Preparation And Characterization Of Some Tertiary 3-Substituent Benzylamine Cyclopalladated Complexes And Their Catalytic Activity In Suzuki And Heck Reaction

The dissertation consists of three parts.1. Preparation and characterization of series 3-substitued tertiary benzylamine cyclopalladated complexes.A series of tertiary 3-substitued benzylamine cyclopalladated complexes were designed and prepared by the reaction of 3-substituted N,N-dimethylbenzylamine with Li₂PdCl₄. The 3-substituent groups include -Me, -Cl, -F, -CO₂Et. All the complexes were characterized by ¹H NMR, ¹³C NMR, IR and elemental analysis. Therein the structures of the 3-Cl, 3-F, 3-Me substituted complexes have been confirmed by X-ray diffraction. The results may provide advisable information for the relationship between the catalyst's stability with activity as well as catalytic mechanism.2. Suzuki coupling reaction catalyzed by the four cyclopalladated complexes tertiary benzylamineFour tertiary benzylamine cyclopalladated complexes have been synthesized and applied in Heck reaction. The initial TG-DTA analysis of the four complexes was also tested. The reaction system and condition were optimized. The results showed that these cyclopalladated complexes are all of good catalytic activities for the Suzuki reaction. Under the optimized condition, the TON value was up to 10⁵. However, when the substrate is chlorinated arene, the catalytic activity is not good as that of brominated one.3. Application of several 3-substitued tertiary benzylamine cyclopalladated complexes on Suzuki coupling reaction and Heck reactionThe prepared cyclopalladated complexes were applied on Suzuki coupling reaction and Heck reaction. Using 4-bromo acetophone with boronic acid as the model reaction, the order of the catalytic activity for 3-substituted cyclopalladated complex was -Me> -Cl> -F>COOEt. In the model reaction of iodobenzene with butyl acrylic, the order of the catalytic activity for 3-substituted cyclopalladated complex was -Cl > -F > -CO₂Et >-Me.Several cyclopalladated complexes of tertiary 3-substituted benzylamine were synthesized, characterized and tested in Suzuki coupling reaction and Heck reaction, and the relationship between the structures with the catalyst activity is discussed. This work provides some information for probing the effective catalysts of C-C bondformation reaction.