Palladium Complexes Based On Furoylhydrazone And Cyclopalladated Complexes Derived From Ferrocene Tertiary Amines:Synthesis,Characterization And Catalytic Activity

In this thesis,the synthesis?characterization and catalytic application of cyclopalladated complexes(CN-?CNO-?NO-and ONO-)containing furoylhydrazone ligands,and CN-cyclopalladated complexes derived from ferrocene tertiary amines were reviewed.The main results are as follows:I Synthesis,characterization and catalytic activity of cyclopalladated complexes containing furoylhydrazone ligands1.Synthesis and characterization of cyclopalladated complexes containing furoylhydrazone ligands(Cat.?-Cat.??)Furoylhydrazone Ligands(H2L?-H2L??)were synthesized by the condensation of furan-2-carbohydrazide and aromatic aldehydes in alcohol,which were treated with Li2PdCl4 and CH3COONa,followed by trapping with PPh3 to afford the corresponding cyclopalladated complexes[CN-(Cat.?-Cat.?),CNO-(Cat.?-Cat.?),NO-(Cat.?-Cat.?)and ONO-(Cat.?-Cat.??)via aryl C-H bond activation or dephenoxylation of the related ligands.All the compounds were fully characterized by elemental analysis?IR?1H-NMR and 13C-NMR spectra,the molecular structures of cyclopalladated complexes(Cat.?-Cat.??)were further confirmed by the single crystal X-ray diffraction.2.Application of cyclopalladated complexes containing furoylhydrazone ligands in carbon-carbon coupling reactionThe catalytic activity of cyclopalladated complexes(Cat.?-Cat.??)in Suzuki-Miyaura and Mizoroki-Heck coupling reactions was examined.It was showed that Cat.? displayed high catalytic activity in Suzuki-Miyaura reaction between aryl bromide and arylboronic acid with K3PO4·7H2O as base.Cyclopalladated complex(Cat.?)could also catalyze the reaction of unactived bromothiophene and aryl chloride with arylboronic acid in 90%yield.On the other hand,cyclopalladated complex(Cat.?)showed high catalytic activity in the Mizoroki-Heck reaction of aryl halides with methyl acrylate and styrene in the presence of Cs2CO3 as base.The catalytic activity of ONO-cyclopalladated complexes containing furoylhydrazone in the coupling reaction of arylboronic acid,phenyl acetylene with aryl acyl chloride was explored.After optimization of the reaction conditions,we determined that Cat.?/Cs2CO3(i-Pr2NH)gave the diarylketone and acetylenic ketone derivatives in excellent yield,these results provided data support for the skeleton construction of aromatic ketones or alkynones.? Synthesis,characterization and catalytic activity of CN-cyclopalladated complexes derived from ferrocene tertiary amines1.Synthesis and characterization of cyclopalladated complexes containing ferrocene tertiary aminesThe ferrocenylimines la-f were prepared by the condensation of ferrocenylmeth-yl(ethyl)amine and 2-furanaldehyde,2-thenaldehyde or benzaldehyde,which were treated with NaBH4,methylation reaction providing the ferrocene tertiary amines(L?-L?),which reacted with Li2PdCl4 and CH3COONa,then treated with PPh3 affording the cyclopalladated complexes containing ferrocene tertiary amines(Cat.?-Cat.?).All the complexes were characterized by elemental analysis,IR,1H-NMR and 13C-NMR spectra.The cyclopalladated complexes(Cat.?-Cat.?)were further confirmed by the single crystal X-ray diffraction.2.Application of cyclopalladated complexes containing ferrocene tertiary amines(Cat.?-Cat.?)in Suzuki-Miyaura coupling reactionThe catalytic activity of cyclopalladated complexes(Cat.?-Cat.?)in the Suzuki-Miy aura reaction of 3,4-dimethoxyphenylboronic acid with aryl halides was evaluated.Cyclopalladated complex(Cat.?)showed high catalytic activity in the coupling reaction,these results providing the theoretical basis for the development of novel cyclopalladated complexes containing ferrocene tertiary amines.