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"Dinucleating Ligand Complexes Having Two Cyclam Rings Connected by Xylylene Group"

“具有两个由亚二甲苯基连接的环素环的双核配体配合物”

基本信息

批准号：
04453041
负责人：
ITO Tasuku
金额：
$ 4.61万
依托单位：
TOHOKU UNIVERSIYU
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

项目摘要

The objective of this study was to synthesize a dinucleating ligand (L) having two cyclam rings in a molecule, to make its demetallic complexes with the cofacial ring arrangement, and to use of the demetallic site. Following results have been obtained.1 We succeeded in the preparation of new dinucleating ligand (L) in which two dimethyl cyclams are connected at 6th position with ortho-xylylene group.2 With use of this ligand, we prepared new dinuclear complexes of nickel(II), zinc(II), cobalt(III), cadmium(II), ruthenium(III).3 Single crystal X-ray analyzes were carried out on three crystalline compounds. In all the structures, two cyclam rings are arranged in a face-to-face manner as expected. The two metallic sites are bridged by halide ion or carbonate ions and intermetallic separations were in the range of 5.4 - 5.8A.4 In order to construct the face-to-face structure, we put methyl groups on the cyclam skeleton on purpose. This synthetic strategy was verified by preparing a similar dinucleating ligand without methyl groups and analysing the X-ray structure of its dinickel(II) complex.5 We obtained the following results on the use of the dimetallic site.(1) Dizinc complex [Zn_2(L)]^<4+> takes up carbon dioxide spontaneously from the air to give mu-carbonato dizinc comple with the cofacial ring arrangement.(2) In the solid state, chloro-bridged dinickel(II) complex [Ni_2(mu-Cl)Cl_2(L)]^+ has a pseudo one dimensional Ni-Cl alternate linear chain structure. Among Ni(II) ions, two types of antiferromagnetic interactions operate with J=-48.2(3), J'=-11.2(3)cm^<-1>.

本研究的目的是在一个分子中合成具有两个环环的双核配体(L)，使其具有共面环排列的脱金属配合物，并利用脱金属位。得到了以下结果我们成功地制备了一个新的双核配体(L)，其中两个二甲基环类在第6位与邻二甲苯基团相连利用该配体，我们制备了镍（II）、锌（II）、钴（III）、镉（II）、钌（III）等新的双核配合物对三种晶体化合物进行了单晶x射线分析。在所有的结构中，两个cyclam环按照预期的方式面对面排列。两个金属位由卤化物离子或碳酸盐离子桥接，金属间分离在5.4 ~ 5.8A.4之间为了构建面对面的结构，我们特意将甲基放在cyclam骨架上。通过制备类似的无甲基双核配体并分析其二镍（II）配合物的x射线结构，验证了该合成策略我们在使用双金属位点时得到了以下结果。(1)二锌配合物[Zn_2(L)]^<4+>从空气中自发吸收二氧化碳，生成具有共面环排列的微碳酸二锌配合物。(2)在固体状态下，氯桥式二镍配合物[Ni_2(mu-Cl)Cl_2(L)]^+具有伪一维Ni-Cl交替线性链结构。在Ni（II）离子中，有两种类型的反铁磁相互作用：J=-48.2(3)， J'=-11.2(3)cm^<-1>。