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二茂基环己氧基稀土化合物的合成、分子结构和催化活性
引用本文:袁福根,陈丽,翁林红,杨静.二茂基环己氧基稀土化合物的合成、分子结构和催化活性[J].有机化学,2003,23(7):646-649.
作者姓名:袁福根  陈丽  翁林红  杨静
作者单位:1. 苏州科技学院化学化工系,苏州,215009
2. 复旦大学化学系,上海,200433
基金项目:江苏省教育厅基金(No.00KJD150003),江苏省青蓝基金(No.HB2001-27),江苏省有机合成重点实验室基金(No.KJS01020)
摘    要:通过Cp_3Ln(Ln=Sm, Yb)和环己醇在THF溶剂中按1:1摩匀比反应,合成了标题 化合物Cp_2LnOC_6H_(11)]_2(Ln=Sm, Yb)。化合物经元素分析、红外光谱分析表 征。镱配合物经X单晶衍射分析。它是一个以氧原子为桥的二聚体,环己烷基呈椅 式构型,O-C(环己烷基)键处于平伏e键位置。在上述基础上,尝试了它对己内 酯的催化聚合反应,发现标题化合物对己内酯聚合具有一定的催化活性。进一步合 成了Cp_2YbOC_6H_(11)]与己内酯的1:4预聚反应产物,发现预聚物催化己内酯聚 合活性比标题化合物大大增强,从而说明催化聚合过程中引发反应速率慢是影响标 题化合物表观催化活性的重要因素。

关 键 词:钐络合物  镱络合物  己内酯  催化活性  X射线衍射分析  环己醇

Synthesis and Molecular Structure of Bis(cyclopentadienyl) Cyclohexyloxy Lanthanide Compounds and Their Catalytic Activity
YUAN,Fu-Gen CHEN,Li WEN,Lin-Hong YANG,Jing.Synthesis and Molecular Structure of Bis(cyclopentadienyl) Cyclohexyloxy Lanthanide Compounds and Their Catalytic Activity[J].Chinese Journal of Organic Chemistry,2003,23(7):646-649.
Authors:YUAN  Fu-Gen CHEN  Li WEN  Lin-Hong YANG  Jing
Institution:Department of Chemistry, University of Science and Technology of Suzhou;Department of Chemistry, Fudan University
Abstract:Reaction of CpjLn (Ln = Sm, Yb) with cyclohexanol in a 1:1 molar ratio afforded the title compounds CpjLnOC^Hn \ (Ln = Sm, Yb). They were characterized by elemental analysis and infrared spectrum. The ytterbium complex was analyzed by X-ray crystallography. It is a dimer with two oxygen atoms bridging two ytterbium atoms. The cyclohexyl group displays chair-shape configuration and the 0-C (cyclohexyl group) bond stretches as a level e-bond. C^LnOCgHn\ (Ln = Sm, Yb) showed rather poor catalytic activity for the polymerization of e- caprolactone. The 1:4 adduct of CpjYbOCgHn^ and e-caprolactone showed much better catalytic activity than its precursor C^YbOCfiHn^. This demonstrates that the slow reaction rate of initiation is an important factor to affect the apparent catalytic activity of Cr^YbOCgHnla for the polymerization of e-caprolactone.
Keywords:SAMARIUM COMPLEX  YTTERBIUM COMPLEX  CAPROLACTONE  CATALYTIC ACTIVITY  XRD  CYCLOHEXANOL
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