Synthesis,Characterization And Catalytic Properties Of Amine Methylene Substituted Pyridvl Rare-Earth Metal Complexes

In this thesis,the reactivity of aminomethylene substituted pyridine with trivalent rare-earth metal amide[?Me₃Si?₂N]₃RE?m-Cl?Li?THF?₃was studied.Aminomethylene substitutedpyridylligands2-[?CH₃?₂NCH₂CH₂NHCH₂]C₅H₄N?L₁?or2-?2,6-ⁱPr₂C₆H₃NHCH₂?C₅H₄N?L₂?were synthesized by the reaction of 2-pyridine-carboxaldehyde with 2-dimethylaminoethylamine or 2,6-diisopropylaniline to form a Schiff base,is then reduced by NaBH₄.The dianionic?-diiminorare-earth complexes{m-?²:?¹:k¹:k¹-2-[?CH₃?₂NCH₂CH₂NCH]C₆H₅N}₂RE₂[N?SiMe₃?₂]₂?RE=Y?1?,Lu?2?,Yb?3?,Er?4?,Dy?5?,Gd?6?,Sm?7?,Nd?8?,Pr?9?,La?10??were prepared through reaction of compound 1 with[?Me₃Si?₂N]₃RE?m-Cl?Li?THF?₃,which underwent the protonation of amino group and dehydrogenation of active methylene.When the ligand L₂ reacted with[?Me₃Si?₂N]₃RE?m-Cl?Li?THF?₃,an aminemethylene substituted pyridyl earth metal complex[2-?2,6-ⁱPr₂C₆H₃NCH₂?C₅H₄N]₂RE[N?SiMe₃?₂]?RE=Y?11?,Er?12??were obtained.The results indicate that the coordination of the heteroatoms of the ligand has a great effect on the formation of the rare earth metal complex of the?-diamine dianion ligand.All complexes were crystallographically determined by spectroscopy,elemental analysis,and X-raysingle crystal diffraction techniques.In order to further expand the application of dianionic?-diiminorare-earthcomplexes,we investigated complexes 1¹0 as catalysts for the cross-dehydrogenation coupling reaction of silane and amine.The experimental results show that these complexes can efficiently catalyze the cross-dehydrogenation coupling reaction between silane and amine,and the catalytic system has widesubstrate adaptability.The catalytic system could suit well for primary amines,secondary amines and aromatic amines,can react with disubstituted silanes.For an aromatic aminewith steric hindrance,the reaction yield was slightly lowered.Additionally,for the reaction of a monosubstituted silane and an amine,it was found that the product could not remain in the phase of coupling a molecule of amine,and the reaction continued to produce a product coupled with two molecules of amine.