"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:
- 金额:$ 4.61万
- 依托单位:
- 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
- 来源:
- 关键词:
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>。
项目成果
期刊论文数量(18)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
H.Kido: "Preparation of a Flexible Dinucleating Ligand,a,a-Bis(1,4,8,11-tetraaza-cyclo-tetradecane-6-yl)-p-xylene(L) and Structure of Its Dinickel(II) Complex,[Ni_2(L)]^<4+>" (投稿中).
H.Kido:“柔性双核配体a,a-Bis(1,4,8,11-四氮杂-环十四烷-6-基)-对二甲苯(L)的制备及其二镍(II)的结构) 复杂,[Ni_2(L)]^<4+>"(当前正在发布)。
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Takashi Kajiwara, Tadashi, Yamaguchi, Hiroaki Kido, Satoshi Kawabara, Reiko Kuroda and Tasuku Ito: ""A Dinucleating Bis(dimethylcyclam) Ligand and Its Dinickel(II) and Dizinc(II) Complexes with the Face-to-face Ring Arrangement"" Inorganic Chemistry. 32.
Takashi Kajiwara、Tadashi、Yamaguchi、Hiroaki Kido、Satoshi Kawabara、Reiko Kuroda 和 Tasuku Ito:“双核双(二甲基环酰胺)配体及其面对面环排列的二镍 (II) 和二锌 (II) 配合物”
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Takashi Kajiwara, Tadashi Yamaguchi, Hiroaki, Kido, Hiroki Oshio and Tasuku Ito: ""Synthesis, Structure, and Magnetic Property of Linear Chloro-Bridged Nickel(II) Tetramer with Dinucleating Bis-dimethylcyclam Ligand"" Submitted for publication.
Takashi Kajiwara、Tadashi Yamaguchi、Hiroaki、Kido、Hiroki Oshio 和 Tasuku Ito:“具有双核双二甲基环酰胺配体的线性氯桥镍 (II) 四聚体的合成、结构和磁性”,已提交出版。
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T.Kajiwara: "A Dinucleating Bis(dimethylcyclam) Ligand and Its Dinickel(II) and Dizinc(II) Complexes with the Face-to-face Ring Arrangement" Inorganic Chemistry. 32. 4990-4991 (1993)
T.Kajiwara:“双(二甲基环酰胺)双核配体及其面对面环排列的二镍(II)和二锌(II)配合物”无机化学。
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Hiroaki Kido, Makoto Takada, Masaaki Suwabe, Tadashi Yamaguchi, and Tasuku Ito: ""Preparation of a Flexible Dinucleating Ligand, alpha, alpha'-Bis(1,4,8,11-tetraazacyclotetradecane-6-yl)-p-xylene(L) and Structure of Its Dinickel(II) Complex, [Ni_2(L)]^<4+
Hiroaki Kido、Makoto Takada、Masaaki Suwabe、Tadashi Yamaguchi 和 Tasuku Ito:“灵活双核配体的制备,α, α-双(1,4,8,11-四氮杂环十四烷-6-基)-对二甲苯
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ITO Tasuku其他文献
ITO Tasuku的其他文献
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{{ truncateString('ITO Tasuku', 18)}}的其他基金
Syntheses of Molecular Assemblies Based on Coordination Compounds, and Their Chemical Function
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- 批准号:
19550057 - 财政年份:2007
- 资助金额:
$ 4.61万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Preparation of Nano-sized Transition Metal Complexes and Their Chemical Functions
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17550052 - 财政年份:2005
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Construction of Nano Strucutures Based on Metal Cluster Complexes and Their Chemistry
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14340203 - 财政年份:2002
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$ 4.61万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Metal-assembled Complexes -Chemisty Based on Inorganic-Organic Hybrid Electronic Structures-
金属组装配合物-基于无机-有机杂化电子结构的化学-
- 批准号:
10149101 - 财政年份:1998
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$ 4.61万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
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过渡金属组装配合物的化学功能
- 批准号:
10149102 - 财政年份:1998
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$ 4.61万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas (A)
Valence Fluctionality of Trinuclear Ruthenium Complex Dimers
三核钌配合物二聚体的价态波动性
- 批准号:
09044054 - 财政年份:1997
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$ 4.61万 - 项目类别:
Grant-in-Aid for international Scientific Research
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08454207 - 财政年份:1996
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$ 4.61万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Syntheses of New Polynuclear and Low-Dimensional Metal Complexes and Chemical Consequences of Metal Ion Assemblage
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02303006 - 财政年份:1990
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$ 4.61万 - 项目类别:
Grant-in-Aid for Co-operative Research (A)
Chemical Consequences of Assemblage of Transition Metal Ions or Metal Complexes
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01430009 - 财政年份:1989
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$ 4.61万 - 项目类别:
Grant-in-Aid for General Scientific Research (A)
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