高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (9): 1501.

• 研究论文 • 上一篇    下一篇

二价钐配合物和异氰酸苯酯的反应——[(CH3C5H4)2(THF)Sm]2[μ-η4-(PhN)OCCO(NPh)]·2THF的合成、晶体结构及其催化性能

袁福根1, 沈琪2, 孙杰3   

  1. 1. 苏州铁道师范学院化学系, 苏州 215009;
    2. 苏州大学化学系, 苏州 215006;
    3. 中国科学院上海有机化学研究所金属有机开放实验室, 上海 200032
  • 收稿日期:2000-06-12 出版日期:2001-09-24 发布日期:2001-09-24
  • 通讯作者: 沈 琪(1940年出生),女,教授,博士生导师,主要从事金属有机化学研究.
  • 基金资助:

    国家自然科学基金(批准号:2967206229872031);铁道部专项基金(批准号:J98Z32);江苏省教育厅高校基金(批准号:00KJD150003);中国科学院上海有机化学研究所金属有机重点实验室基金资助

Reaction of Divalent Samarium Complexes with Phenyl Isocyanate Synthesis, Molecular Structure and Catalytic Activity of [(CH3C5H4)2(THF)Sm]2[μ-η4-(PhN)OCCO(NPh)]·2THF

YUAN Fu-Gen1, SHEN Qi2, SUN Jie3   

  1. 1. Department of Chemistry, Suzhou Railway Teacher's College, Suzhou 215009, China;
    2. Departmentof Chemistry, Suzhou University, Suzhou 215006, China;
    3. The Open Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
  • Received:2000-06-12 Online:2001-09-24 Published:2001-09-24

摘要: 报道了二价配合物(CH3C5H4)2Sm(THF)和SmI2(THF)x与异氰酸苯酯的反应.(CH3C5H4)2Sm(THF)和异氰酸苯酯反应生成配合物[(CH3C5H4)2(THF)Sm]2[μ-η4-(PhN)OCCO(NPh)]·2THF(1),而SmI2(THF)x则被异氰酸苯酯氧化为[SmI2(THF)5][SmI4(THF)2].(CH3C5H4)2Sm(THF)和配合物1都能催化异氰酸苯酯的齐聚反应.(CH3C5H4)2Sm(THF)和异氰酸苯酯作用生成配合物1的反应可以认为是(CH3C5H4)2Sm(THF)催化异氰酸苯酯齐聚的引发反应,而配合物1是该齐聚反应的活性中间体.X射线衍射分析表明,配合物1是一个由草酰胺双负离子桥联的双金属化合物.

关键词: 钐, 催化, 齐聚, 异氰酸苯酯

Abstract: This article describes the reaction of divalent complexes (CH3C5H4)2Sm(THF) and SmI2(THF)x with phenyl isocyanate.(CH3C5H4)2Sm(THF) reacts with phenyl isocyanate to give the product of [(CH3C5H4)2(THF)Sm]2[μη4 (PhN)OCCO(NPh)]·2THF(1), while SmI2(THF)x was oxidated to be [SmI2(THF)5][SmI4(THF)2] in PhNCOsolution. (CH3C5H4)2Sm(THF) and complex 1 display a catalytic activity for the oligomerization of phenyl isocyanate. The reaction of(CH3C5H4)2Sm(THF) with PhNCO to form complex 1 can be thought as the initiation reaction and complex 1 may be considered to be the real active species for the PhNCOoligomerization with the catalyst of(CH3C5H4)2Sm(THF). The structure of complex 1 was determined by X-ray diffraction analysis and confirmed to be a bimetallic complex with a dianionic oxamide ligand.

Key words: Samarium, Catalytic, Oligomerization, Phenyl isocyanate

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