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新型不对称席夫碱过渡金属配合物的合成、表征及晶体结构
Synthesis , Characterization and Crystal Structure of Transition Metal Complexes of New Asymmetric Schiff Bases
【作者】 梁永庆；
【导师】 赵建社；
【作者基本信息】 西北大学 ， 物理化学， 2004， 硕士
【摘要】 过渡金属与席夫碱配体形成的配合物以其多样的结构和广泛的用途愈来愈受到人们的重视。该类配合物在催化、生物活性及功能材料等领域都有广泛的应用前景。 本文首次合成了一种邻氨基苯甲酸衍生物——2-氨基-N-苯基-苯甲酰胺，并在此基础上合成了十二个新型席夫碱化合物以及不对称席夫碱——2-氨基-N-苯基-苯甲酰胺单缩水杨醛的同分异构体。选用其中两个化合物：2-氨基-N-苯基-苯甲酰胺双缩水杨醛（HL1），2-氨基-N-苯基-苯甲酰胺缩 5-硝基水杨醛（HL2），与过渡金属(Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+共合成配合物14种。分别是：[Cr(Lla)2]·ClO4·2H2O 1、Mn(Lla)2 2、[Fe(Lla)2]·ClO4·H2O 3、Co(Lla)2 4、Ni(Lla)2 5、Cu(Lla)2 6、Zn(Lla)2 7、[Cr（L2）2]·ClO4·2H2O 8、Mn（L2）2 9、[Fe（L2）2]·ClO4·2H2O 10、Co（L2）2 11、Ni（L2）2 12、[Cu（L2）2]·H2O 13、Zn（L2）2 14。对上述配合物均进行了元素分析、红外光谱、紫外光谱以及荧光光谱等表征。根据实验事实，预测了配合物的性质。对部分配合物进行了热重分析测试，推测了配合物分解过程。 测定了2-氨基-N-苯基-苯甲酰胺双缩水杨醛（HL1）和三种配合物[Fe(Lla)2]·ClO4·H2O3、[Fe（L2）2]·ClO4·2H2O 10、[Cu（L2）2]·H2O 13的晶体结构。发现2-氨基-N-苯基-苯甲酰胺双缩水杨醛（HL1）、[Fe（L1）2]·ClO4·H2O 3和[Fe（L2）2]·ClO4·2H2O 10通过氢键连接为一维链状超分子。配休HL1和配体HL2在配合物[Fe(Lla)2]·ClO4·H2O 3和[Fe（L2）2]·ClO4·2H2O 10中均为三齿配体。但是在配合物[Cu（L2）2]·H2O 13中，由于Jahn-Teller效应和配体的空间位阻作用，一分子的配体以两齿形式和Cu（Ⅱ）进行配位，形成五配位的化合物。
【Abstract】 The coordination compounds, synthesized with transition metal and Schiff-bases as raw materials, are more and more important for their various structures and extensive uses. The applied foreground of these compounds will be extensive in the field of catalysis, bioactivity and material etc. Among which, it is dramatically interesting that the complexes use as the polyethylene catalysis.In this paper, a new o-amino benzoic acid derivative, 2-amino-N-phenyl-benzamide, has been obtained. And twelve new asymmetric Schiff bases containing 2-amino-N-phenyl-benzamide have been synthesized and characterized as well as an isomeric compound of 2-(2-hydroxy-benzylideneamino)-N-phenyl-benzamide. Two of them, the isomeric compound of 2-(2-hydroxy-benzylideneamino)-N-phenyl-benzamide(HL1) and 2-(2-hydroxy-5-nitryl-benzyl-ideneamino)-N-phenyl-benzamide(HL2), are used to synthesize the complexes with transition metal ions(Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+), and fourteen complexes are achieved. [Cr(L1a)2].ClO4.2H2O1, Mn(Lla)22, [Fe(Lla)2].ClO4.H2O3, Co(Lla)24, Ni(Lla)25, Cu(Lla)26, Zn(Lla)27, [Cr(L2a)2].ClO4.2H2O8, Mn(L2)29, [Fe(L2)a].ClO4.2H2O 10, Co(L2)2 11, Ni(L2)212, [Cu(L2)2].H2O13, Zn(L2)214.These complexes are all determined by elemental analysis, infrared spectra, UV spectra and fluorescence spectra. The properties of these compounds are forecasted by experiment facts. The thermal decomposition of some complexes has been investigated by TG-DSC. Their thermal decomposition processes have been presumed by experiment factsThe crystal structures of one ligand and three complexes have been determined. They are HL1.C2H6OH, [Fe(Lla)2].ClO4.H2O 3, [Fe(L2)2].ClO4.2H2O 10 and [Cu(L2)2].H2O 13. In HL1.C2H6OH, compound 3 and 10, it has been found that all compounds were formedone-dimensional chain supramolecules combined by intermolecular hydrogen bonds. The ligand HL1 performs as a tridentate ligand in complex 3 as well as HL2does in complex 10. In complex 3 and 10, the central Fe(III) ions are in six coordination environment. However, one of the ligands is acted as a bidentate ligand in compound 13 because of the Jahn-Teller effect and the steric interference of the ligand. Therefore, the central Cu(II) ions are in five coordination environment.
【Key words】 transition metal compounds； Schiff-base ligands； crystal structure； synthesis reaction mechanism； thermo-analysis；
- 【网络出版投稿人】 西北大学 【网络出版年期】2004年 04期
- 【分类号】O641.4
- 【被引频次】2
- 【下载频次】399