含氮杂环衍生双齿配体及其铜和钯配合物的合成、表征与催化研究

发布时间：2018-01-11 18:29

  本文关键词：含氮杂环衍生双齿配体及其铜和钯配合物的合成、表征与催化研究　出处：《山西师范大学》2016年硕士论文　论文类型：学位论文

  更多相关文章： 含氮杂环 双齿配体 铜、钯配合物 催化

【摘要】：含氮杂环衍生配体具有高的配位能力和多变的结构组合,可以与过渡金属形成单齿、双齿、三齿、以及多齿配合物,此类配合物稳定性高且具有良好的催化活性,所以含氮杂环金属配合物在金属有机化学领域备受关注。本文主要研究含氮杂环衍生双齿配体及其铜和钯配合物的合成、表征与催化研究。本论文包含以下三个部分:第1部分前言本章介绍了含氮杂环衍生配体及其铜和钯配合物的最新研究进展。第2部分N,O-双齿配体及其铜和钯配合物的合成、表征与催化研究1.以2-氯甲基吡啶盐酸盐、4-氯甲基噻唑盐酸盐为原料,分别与四氢吡咯、吗啡啉反应,合成了N,O-双齿配体N-(2-pyridylmethyl)pyrrolidine-N-oxide(L1)、N-(2-pyridylmethyl)morpholin-N-oxide(L2)、N-(4-thiazolylmethyl)pyrrolidine-N-oxide(L3)、N-(4-thiazolylmethyl)morpholin-N-oxide(L4)。并且使用熔点、核磁共振、元素分析以及红外光谱对其结构进行表征。2.以L1、L2、L3、L4为配体与二氯化铜反应,制备了铜配合物1、2、3、4,通过熔点、X-射线单晶衍射、元素分析以及红外光谱对铜配合物进行了表征。四个铜配合物在苯胺与苯硼酸的Chan-Lam反应中表现一定的催化活性,其中2的催化活性最高。3.以L1、L2、L3、L4为配体与Pd(CH3CN)2Cl2反应,制备了钯配合物5、6、7、8。同时,利用熔点、元素分析以及红外光谱对此四个钯配合物进行了表征;利用X-射线单晶衍射确定了5的晶体结构。四个钯配合物对溴代芳烃与烯烃衍生物的Heck反应都具有较优的催化活性,其中7和8的催化活性最高。第3部分N,N'-双齿配体及其钯配合物的合成、表征与催化研究1.以2-氯甲基吡啶盐酸盐和4-氯甲基噻唑盐酸盐为原料,分别与1,2,4-三氮唑和1,2,3-苯并三氮唑反应,合成N,N'-双齿化合物2-(1,2,4-triazole-1-ylmethyl)pyridine(L5)、2-(1,2,3-benzotriazole-1-ylmethyl)pyridine(L6)、4-(1,2,4-triazole-1-ylmethyl)thiazole(L7)、4-(1,2,3-benzotriazole-1-ylmethyl)thiazole(L8),并且通过熔点、核磁共振、元素分析以及红外光谱对其结构进行了表征。其中,利用乙酸乙酯重结晶得到L6和L8的单晶,使用X-射线单晶衍射确定了它们的结构。2.以L5、L6、L7、L8为配体与Pd(CH3CN)2Cl2反应,制备了钯配合物9、10、11、12,使用熔点、元素分析以及红外光谱对此四个钯配合物进行了表征。四个钯配合物在溴代芳烃与烯烃衍生物的Heck反应表现出一定的催化活性,其中12展现出了较优的催化性能。
[Abstract]:Nitrogen-containing heterocyclic derivative ligands have a high coordination capacity and multiple structural combinations, and can form monodentate, didentate, tridentate, and polydentate complexes with transition metals. These complexes have high stability and good catalytic activity. Therefore, nitrogen-containing heterocyclic metal complexes have attracted much attention in the field of metal-organic chemistry. In this paper, the synthesis of nitrogen-containing heterocyclic didentate ligands and their copper and palladium complexes were studied. Characterization and catalytic studies. This thesis consists of the following three parts: in the first part, the introduction to this chapter introduces the latest research progress of nitrogen-containing heterocyclic derivative ligands and their copper and palladium complexes. Synthesis, characterization and Catalytic study of 2-Chloromethylpyridine Hydrochloride (2-Chloromethylpyridine) Hydrochloride, 4-Chloromethylthiazole Hydrochloride, reaction with Tetrahydropyrrole and morphine, respectively. N (N) -pyridylmethylpyrrolidine-N-oxide1 (N-pyridylmethylpyrrolidine-N-oxide1) was synthesized. N-pyridylmethylmorpholin-N-oxide-L2). N- (4-thiazolylmethylpyrrolidine-N-oxide-L3). N-A4-thiazolylmethyl-morpholin-N-oxide-L4C. Melting point, nuclear magnetic resonance (NMR). Elemental analysis and IR spectra were used to characterize the structure of the complex. The copper complex 1C 2N 3N 4 was prepared by the reaction of L 1O 2, L 2N, L 3, L 4 with copper dichloride, and the melting point of the complex was obtained by means of melting point. The copper complexes were characterized by X-ray single crystal diffraction, elemental analysis and infrared spectroscopy. The four copper complexes exhibited certain catalytic activity in the Chan-Lam reaction of aniline with phenylboric acid. The palladium complex 5H6 / 7 / 8 was prepared by the reaction of L1 / L2 (L2) and L3 / L4 with Pd(CH3CN)2Cl2. At the same time, the melting point was used to prepare the palladium complex. The four palladium complexes were characterized by elemental analysis and infrared spectroscopy. The crystal structure of 5 was determined by X-ray single crystal diffraction. The four palladium complexes had excellent catalytic activity for the Heck reaction of bromoarene with alkene derivatives. Among them, 7 and 8 have the highest catalytic activity. Part 3: synthesis of NNT-Dilate ligands and their Palladium complexes. Characterization and Catalytic study 1. Using 2-chloromethyl pyridine hydrochloride and 4-chloromethylthiazole hydrochloride as raw materials, N was synthesized by reaction with 1o 2N 4- triazole and 1H 2N 3- benzotriazole, respectively. Na-didentate compound 2-Tilazole-1-ylmethylpyridine (L5). 3-benzotriazole-1-ylmethylpyridine (L6). 4-triazole-1-ylmethylthiazoleine (L7). 3-benzotriazole-1-ylmethylthiazoleine L8, and through melting point, NMR. The structure of L6 and L8 was characterized by elemental analysis and infrared spectroscopy. The crystal structures of L6 and L8 were obtained by recrystallization of ethyl acetate, and their structures were determined by X-ray single crystal diffraction. Palladium (鈪，

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