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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>.

本研究的目的是合成一个分子中含有两个cyclam环的双核配体（L），制备其具有共面环排列的脱金属配合物，并利用脱金属位点。1.成功地合成了两个二甲基环胺在6位上与邻二甲苯基相连的双核配体（L）; 2.利用该配体合成了镍（II）、锌（II）、钴（III）、镉（II）、钌（III）的双核配合物; 3.对三个晶体进行了单晶X射线衍射分析。在所有的结构中，两个cyclam环以预期的面对面的方式排列。两个金属中心通过卤素离子或碳酸根离子桥接，金属间化合物的分离度在5.4 - 5.8 A的范围内。4为了构建面对面的结构，我们故意在cyclam骨架上引入甲基。通过制备类似的不含甲基的双核配体并分析其二镍（II）络合物的X射线结构，验证了这种合成策略。5我们在使用双金属位点时获得了以下结果。(1)二锌配合物[Zn_2（L）]^<4+>自发吸收空气中的二氧化碳，生成具有共面环排列的μ-碳酸二锌配合物。(2)在固态下，氯桥二镍（II）配合物[Ni_2（μ-Cl）Cl_2（L）]^+具有准一维Ni-Cl交替线性链状结构。在Ni（II）离子中，两种类型的反铁磁相互作用以J=-48.2（3），J '=-11.2（3）cm^2起作用<-1>。