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Synthesis and structural characterization of beta-diketiminate-lanthanide Amides and their catalytic activity for the polymerization of methyl methacrylate and epsilon-caprolactone

By Yao YM, Zhang ZQ, Peng HM, Zhang Y, Shen Q and Lin J


The synthesis and catalytic activity of lanthanide monoamido complexes supported by a beta-diketiminate ligand are described. Donor solvents, such as DME, can cleave the chloro bridges of the dinuclear beta-diketiminate ytterbium dichloride {[(DIPPh)(2)nacnac]YbCl(mu-Cl)(3)Yb[(DIPPh)(2)nacnac](THF)} (1) [(DIPPh)(2)nacnac = N,N-diisopropylphenyl-2,4-pentanediimine anion] to produce the monomeric complex [(DIPPh)(2)nacnac]YbCl2(DME) (2) in high isolated yield. Complex 2 is a useful precursor for the synthesis of beta-diketiminate-ytterbium monoamido derivatives. Reaction of complex 2 with 1 equiv of LiNPr2i in THF at room temperature, after crystallization in THF/toluene mixed solvent, gave the anionic beta-diketiminate-ytterbium amido complex [(DIPPh)(2)nacnac]Yb(NPr2i)(mu-Cl)(2)Li(THF)(2) (3), while similar reaction of complex 2 with LiNPh2 produced the neutral complex [(DIPPh)(2)nacnac]Yb(NPh2)Cl(THF) (4). Recrystallization of complex 3 from toluene solution at elevated temperature led to the neutral beta-diketiminate-lanthanide amido complex [{(DIPPh)(2)nacnac}Yb(NPr2i)(mu-Cl)](2) (5). The reaction medium has a significant effect on the outcome of the reaction

Topics: RING-OPENING POLYMERIZATION, OLEFIN POLYMERIZATION, BOND-CLEAVAGE, INTRAMOLECULAR HYDROAMINATION, POLY(METHYL METHACRYLATE), MOLECULAR-STRUCTURES, REAL CATALYSTS, EARTH-METALS, COMPLEXES, LIGAND, Ring-opening polymerization, Bond cleavage, Polymethylmethacrylate, Complexes, ligand, 开环聚合, Ring opening polymerization, 聚甲基丙烯酸甲酯, Methylmethacrylates, PMMA (Polymer), Poly(methyl alpha-methacrylate), Poly(methyl methacrylate), POLYMETHYL METHACRYLATE, POLYMETHYLMETHACRYLAT, lucite (trademark), plexiglass (trademark), Linear complexes, 配体
Year: 2006
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