"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”

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453041/
• 关键词: 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

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环的双核配体(L)，制备具有界面环排列的非金属配合物，并利用非金属中心。1.我们成功地合成了两个二甲基环与邻二甲苯基相连的新型双核配体(L)。2.利用该配体，我们合成了镍(II)、锌(II)、钴(III)、镉(II)、钚(III)的新型双核配合物。3对三种晶体进行了单晶X射线分析。在所有结构中，如预期的那样，两个自行车环以面对面的方式排列。这两个金属中心通过卤离子或碳酸盐离子桥联，金属间距离在5.4-5.8A.4之间。4为了构建面对面的结构，我们特意在环状骨架上添加了甲基。通过制备类似的无甲基去核配体和分析其镍(II)络合物的X-射线结构，验证了这一合成策略。5我们在双金属中心的使用上得到如下结果：(1)二锌配合物[Zn_2(L)]^&lt；4+&gt；；在Ni(II)离子中，存在两种反铁磁相互作用，J=-48.2(3)，J‘=-11.2(3)cm^&lt；-1&gt；

项目成果

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）。

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”

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。

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。

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