Synthesis, Structure And Catalytic Activity Of Organolanthanide Complexes With Substituted 1, 3-Diaminopropane Ligands

In this artical we retrospect the origination and the development of organolanthnide complexes,introduced the catalysis of the organolanthanide complexes in nowdays.Herein we changed the organolanthanide by which we want to improve the catalysity.All experiments were carried out under the dry and oxygen-free argon atmosphere by using standard Schlenk techniques.Reaction of H₂NCH₂CH₂CH₂NH₂ with 2 equiv of n-BuLi in THF at -78℃yielded LiNHCH₂CH₂CH₂NHLi.And then added 2 equiv(i-Pr)₃SiCl at 0℃resulted (i-Pr)₃SiNHCH₂CH₂CH₂NHSi(z-Pr)₃.Interaction of SmCl₃ with 2 equiv of (i-Pr)₃SiLiNHCH₂CH₂CH₂NHLiSi(i-Pr)₃ in refluxing THF for 24 hours,after recrystallization from Hexane,gave an Samarium(â…¢)complex [(i-Pr)₃SiNCH₂CH₂CH₂NSi(i-Pr)₂]₂Sm^â…¢?Li(THF)₄(1)in 65%yield.Interaction of EuCl₃ with 2 equiv of(i-Pr)₃SiNHCH₂CH₂CH₂NHSi(i-Pr)₃ in THF at 50℃for 24 hours,gave a Europium(â…¢)complex [(i-Pr)₃SiNCH₂CH₂CH₂NSi(i-Pr)₃]₂Eu^Ⅲ·Li(THF)₄(2)in 55%yield.Reaction of LiNHCH₂CH₂CH₂NHLi with 2 equiv Me₃SiCl in THF at -78℃yielded Me₃SiNHCH₂CH₂CH₂NHSiMe₂ in 80%yield.And then added 2 equiv Me₃SiCl at 0℃resulted Me₃SiNHCH₂CH₂CH₂NHSiMe₃.Interaction of EuCl₃ with 2 equiv of Me₃SiLiNHCH₂CH₂CH₂NHLiSiMe₃ in refluxing THF for 24 hours, after recrystallization from Hexane,gave an Europium(â…¢)complex [Me3SiNCH₂CH₂CH₂NSiMe₃Eu^â…¢Cl(THF)]₂(3)in 66%yield.Interaction of SmCl₃ with 2 equiv of Me₃SiLiNHCH₂CH₂CH₂NHLiSiMe₃ in refluxing THF for 24 hours,after recrystallization from Hexane,gave an Samarium(â…¢) complex[Me₃SiNCH₂CH₂CH₂NSiMe₃Sm^â…¢(THF)Cl]₂·2LiCl(4)in 60%yield. Interaction of YbCl₃ with 2 equiv of Me₃SiLiNHCH₂CH₂CH₂NHLiSiMe₃ in refluxing THF for 24 hours,after recrystallization from Hexane,gave an Ytterbium(â…¢)complex[Me₃SiNCH₂CH₂CH₂NSiMe₃Yb^â…¢(THF)Cl]₂ ? 2LiCl(5) in 56%yield.Interaction of YCl₃ with 2 equiv of Me₃SiLiNHCH₂CH₂CH₂NHLiSiMe₃ in refluxing THF for 24 hours,after recrystallization from Hexane,gave an Yttrium(â…¢)complex [Me₃SiNCH₂CH₂CH₂NSiMe₃Y^â…¢(THF)Cl]₂ ? 2LiCl(6)in 58%yield.The structures of complexes 1 were determined by X-ray diffraction.Complexes 3,4,5,6 were fully characterized by elemental and spectroscopic analyses.On the basis of the above experimental results,these experiments provides a methodology to prepare the organolanthanide complexes with substituted 1,3-Diaminopropane ligands.The activities of the organolanthanide complexes as single-component catalysts in catalyzing MMA andε-CL polymerization were examined.It was found that the activities of the catalysts,stereo-regularity of PMMA,and the molecular weight of polymers were dependent on the solvents,temperature and the central metal of the catalysts.