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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.

双铁-双氧和双铜-双氧配合物在生物和催化过程中对0-羟基D22-羟基D2的可逆结合和活化起着重要作用。我们开发了各种二铁（II）和二铜（I）络合物作为0 - 20-D22-D2转运蛋白（如血红蛋白）的功能模型（Fe γ D22 γ D2）和血蓝蛋白（Cu单加氧酶D22）和单加氧酶如甲烷单加氧酶（Fe D22 D2或Cu D2 n D2）。二铁络合物：我们试图通过一系列双核配体来控制μ-过氧二铁（III）配合物对不可逆氧化的热稳定性和二铁（II）配合物的双氧亲和力。研究发现，这些配合物的不可逆氧化热稳定性和分子氧亲和力高度依赖于双核配体和桥连羧酸盐的立体化学和电子给体能力。合成了一系列具有三足四齿配体（L）的铜（I）配合物（[Cu（L）]配位D1+[Cu（L）]配位D1），并研究了它们与0-[Cu（L）]配位D2的反应性。结果发现，三脚架配体的性质和立体化学影响铜-二氧配合物的形成，结构和反应性。我们成功地制备了超氧代铜（II）、μ-过氧代二铜（II）和双（μ-氧代）二铜（III）配合物。双（μ-氧代）二铜（III）配合物对配位体表现出单加氧酶活性，并且通过鼓泡NH_2D_2D_2气体与前体铜（I）配合物表现出可逆转化。这是第一个表现出双（μ-氧代）二铜（III）和铜（I）络合物之间可逆转化的实施例。