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首页> 外文学位 >Synthese et caracterisation de complexes metalliques avec le ligand 2,2'-biimidazole et son derive 1,1'-dimethyl-2,2'-biimidazole.
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Synthese et caracterisation de complexes metalliques avec le ligand 2,2'-biimidazole et son derive 1,1'-dimethyl-2,2'-biimidazole.

机译：具有2,2'-联咪唑配体及其1,1'-二甲基-2,2'-联咪唑衍生物的金属配合物的合成和表征。

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摘要

A large variety or new complexes of zinc, cadmium and chromium have been prepared from the reactions of the corresponding salts with the ligand 2,2'-biimidazole (H2biim). The reaction of H2biim with Cd(BF4) 2 led to the formation of the tris-chelate compound [Cd(H2biim) 3]2(SiF6)(BF4)2·6EtOH. The [Cd(H2biim)3]2+ and SiF6 2- ions define an extended hydrogen-bonded network, in which the B F- ions surrounded by disordered ethanol molecules occupy large cavities.;The reaction of Zn(ClO4)2 with Me2biim produced the dinuclear compound [(Me2biim)Zn(mu-Me2biim) 3Zn(Me2biim)](ClO4)4, containing two monodentate and three bridging Me2biim ligands bonded to Zn atoms in a distorted tetrahedral environment. A related neutral (NO3) 2Cd(mu-Me2biim)3Cd(NO3)2 complex containing only bridging Me2biim ligands was also synthesized. The coordination around each Cd atom is a distorted octahedron containing one monodentate and one bidentate nitrato ligands. Two ionic trinuclear Cd(II) compounds were also obtained, which include two sets of three bridging Me 2biim ligands connecting a central Cd atom to two terminal Cd centers. An extra Me2biim ligand is chelated to each terminal metal and the sixth coordination site is occupied by aqua ligands in the symmetric [(Me 2biim)(H2O)Cd(mu-Me2biim)3Cd(mu-Me 2biim)3Cd(CH2OH)(Me2biim)] (ClO 4)6 complex, whereas one aqua ligand is replaced by a methanol ligand in the non-symmetric [(Me2biim)(H2O)Cd(mu-Me 2biim)3Cd(mu-Me2biim)3Cd(CH 3OH)(Me2biim)] (ClO4)6 compound. In the chelating ligands, dihedral angles of ∼38° between the two imidazole rings reduce the repulsion between the N-methyl groups, but considerable strain remains, as evidenced from one of the Cd--N bond being much longer than the other. In the various compounds, dihedral angles of 60-80° are found between the two imidazole rings in the bridging ligands.;A dinuclear complex [Cu2(Me2biim)4(H 2O)2](NO3)4 in which two Cu(II) centers are bridged by four Me2biim ligands was also isolated. Each of these bridging ligands provides one N donor to each Cu center, generating the base of an approximate square pyramid, whose apical position is occupied by an aqua ligand. The nitrate ions and uncoordinated water molecules form a network of hydrogen bonds, in which the aqua ligands are also involved.