(2){L : 1, 2-bis [2-(bis (2-pyridyl) methyl)-6-pyridyl]ethane} were isolated from the reaction of [Fe_2 (O)(OAc)_2 (L)](CF_3SO_3)_2 (1b) with H_2O_2 in MeCN in the presence of Et_3N.Compound 2 was characterized by elemental analysis, FAB MS, elctronic absorption, resonance Raman, and Mossbauer spectra. The spontaneous decomposition of 2 in MeCN monitored at 605 nm obeys good first-order kinetics with k=2.5x10^<-5> s^<-1> at 300 K (the half-life time τ_<1/2>=7.7 h), demonstrating that 2 is thermally stable. Upon addition of RCOCl (R=m-ClC_6H_4, CH_3, and CCl_3) in the presence of DMF (or DMA), 2 is activated to monooxygenate cyclohexene and cyclohexane to the corresponding alcohols and ketones.

合成了各种六吡啶二核配体及其二铜配合物，以获得模拟 III 型铜蛋白的可逆 O_2 结合和 O_2 激活的功能模型。在铜配合物的反应和结构的基础上，表明μ-η^2：η^2-过氧二铜配合物作为III型蛋白的活性物质，其反应受到多种因素的指导，例如Cu配位几何形状、两个Cu离子的方向、Cu-Cu距离和氮供体配体的电子效应。此外，有人认为Cu-Cu距离和Cu配位几何形状的畸变对于控制μ-η^2：η^2-peroxodicopper络合物的可逆O_2结合可能很重要。一种热稳定的(μ-1, 2-peroxo)二铁(III)络合物[Fe_2 [Fe_2(O)(OAc)_2(L)](CF_3SO_3)(2){L : 1, 2-双[2-(双(2-吡啶基)甲基)-6-吡啶基]乙烷}由[Fe_2(O)(OAc)_2(L)](CF_3SO_3)_2(1b)与H_2O_2在MeCN中的反应分离得到 Et_3N.Compound 2 的存在通过元素分析、FAB MS、电子吸收、共振拉曼和穆斯堡尔光谱进行表征。在605 nm处监测到的MeCN中2的自发分解在300 K下遵循良好的一级动力学，k=2.5x10^<-5> s^<-1>（半衰期τ_<1/2>=7.7 h），表明2是热稳定的。在DMF（或DMA）存在下添加RCOCl（R=m-ClC_6H_4、CH_3和CCl_3）后，2被活化，将环己烯和环己烷单氧化成相应的醇和酮。