Structure and Reactivity of Palladium Complexes Bearing Asymmetric Anilido-Imine Bidentate Ligands

• Main Authors: Chia-Li Chiou, 邱佳儷
• Other Authors: 陳竹亭
• Format: Others
• Language: zh-TW
• Published: 2005
• Online Access: http://ndltd.ncl.edu.tw/handle/59924195764457822750

碩士 === 國立臺灣大學 === 化學研究所 === 93 === With recent versatile applications in bioinorganic, main group, and transition metal chemistry, the research in β-diketiminato ligands of N-N bidentates and the salicylaldiminato ligands of N-O bidentates has been rising dramatically. We have successfully synthesized a series of ligands with functional combination of anilido-imine (o-C6H3R''2)NHC6H4CH=N(o-C6H3R2) ( 2a R'' = iPr, R = iPr; 2b R'' = CH3, R = iPr; 2c R'' = iPr, R = CH3; 2d R'' = CH3, R = CH3, 2e R'' = CH3, R = H) and their related anionic form LiN(o-C6H3R''2)C6H4CH=N(o-C6H3R2) (L3) ( 3a R'' = iPr, R = iPr; 3b R'' = CH3, R = iPr; 3c R'' = iPr, R = CH3; 3d R'' = CH3, R = CH3) via deprotonation. The photoluminscence nature of complexes 3 corresponding to their structures has been studied. These coordination of derivates (3) can generate a square-planar complex (L)Pd(CH3)(PPh3)(4) by reacting with (COD)Pd(Me)Cl and PPh3. NMR measurements show that the methyl ligand is trans to the imine. The reactions of L3 with [(η3-C3H4R")PdCl]2 afford two geometric isomers of η3-allyl species which have been well characterized by sophisticated 2D-NMR. The steric and electronic effects of the anilido-imine ligands can influence the regioselectivity as well as the ratio of isomers. The palladium complexes (4) are active to the Heck and Suzuki cross-coupling reactions, and its TON can reach to 103~104. These catalysts (4) also show activity about 105gPNmol-1h-1 to the polymerization of norborene.