Development of Highly Functionalized Dimetal Complexes

高功能化双金属配合物的开发

• 批准号: 12640536
• 负责人: SUZUKI Masatatsu
• 金额: $ 2.3万
• 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: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640536/
• 关键词: Heterodimital complexes; Magnetism; Ferromagnetic interaction; Crystallography; Didopeer(III)complex; Monooxyganse; Activation of dioxygen; Oxidation reaction; (μ-oxo)(μ-hydroxo)Fe_2(III); (μ-oxo)(μ-peroxo)Fe_2(III); (μ-hydroxo)(μ-peroxo)Fe_2(II

The purpose of this research project is development of highly functionalized di-and polynuclear metal complexes by controlling the nature of the coordination environment around metal ions.Control of Magnetic interaction of heterbdinuclear meatl complexes : A series of heterodinuclear bis(μ-hydroxo)Cr(III)Ni(II) complexes, [(phen)_2Cr(μ-OH)_2Ni(Me_n-tpa)](ClO_4)_3, with sterically bulky tpa (tris(2 pyridylmethyl)amine) derivatives having 6-methyl group(s) (n = 0 - 3) was prepared. Introduction of the 6 methyl group(s) onto the pyridyl group(s) results in systematic elongation of the Ni-N bond distances, leading to the systematic magnetic interaction change from weak antiferromagnetic interaction to relatively strong ferromagnetic interaction. This can be interpreted in terms of lie lowering of the d-orbital energies on the nickel centers, which leads to a decrease of the antiferromagnetic contribution. The present results shows that the magnetic interaction-can be controlled by the d-orbital energies of the. Metal ions by modifying the coordination environments.Control of dioxygen reactivity of cbppef(I) complexes : A copper(I) complex ([Cu(L)]^+) having a tripodal tetradentate ligand (bis(6-methyl-2-pyridylmethyl)(2-pyridylethyl)amine) reacted with dioxygen at -80℃ to genertate a bis(μ-oxo)dicopper(III) complex whose structure was determined by X-ray crystallography. The bis(μ-oxo)dicopper(III) complex showed a reversible conversion with a precursor copper (I) complex by bubbling N_2 gas at -80 - 55℃ and also showed a monooxygenase activity for the supporting ligand at higher temperature. Such reversible 4 electron reduction and oxidation of between O_2 and O^<2-> is of particular importance for dioxygen activation and water oxidation chemistry.

本研究课题的目的是通过控制金属离子周围配位环境的性质来开发高度功能化的双核和多核金属配合物。异双核金属配合物的磁相互作用的控制：一系列异双核双（μ-羟基）Cr（III）Ni（II）配合物[（phen）_2Cr（μ-OH）_2Ni（Me_n-tpa）]（ClO_4）_3与tpa（三（2-吡啶甲基）胺）6-甲基衍生物（n = 0 - 3）反应，合成了一系列具有立体结构的化合物。在吡啶基上引入6位甲基后，Ni-N键长发生系统性的延长，导致体系的磁相互作用由弱的反铁磁相互作用转变为相对较强的铁磁相互作用。这可以解释为镍中心的d轨道能量降低，从而导致反铁磁贡献的减少。结果表明，磁相互作用可以由分子的d轨道能量控制。cbppef（I）配合物的氧反应活性的控制：具有三足四齿配体（双（6-甲基-2-吡啶基甲基）（2-吡啶基乙基）胺）的铜（I）配合物（[Cu（L）]^+）在-80℃下与氧反应生成双（μ-氧代）二铜（III）配合物，其结构由X射线晶体学确定。双（μ-氧代）二铜（III）配合物在-80 ~55 ℃下通过通入N_2可与前体铜（I）配合物发生可逆转化，并在较高温度下对支持配体表现出单加氧酶活性。这种O_2和O_2之间的可逆4电子还原和氧化<2->对于分子氧活化和水氧化化学特别重要。

项目成果

H.Furutachi, M.Suzuki, et al.: "Bis(μ-oxo)(μ-hydroxo)triiron(III) and (μ-oxo)(μ-hydroxo)diiron(III) Core Complexes with Tripodal Ligands Having a Terminal Calboxylate Group."Chemistry Letters. 1132-1133 (2000)

H.Furutachi、M.Suzuki 等人：“具有三足配体的双（μ-氧代）（μ-羟基）三铁（III）和（μ-氧代）（μ-羟基）二铁（III）核心配合物末端碳酸基团。“化学快报。1132-1133（2000）

H.Okawa., M.Suzuki, et al.: "A Heterodinuclear Co^<II>Cu^I Complex with Co(Salen) in Macrocyclic Framework. Oxygenation Studies in Comparison with Analogous Cu^<II>CU^I and Co^<II>Pb^<II> Complexes"Inorganic Chemistry. 39. 4520-4526 (2000)

H.Okawa.、M.Suzuki 等人：“大环框架中具有 Co(Salen) 的异双核 Co^<II>Cu^I 复合物。与类似 Cu^<II>CU^I 和 Co 比较的氧化研究

M.Suzuki,H.Furutachi,H.Okawa,: "Bimetallic Dioxygen Complexes Derived from 'End-off' Compartmental Ligands"Coordination Chemistry Review.. 200-202. 105-129 (2000)

M.Suzuki、H.Furutachi、H.Okawa，：“源自‘结束’隔室配体的双金属双氧配合物”配位化学评论.. 200-202。

M.Jalil, S.Fujinami, et al.: "An Imidazole-based P-N Bridging Ligand and its Binuclear Copper(I), Silver(I) and Palladium(I) Complexes : Synthesis, Characterizations and X-ray Structures"Polyhedron. 20. 627-633 (2001)

M.Jalil、S.Fujinami 等人：“基于咪唑的 P-N 桥连配体及其双核铜 (I)、银 (I) 和钯 (I) 配合物：合成、表征和 X 射线结构”多面体。

M.Jalil, S.Fujinami, et al.: "A New Tripod PPN Bridging Ligand ansi its Copper, Silver and Palladium Complexes : Synthesis, Characterizations and X-ray Structures"Polyhedron. 20. 1071-1078 (2001)

M.Jalil、S.Fujinami 等人：“一种新的 Tripod PPN 桥接配体及其铜、银和钯配合物：合成、表征和 X 射线结构”多面体。