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Studies on Heterodinuclear Metal Complexes

异双核金属配合物的研究

基本信息

批准号：
07454178
负责人：
OKAWA Hisashi
金额：
$ 4.8万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

(1) Phenol-based dinucleating macrocycles, derived from the 2 : 1 : 1 condensation of 2,6-diformyl-4-methylphenol, H_2N-(CH_2)_m-NH_2(m=2,3) and H_2N-(CH_2)_n-NH_2(n=3,4), formed heterodinuclear Ni(II)Mn(II), Cu(II)Mn(II), Ni(II)Co(II), Cu(II)Co(II) and Cu(II)Ni(II) complexes whose molecular structures were determined by X-ray chrystallography and physicochemical properties were examined. Cryomagnetic studies revealed antiferromagnetic interaction in the complexes except for Ni(II)Mn(II) and Ni(II)Co(II). All the complexes were stable in solution and form unusual oxidation-state complexes such as Ni(I)Co(II), Ni(I)Co(I), etc. The Cu(II)Ni(II) complex showed a very strong antiferromagnetic interaction to exist as the spin-doublet ground state at liquid nitrogen temperature. ESR study for the S_T=1/2 state showed a spin-delocalization over the CuNi core.(2) A Co(II)Pb(II) complex of a related macrocycle, having two dissimilar metal-binding sites of the N_2O_2 and N_2O_3 donor sets sharing two phenolic oxygens, was prepared. It acts as a reversible dioxygen-carrier in solid state owing to a neighboring effect of the Pb(II) ion.(3) Phenol-based dinucleating macrocycles, with two dissimilar N(amine)_2O_2 and N(imine)_2O_2 metal-binding sites sharing two phenolic oxygens, were prepared and a series of Cu(II)M(II)(M=Mn, Co, Ni, Cu, Zn) complexes were derived. CV for the complexes showed a considerable stabilization on electrode and formation of unusual oxidation-state compounds like Cu(I)Mn(II) etc.

(1)基于苯酚的双核大环，衍生自2：1：2，6-二甲酰基-4-甲基苯酚与H_2N-（CH_2）_m-NH_2（m= 2，3）和H_2N-（CH_2）_n-NH_2（n= 3，4）发生1次缩合反应，生成异双核Ni（II）Mn（II），Cu（II）Mn（II），Ni（II）Co（II），用X射线衍射法测定了Cu（Ⅱ）Co（Ⅱ）和Cu（Ⅱ）Ni（Ⅱ）配合物的分子结构，并测定了配合物的理化性质。冷磁研究表明，反铁磁相互作用的配合物中，除了Ni（II）Mn（II）和Ni（II）Co（II）。所有配合物在溶液中均稳定，形成了Ni（I）Co（II）、Ni（I）Co（I）等不寻常的氧化态配合物，Cu（II）Ni（II）配合物在液氮温度下表现出很强的反铁磁相互作用，以自旋二重态基态存在。对S_T=1/2态的ESR研究表明，CuNi核上存在自旋离域。(2)合成了一种大环化合物的Co（II）Pb（II）配合物，该配合物具有两个不同的金属结合位点，即N_2O_2和N_2O_3供体组共享两个酚氧。由于Pb（II）离子的邻位效应，它在固态下充当可逆的双氧载体。(3)合成了具有两个不同金属结合位点的N（胺）_2O_2和N（亚胺）_2O_2的酚基双核大环化合物，并合成了一系列Cu（II）M（II）（M=Mn，Co，Ni，Cu，Zn）配合物。循环伏安表明配合物在电极上有相当大的稳定性，并形成了Cu（I）Mn（II）等不寻常的氧化态化合物。