Addition Reactions And Applications Of The Derivatives Of Pyridine Or Hexamethyldisilazane With Nitriles

The thesis involves addition reactions of derivatives of 2-aminopyridine and hexamethyl disilazane with nitriles free-from a-H at different ratioes,further methathesis reaction with various anhydrous salts.A series of aminopyridyl,guanidinate and 1,3,5-triazapentadienyl complexes were synthesized and their physical and chemical properties were investigated.Ten novel organometallic compounds were obtained and their structures were fully characterized by 1H NMR,13C NMR and X-ray single crystal diffraction,and their melting points were determined as well.Three of which were used as catalysts in the polymerization of ethylene under various conditions including co-catalyst,reaction temperature and reaction time.The text is divided into four chapters:Chapter 1.General introduction and developments of guanidinate,1,3,5-triazapentadienyl and aminopyridyl complexes.Chapter 2.Developments of aminopyridyl ligands and their transition metal complexes.Six new compounds including Mn(?),Fe(?),Ni guanidinate and 1,3,5-triazapentadienyl complexes(Scheme 1)were obtained via the reactions of(2-C5H4N)N(H)SiMe3 and Me2NCN or 1-Piperidinecarbonitrile,methathesis reaction with MnCl2,FeCl2 and NiCl2.Their molecular structures were fully characterized by 1H and 13C NMR,and X-ray single crystal diffraction.Chapter 3.Developments and significance of the aminopyridyl ligands,their early transition metal complexes and utilities in olefin polymerization.Two novel zirconium 1,3,5-triazapentadienyl and aminopyridyl compounds 3a and 3b(Scheme 2)were obtained by the reaction of(2-C5H4N)N(H)SiMe3,Me2NCN or 1-Piperidinecarbonitrile and ZrCl4.Compound 3b was used as catalyst in the polymerization of ethylene under different conditions such as co-catalyst,reaction temperature and reaction time,finally showed its highest catatlytic activity of 1.47×105 g PE·mol-1·h-1.Chapter 4.General introduction and developments of ligand LiN(SiMe3)2 and its metal complexes.Two new stannum triazine and 1,3,5-triazapentadienyl compounds 4a and 4b(Scheme 3)were obtained via the reactions of LiN(SiMe3)2,Me2NCN and SnCl2.Their molecular structures were fully characterized by X-ray single crystal diffraction,1H,13C and 119Sn NMR.Reagents and conditions:?BunLi,0?;Me2NCN,Et2O,ca.-78?;1/2 NiCl2,Et2O,ca.-78?.?BunLi,0?;1-Piperidinecarbonitrile,Et2O,ca.-78?;1/2 NiCl2,Et2O,ca.-78?.?BunLi,0?;Me2NCN,Et20,ca.-78?;FeCl2,Et20,ca.-78?.?BunLi,0?;Me2NCN,Et2O,ca.-78?;MnCl2,Bt2O,ca.-78?.?BunLi,0?;Me2NCN,Et20,ca.-78?;1/2 FeCl2,Et20,ca.-78?.?BunLi,0?;1-Piperidinecarbonitrile,Et2O,ca.-78?;1/2 FeCl2,Et20,ca.-78?;CH2CI2.Reagents and conditions:?Me2NCN,Et2O,ca.-78?;ZrCl4,Et20,ca.-78?;CH2Cl2.?1-Piperidinecarbonitrile,Et2O,ca.-78?;1/2 ZrCl4,Et2O,ca.-78?;CH2Cl2.Reagents and conditions:?2Me2NCN,Et2O,ca.-78?;1/2SnCl2,Et20,ca.-78?.?2Me2NCN,Et2O,ca.-78?;SnCl2,Et2O,ca.-78?.