Synthesis And Characterization Of Amidate Lanthanide Complexes (La/Gd) And Their Potential Use As Precursors For High-κ Material And Catalyst For The Polymerization Of ε-caprolactone

In this thesis, there are two main parts. Part one: a series of amidate lanthanide （Ln=La or Gd）complexes were designed and synthesized. The complexes obtained were characterized by elementalanalysis and X-ray single crystal analysis. Two complexes were selected as precursors to growrare-earth oxides films using MOCVD technique. The films were characterized by SEM and XPS.Part two: a series of mixed ligand lanthanide complexes were synthesized and characterized by1HNMR,13C{H} NMR, elemental analysis and X-ray single crystal analysis. Some of them werechoosed as catalysts in ε-caprolactone ring-opening polymerization and the poly（CL） were determinedby GPC.Part one: Synthesis and characterization of rare-earth amidate complexes （Ln=La, Gd）and their potential use as precursors for rare-earth oxides using MOCVD and ALDA series of amidate lanthanide （Ln=La or Gd） complexes were synthesized through lithium saltmetathesis route and silylamide route: LaLi[N（SiMei₃）₂]₃[Bu（NCO）Ph]·3THF （2a）,La₂[Cy（NCO）iPr]₆[Cy（HNCO）iPr]（2b）, Gd₂[Cy（NCO）iPr]₆（2c）, Gd₃O[N（SiMe₃）t₂]₃[Bu（NCO）Ph]₄（2d）, Gd2[tBu（NCO）Ph]6[tBu（HNCO）Ph]（2e）, Gd[tBu（NCO）tBu]3·2THF （2f） andLa[tBu（NCO）tBu]3·2THF （2g）, and all their crystal structures were measured. Complexes2f and2gwere analysised by ThemoGravimetry （TG） to study their thermal decomposition process and thenused as MOCVD precursors for the deposition of rare-earth oxides films. The thin films obtainedwere characterized by SEM and XPS.Part two: Synthesis and characterization of bis-and mono（amidate） lanthanide （Ln=La,Gd） complexes and their application in the polymerization of ε-caprolactoneA series of mixed ligand lanthanide complexes were synthesized through amidate andLa[N（SiMe3）2]3or Gd[N（SiMe₃）₂]₃: La[N（SiMe₃）₂]₂[R′（NCO）R]·xTHF （1, R=Ph, R′=tBu;2, R=Ph,R′=iPr;3, R=iPr, R′=iPr;4, R=iPr, R′=tBu, x=1）, La[N（SiMe₃）₂][R′（NCO）R]₂（5, R=tBu, R′=tBu;6, R=tBu, R′=iPr;7, R=iPr, R′=iPr）, La₂[N（SiMet₃）₂]₂[Bu（NCO）iPr]₃[O（SiMe₃）]（8） andGd[N（SiMe₃）₂][R′（NCO）R]₂（9, R=iPr, R′=iPr;10, R=Ph, R′=iPr）, and crystal structures of2,5,6,7,8,9and10were measured. Then1,2,3,5,7,9and10were selected as catalysts to polymerizeε-caprolactone with different ratio （[M]/[I]=100,250and500）, and the weights of poly（CL） weredetermined by GPC. The poly（CL） obtained with initiator1and a10:1monomer to initiator ratio wascharacterized by1H NMR, and the mechanism for the formation of hydroxyl-telechelic poly（CL） was also studied.