Synthesis,Structure And Application Of Novel Nitrogen Heterocyclic Metallic Compounds

In this work,12 new metal compounds were synthesized and studied.The thesis involves addition reactions of derivatives of aniline Ph N?Li?Si Me₃?L1?with Me₂NCN or 1-piperidinecarbonitrile at ratio of 2:1,further methathesis reaction with Ti Cl₄?THF?₂ at ratio of 1:3 to give compounds2a-2c,and 2d-2d'.The thesis also involves reachtions of derivatives of aniline and 2-aminopyridine?2-C₅H₄N?N?H?Si Me₃?L²?with BuⁿLi at ratio of1:1,further addition reactions with Me₂NCN or 1-piperidinecarbonitrile at ratio of 1:1,further methathesis reaction with Cr Cl₂?Fe Cl₂?CuCl₂ and Sn Cl₂ at differentratioestogivecompounds3a-3h.Twelvenovel1,3,5-triazapentadienyl organometallic compounds were synthesized and their structures were fully characterized by ¹H NMR,¹³C NMR,X-ray single crystal diffraction and elemental analysis,and their melting points were determined as well.Two 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 aminopyridyl complexes and organometallic compounds of titanium.Chapter 2.Developments of Ti compounds.Three new compounds including Ti,guanidinate and 1,3,5-triazapentadienyl complexes?Scheme 1?were obtained via the reactions of Ph N?Li?Si Me₃ and Me₂NCN or 1-Piperidinecarbonitrile,methathesis reaction with Ti Cl₄?THF?₂.Compound2d-2d'was obtained via the same way as the synthesis of 2b,and reaction with CH₃Li.Their molecular structures were fully characterized by ¹H and¹³C NMR,and X-ray single crystal diffraction.Compound 2a and 2c were used as catalyst in the polymerization of ethylene under different conditions such reaction temperature and Al/Ti,finally showed there highest catatlyticChapter 3.Developments of aminopyridyl ligands.Eight new compounds including Cr?II?,Fe?II?,Cu?II?,Sn?II?and 1,3,5-triazapentadienyl complexes?Scheme 2?were obtained via the reactions of?2-C₅H₄N?N?H?Si Me₃ with Buⁿ Li and Me₂NCN or 1-Piperidinecarbonitrile,methathesis reaction with Cr Cl₂,Fe Cl₂,CuCl₂ and Sn Cl₂.Their molecular structures were fully characterized by ¹H and ¹³C NMR,and X-ray single crystal diffraction.Scheme 1 Synthetic routes to complexes 2a-2c,and 2d-2d'Reagents and conditions:i 2Me₂NCN,Et₂O,ca.-78?;1/3 Ti Cl₄?THF?₂,Et₂O,ca.-78??.ii 2Me₂NCN,Et₂O,ca.-78?;1/3 Ti Cl₄?THF?₂,Et₂O,ca.-78?.iii 2 1-Piperidinecarbonitrile,Et₂O,ca.-78?;1/3 Ti Cl₄?THF?₂,Et₂O,ca.-78?.iv 2Me₂NCN,Et₂O,ca.-78?;Ti Cl₄?THF?₂,Et₂O,ca.-78?;1/3 CH₃Li,Et₂O,ca.0?.Scheme 2 Synthetic routes to complexes 3a-3hReagents and conditions:i Buⁿ Li,Et₂O,0?;Me₂NCN,Et₂O,ca.-78?;1/2 Cr Cl₂,Et₂O,ca.-78?.ii Buⁿ Li,Et₂O,0?;1-Piperidinecarbonitrile,Et₂O,ca.-78?;1/2 Cr Cl₂,Et₂O,ca.-78?.iii Buⁿ Li,THF,0?;Me₂NCN,THF,ca.-78?;1/2 Fe Cl₂,THF,ca.-78?;CH₂Cl₂.iv Buⁿ Li,Et₂O,0?;Me₂NCN,Et₂O,ca.-78?;1/2 CuCl₂,Et₂O,ca.-78?.v Buⁿ Li,Et₂O,0?;Me₂NCN,Et₂O,ca.-78?;1/2 CuCl₂,Et₂O,ca.-78?.vi Buⁿ Li,Et₂O,0?;1-Piperidinecarbonitrile,Et₂O,ca.-78?;1/2 CuCl₂,Et₂O,ca.-78?.vii Buⁿ Li,Et₂O,0?;Me₂NCN,Et₂O,ca.-78?;Sn Cl₂,Et₂O,ca.-78?.