Studies On Syntheses And Catalytic Reactivity Of Titanium, Magnesium And Samarium-Magnesium Complexes Incorporating Pyrrolyl Ligands

The thesis mainly focused on the syntheses and catalytic reactivity of titanium,magnesium and samarium-magnesium complexes incorporating pyrrolyl ligands. It’scomposed of following three parts.Firstly, five pyrrolyl ligands HL1-HL5（HL1=N-（1H-Pyrrol-2-ylmethylene）-（2-pyridinyl）methanamine, HL2=N-（1H-Pyrrol-2-ylmethyl-ene）-2-pyridinethanamine,HL3=2-Pyrrolecarbaldmethylimine, HL4=N-（（1H-pyrrol-2-yl）methylene）（phenyl）-methanamine, HL5=N-（（1H-pyrrol-2-yl）methylene）-2-phenyl-ethanamine） weredesigned and five novel magnesium complexes Mg（L1）2（1）, Mg（L2）2（2）,Mg（L3）₂（THF）₂（3）, Mg（L4）₂（THF）₂（4）, Mg（L5）₂（THF）₂（5） were synthesized. Allcomplexes have been characterized by elemental analyses and NMR studies. Thesolid-state structures of complexes2,3and4have been further established by singleX-ray crystallography. All complexes were found to be active catalysts for thering-opening polymerization of ε-caprolactone, especially in THF and DME.Secondly, five novel titanium complexes Ti（OiPr）2（L1）2（6）, Ti（OⁱPr）₂（L2）₂（7）,Ti（OiPr）2（L3）2（8）, Ti（OⁱPr）₂（L4）₂（9）, Ti（OⁱPr）₂（L5）₂（10） incorporating pyrrolyl ligandswere synthesized. All complexes have been characterized by elemental analyses andNMR studies. The solid-state structures of complexes6and9have been furtherestablished by single X-ray crystallography. The catalytic activity of6-10to thering-opening polymerization of ε-caprolactone was investigated.Thirdly, the complex [MgⁿBu（Hbptd）2Sm（THF）₃]（12）（H₃bptd=1,9-bis（2-pyrrol-y-l）-2,5,8-triazanona-1,8-diene）, which is the first magnesium-samarium heterometalliccomplex derived from Sm（Hbptd）（H₂bptd）（11） was synthesized. The catalytic activityof12to the intramolecular hydroamination reaction and the ring-openingpolymerization of ε-caprolactone were also investigated.