(Abstract shortened by UMI.).;The tris-chelate [Cr(H2biim)3](NO3) 3 complex was obtained by reacting CrCl3·3THF with [Ag(H2biim)](NO3) in methanol. In the solvent-free material, each ligand forms two N--H···O bonds to a nitrate ion and generates locally neutral [Cr(H2biim)3](NO 3)3 units. A methanol solvate was also obtained, in which intermolecular interactions involve optimal use of the hydrogen-bonding ability of the [Cr(H2biim)3]3+ cations, NO 3- anions and methanol molecules. In both cases, there is no long-range regular organization of the different units. Deprotonation of [Cr(H2biim)3](NO3)3 with NaOCH 3 yielded the neutral compound Cr(Hbiim)3. Its powder X-ray diffraction pattern is similar to that of Ru(Hbiim)3, suggesting that it also consists of mutually perpendicular interlocked honeycomb sheets. Recrystallization by slow diffusion of diisopropyl ether into a methanol solution yielded a porous material of composition Cr(Hbiimh)3·2.6C 6H14O, in which superposed honeycomb sheets create infinite channels (∼ 13 A diameter) filled with disordered solvent molecules. A totally different structure was adopted by the solvate Cr(Hbiim)3·C 6·2H2O, where the benzene molecules are encapsulated in a cavity created by five completed molecules.
机译：从相应的盐与配体2,2'-联咪唑（H2biim）的反应制备了锌，镉和铬的多种或新型络合物。 H2biim与Cd（BF4）2的反应导致形成三螯合物[Cd（H2biim）3] 2（SiF6）（BF4）2·6EtOH。 [Cd（H2biim）3] 2+和SiF6 2-离子定义了一个扩展的氢键网络，其中被无序乙醇分子包围的B F-离子占据大的腔体。Zn（ClO4）2与Me2biim的反应制备了双核化合物[（Me2biim）Zn（mu-Me2biim）3Zn（Me2biim）]（ClO4）4，它在扭曲的四面体环境中包含两个单齿和三个桥接Me2biim配体，这些配体与Zn原子键合。还合成了仅包含桥接Me2biim配体的相关中性（NO3）2Cd（mu-Me2biim）3Cd（NO3）2络合物。每个Cd原子周围的配位是一个扭曲的八面体，其中包含一个单齿和一个双齿硝酸根配体。还获得了两个离子三核Cd（II）化合物，其中包括两组将中心Cd原子连接到两个Cd中心的三个桥接Me 2biim配体。额外的Me2biim配体螯合到每个末端金属上，第六个配位位点被对称[[Me 2biim）（H2O）Cd（mu-Me2biim）3Cd（mu-Me 2biim）3Cd（CH2OH）（Me2biim）的水配体占据）]（ClO 4）6配合物，而在非对称[[Me2biim）（H2O）Cd（mu-Me 2biim）3Cd（mu-Me2biim）3Cd（CH 3OH）（ Me2biim）]（ClO4）6化合物。在螯合配体中，两个咪唑环之间的二面角〜38°减少了N-甲基之间的排斥，但仍然存在相当大的应变，从Cd-N键之一比另一个长得多的事实就可以看出。在各种化合物中，桥接配体中的两个咪唑环之间的二面角为60-80°。；双核络合物[Cu2（Me2biim）4（H 2O）2]（NO3）4，其中两个Cu（II ）中心也被四个Me2biim配体桥接。这些桥联配体中的每一个为每个Cu中心提供一个N供体，生成一个近似方形的金字塔底，其顶端位置被水配体占据。硝酸根离子和未配位的水分子形成氢键网络，其中还包含水族配体。（UMI缩短。）；获得了三螯合物[Cr（H2biim）3]（NO3）3配合物。使CrCl3·3THF与[Ag（H2biim）]（NO3）在甲醇中反应。在无溶剂材料中，每个配体与硝酸根离子形成两个N·H··O键，并生成局部中性的[Cr（H2biim）3]（NO 3）3单元。还获得了一种甲醇溶剂化物，其中分子间的相互作用涉及[Cr（H2biim）3] 3+阳离子，NO 3-阴离子和甲醇分子的氢键结合能力的最佳利用。在这两种情况下，不同单位之间都没有长期的定期组织。用NaOCH 3将[Cr（H2biim）3]（NO3）3质子化，得到中性化合物Cr（Hbiim）3。它的粉末X射线衍射图谱与Ru（Hbiim）3相似，表明它也由相互垂直的互锁蜂窝片组成。通过将二异丙基醚缓慢扩散到甲醇溶液中进行重结晶，得到组成为Cr（Hbiimh）3·2.6C 6H14O的多孔材料，其中叠置的蜂窝板会形成无限大的通道（直径约13 A），其中充满了无序的溶剂分子。溶剂化物Cr（Hbiim）3·C 6·2H2O采用完全不同的结构，其中苯分子被封装在由五个完整分子形成的空腔中。

著录项

  • 作者

    Gruia, Letitia M.;

  • 作者单位

    Universite de Montreal (Canada).;

  • 授予单位 Universite de Montreal (Canada).;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2008
  • 页码 296 p.
  • 总页数 296
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 肿瘤学;
  • 关键词

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