Development of Highly Functionalized Dimetal Complexes

高功能化双金属配合物的开发

基本信息

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

项目摘要

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.

该研究项目的目的是通过控制金属离子周围的配位环境的性质来开发高度功能化的DI-METAL络合物。异源性核肉类复合物的磁相互作用的控制：一系列异源性核BIS（μ-Hydroxo）CR（III）CR（III）Ni（III）Ni（III）Ni（III）Ni（III）Ni（III）Ni（III）Ni（III） [（pEN）_2CR（μ-OH）_2Ni（ME_N-TPA）]（clo_4）_3，准备了具有6-甲基基（s）（n = 0-3）的空间较大的TPA（Tris（2吡啶基甲基）胺）衍生物。将6个甲基引入到吡啶基组上导致Ni-N键距离的系统伸长，从而导致系统的磁相互作用从弱抗抗铁磁相互作用到相对强的铁磁相互作用。这可以用降低镍中心的D轨道能量的降低来解释，从而导致抗铁磁贡献的减少。目前的结果表明，磁相互作用键盘由d轨道能量控制。金属离子通过修改协调环境。CBPPEF（I）复合物的双氧反应性的对比：铜（I）复合物（I）复合物（[Cu（l）^+）具有三座二义酸盐配体（BIS（BIS）（Bis（6-甲基-2-吡啶基甲基）（2-吡啶基）（2-吡啶基）Amine Amine a dioxy的dioxy， BIS（μ -oxo）双子（III）配合物的结构BIS（μ -oxo）双子器（III）复合物在-80-55℃时通过泡泡N_2气体通过前体铜（I）复合物进行可逆转化，并且还显示出在高温下支撑浓度的单氧化合酶活性。这种可逆的4电子还原和O_2和O^<2->之间的电子氧化对于二氧化剂激活和水氧化化学特别重要。