本文關(guān)鍵詞：含氮雜環(huán)衍生雙齒配體及其銅和鈀配合物的合成、表征與催化研究　出處：《山西師范大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

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【摘要】：含氮雜環(huán)衍生配體具有高的配位能力和多變的結(jié)構(gòu)組合,可以與過(guò)渡金屬形成單齒、雙齒、三齒、以及多齒配合物,此類配合物穩(wěn)定性高且具有良好的催化活性,所以含氮雜環(huán)金屬配合物在金屬有機(jī)化學(xué)領(lǐng)域備受關(guān)注。本文主要研究含氮雜環(huán)衍生雙齒配體及其銅和鈀配合物的合成、表征與催化研究。本論文包含以下三個(gè)部分:第1部分前言本章介紹了含氮雜環(huán)衍生配體及其銅和鈀配合物的最新研究進(jìn)展。第2部分N,O-雙齒配體及其銅和鈀配合物的合成、表征與催化研究1.以2-氯甲基吡啶鹽酸鹽、4-氯甲基噻唑鹽酸鹽為原料,分別與四氫吡咯、嗎啡啉反應(yīng),合成了N,O-雙齒配體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)。并且使用熔點(diǎn)、核磁共振、元素分析以及紅外光譜對(duì)其結(jié)構(gòu)進(jìn)行表征。2.以L1、L2、L3、L4為配體與二氯化銅反應(yīng),制備了銅配合物1、2、3、4,通過(guò)熔點(diǎn)、X-射線單晶衍射、元素分析以及紅外光譜對(duì)銅配合物進(jìn)行了表征。四個(gè)銅配合物在苯胺與苯硼酸的Chan-Lam反應(yīng)中表現(xiàn)一定的催化活性,其中2的催化活性最高。3.以L1、L2、L3、L4為配體與Pd(CH3CN)2Cl2反應(yīng),制備了鈀配合物5、6、7、8。同時(shí),利用熔點(diǎn)、元素分析以及紅外光譜對(duì)此四個(gè)鈀配合物進(jìn)行了表征;利用X-射線單晶衍射確定了5的晶體結(jié)構(gòu)。四個(gè)鈀配合物對(duì)溴代芳烴與烯烴衍生物的Heck反應(yīng)都具有較優(yōu)的催化活性,其中7和8的催化活性最高。第3部分N,N'-雙齒配體及其鈀配合物的合成、表征與催化研究1.以2-氯甲基吡啶鹽酸鹽和4-氯甲基噻唑鹽酸鹽為原料,分別與1,2,4-三氮唑和1,2,3-苯并三氮唑反應(yīng),合成N,N'-雙齒化合物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),并且通過(guò)熔點(diǎn)、核磁共振、元素分析以及紅外光譜對(duì)其結(jié)構(gòu)進(jìn)行了表征。其中,利用乙酸乙酯重結(jié)晶得到L6和L8的單晶,使用X-射線單晶衍射確定了它們的結(jié)構(gòu)。2.以L5、L6、L7、L8為配體與Pd(CH3CN)2Cl2反應(yīng),制備了鈀配合物9、10、11、12,使用熔點(diǎn)、元素分析以及紅外光譜對(duì)此四個(gè)鈀配合物進(jìn)行了表征。四個(gè)鈀配合物在溴代芳烴與烯烴衍生物的Heck反應(yīng)表現(xiàn)出一定的催化活性,其中12展現(xiàn)出了較優(yōu)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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