Synthesis, Characterization And Catalytic Studies Of Nitrogen-Heterocyclic-Derived Bidentate Ligands And Their Copper And Palladium Complexes

Nitrogen-heterocyclic-derived ligands may react with transition metal to produce monodentate, bidentate, tridentate, and polydentate complexes, become of their high coordination ability and various structure combination. These complexes have high stability and good catalytic activity. So the transition metal complexes with N-heterocyclic derivatives had attracted much attention in organometallic chemistry. The synthesis, characterization and catalytic studies of nitrogen-heterocyclic-derived bidentate ligands and their copper and palladium complexes were researched in this paper.This paper includes the following three parts:Part 1 IntroductionIn this chapter, the recent progress of nitrogen-containing heterocyclic derivative ligands and their copper and palladium complexes were reviewed.Part 2 Synthesis, characterization and catalytic studies of N, Oligands and their copper and palladium complexes1. 2-chloromethylpyridine/ 4-chloromethylthiazole hydrochloride reacted with pyrrolidine/ morpholine to obtain 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), respectively. The structure of L1-L4 was characterized by melting point, NMR, elemental analysis and infrared spectroscopy.2. Four copper complexes 1, 2, 3, 4 were prepared by the reaction of ligands L1-L4 with copper chloride and characterizad by melting point, X-ray diffraction, elemental analysis and infrared spectra.These complexes 1-4 showed catalytic activity for aniline with phenylboronic acid Chan-Lam reaction. Among them, complexe 2 was the best catalyst.3. Compounds L1, L2, L3, L4 reacted with Pd(CH3CN)2Cl2to produce palladium complexes 5, 6, 7, 8, which were characterized by melting point, element analysis and infrared spectra. The crystal structure of5 was further determined by X-ray diffraction. Four new palladium complexes had catalytic activity for Heck reaction of aryl bromide and olefin derivatives in which the catalytic activity of 7 and 8 is higher.Part 3 Synthesis, characterization and catalytic studies of N, N'-ligands and their palladium complexes1. 2-chloromethylpyridine/ 4chloromethylthiazole hydrochloride reacted with 1, 2, 4-triazole/ 1, 2, 3-benzotriazole to give compounds2-(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), respectively. These compounds were characterized by melting point, NMR, elemental analysis and infrared spectroscopy. Single-crystals of L6 and L8 were obtained by volatilization of ethyl acetate. Their molecular structures were determined by X- ray single crystal diffraction.2. The reaction of compounds L5, L6, L7, L8 and Pd(CH3CN)2Cl2obtained complexes 9, 10, 11, 12, respectively. Four palladium complexes were determined by melting point, elemental analysis and infrared spectra. We explore the catalytic activity of 9-12 in Heck reaction of aryl bromide and olefin derivatives. Among them,complexe 12 is the best catalyst.