Synthesis, characterization and catalytic activity of organolanthanide(II) complexes with heterocyclic-functionalized fluorenyl ligands

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• 作者：Yun Wei ; Zeyan Yu ; Shaowu Wang ; Shuangliu Zhou ; Gaosheng Yang ; Lijun Zhang ; Guodong Chen ; Huimin Qian ; Jiaxi Fan
• 关键词：Synthesis ; Catalysis ; Polymerization ; Organolanthanide(II) complexes ; Ligands
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：15 June 2008
• 卷：693
• 期：13
• 页码：2263-2270
• 文件大小：387 K

摘要

Two series of new organolanthanide(II) complexes with tetrahydro-2H-pyranyl- or N-piperidineethyl-functionalized fluorenyl ligands were synthesized via one-electron reductive elimination reaction. Treatments of [(Me₃Si)₂N]₃Ln^III(μ-Cl)Li(THF)₃ with 2 equiv. of C₅H₉OCH₂C₁₃H₉ (1) or C₅H₁₀NCH₂CH₂C₁₃H₉ (2), respectively, in toluene at about 80 °C produced, after workup, the corresponding organolanthanide(II) complexes with formula [η⁵:η¹-C₅H₉OCH₂C₁₃H₈]₂Ln^II (Ln = Yb (3), Ln = Eu (4)) and [η⁵:η¹-C₅H₁₀NCH₂CH₂C₁₃H₈]₂Ln^II (Ln = Yb (5), Ln = Eu (6)) in good yields. All the compounds were fully characterized by spectroscopic methods and elemental analyses. The structures of complexes 3, 4, and 6 were additionally determined by single-crystal X-ray analyses. It represents the first example of solvent-free organolanthanide(II) complexes with fluorenyl ligands. The catalytic properties of the organolanthanide(II) complexes on the polymerization of ε-caprolactone and methyl methacrylate have been studied. The temperatures, solvents and coordination effects on the catalytic activities of the complexes were examined.