| Project/Area Number |
04453041
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | TOHOKU UNIVERSIYU |
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Principal Investigator |
ITO Tasuku Tohoku University, Department of Chemistry, Faculty of Science, Professor, 理学部, 教授 (90007328)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAGUCHI Tadashi Tohoku University, Department of Chemistry, Faculty of Science, Researcj Associa, 理学部, 助手 (40230362)
KIDO Hiroaki Tohoku University, Department of Chemistry, Faculty of Science, Research Associa, 理学部, 助手 (40004444)
大塩 寛紀 東北大学, 理学部, 助教授 (60176865)
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| Project Period (FY) |
1992 – 1993
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| Project Status |
Completed (Fiscal Year 1993)
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| Budget Amount *help |
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1993: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1992: ¥5,600,000 (Direct Cost: ¥5,600,000)
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| Keywords | Dinuclear Complex / Polynuclear Metal Complex / Dinucleating Ligand / 金属錯体 / 対面型双環構造 / 二酸化炭素とりこみ |
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| Research Abstract |
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>.
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