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

基本信息

批准号：
10640540
负责人：
SUZUKI Masatatsu
金额：
$ 2.37万
依托单位：
KANAZAWA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

Diiron-dioxygen and dicopper-dioxygen complexes play an important role in the reversible binding and activation of 0ィイD22ィエD2 in biological and catalytic processes. We developed various diiron(II) and dicopper(I) complexes as functional models for 0ィイD22ィエD2 transport proteins such as Hemerythrin (FeィイD22ィエD2) and hemocyanin (CuィイD22ィエD2) and monooxygenase such as methane monooxygenases (FeィイD22ィエD2 or CuィイD2nィエD2).Diiron Complexes : We have tried to control the thermal stability of μ-peroxo diiron(III) complexes against the irreversible oxidation and the dioxygen affinity of diiron(II) complexes by a series of dinucleating ligands. It was found that thermal stability toward irreversible oxidation and dioxygen affinity of those complexes are highly dependent on the stereochemistry and the electron donor ability of dinucleating ligands and bridging carboxylate. Finally we have succeeded in preparation and structural characterization of a cis-μ-l,2-peroxo diiron complex that binds 0ィイD22ィエD2 reversibly at ambient temperature.Dicopper Complexes : A series of copper(I) complexes ([Cu(L)]ィイD1+ィエD1) having tripodal tetradentate ligands (L) was synthesized and reactivity of their complexes with 0ィイD22ィエD2 was investigated. It was found that the nature and stereochemistry of the tripod ligands influence the formation, structures, and reactivity of copper-dioxygen complexes. We have succeeded in preparation of superoxocopper(II), μ-peroxodicopper(II), and bis(μ-oxo)dicopper(III) complexes. The bis(μ-oxo)dicopper(III) complex showed a monooxygenase activity for the coordinated ligand and also showed the reversible conversion with a precursor copper (I) complex by bubbling NィイD22ィエD2 gas. This is the first example which exhibit reversible conversion between bis(μ-oxo)dicopper(III) and copper(I) complexes.

二铁-二氧和二铜-二氧复合物在生物和催化过程中 D22 的可逆结合和激活中发挥着重要作用。我们开发了各种二铁 (II) 和二铜 (I) 复合物作为 0 D22D2 转运蛋白（如血红蛋白）的功能模型。 (FeD22D2) 和血蓝蛋白（CuiD22iD2）和单加氧酶，例如甲烷单加氧酶（FeiiD22iD2 或 CuiiD2niiD2）。 Diiron 配合物：我们尝试通过以下方法控制 μ-peroxo diiron( III) 配合物的热稳定性，以防止不可逆氧化和 Diiron (II) 配合物的双氧亲和力发现一系列双核配体。这些配合物的不可逆氧化热稳定性和双氧亲和力高度依赖于双核配体和桥连羧酸酯的立体化学和电子供体能力。在环境温度下可逆结合的复合物。二铜复合物：一系列铜 (I) 复合物合成了具有三足四齿配体(L)的([Cu(L)]D1+D1)，并研究了它们与D22的配合物的反应性。结果发现，三足配体的性质和立体化学影响其形成、结构和反应性。我们成功制备了超氧铜(II)、μ-过氧二铜(II)和双(μ-氧代)二铜(III)络合物双(μ-氧代)二铜(III)络合物对配位配体表现出单加氧酶活性，并且还通过鼓泡ND22表现出与前体铜(I)络合物的可逆转化。这是第一个在双(μ-氧代)二铜(III) 和铜(I) 络合物之间表现出可逆转化的例子。