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

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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>.