化学学报 ›› 2014, Vol. 72 ›› Issue (8): 883-905.DOI: 10.6023/A14060434 上一篇    下一篇

综述

稀土金属有机配合物化学60年

钱长涛, 王春红, 陈耀峰   

  1. 中国科学院上海有机化学研究所 金属有机国家重点实验室 上海 200032
  • 收稿日期:2014-06-03 出版日期:2014-08-14 发布日期:2014-07-07
  • 通讯作者: 钱长涛, 陈耀峰 E-mail:qianct@sioc.ac.cn;yaofchen@mail.sioc.ac.cn

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

Qian Changtao, Wang Chunhong, Chen Yaofeng   

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2014-06-03 Online:2014-08-14 Published:2014-07-07

60年来稀土金属有机配合物化学取得重要发展. 辅助配体从环戊二烯基,五甲基环戊二烯基,茚基发展到各种非茂配体,如双酚,β-二亚胺,胍基,脒基等. 配合物的种类从简单的三茂稀土配合物发展到各种形式的二茂稀土配合物和单茂稀土配合物. 非茂配体的应用不仅拓展了稀土金属有机配合物的结构种类,还极大推动稀土金属有机配合物在高分子和有机合成中的应用. 稀土金属有机配合物可有效催化烯烃均聚与共聚,共轭双烯烃以及极性单体的选择性聚合. 稀土金属有机配合物还能催化氢化,氢胺化和膦氢化等重要有机反应. 本文对稀土金属有机配合物化学过去60年的发展进行综述.

关键词: 稀土金属有机配合物, 镧系茂金属配合物, 配体设计, 合成, 催化

Rare-earth elements include scandium, yttrium and fifteen lanthanides. Since Wilkinson and Birmingham reported the fist example of rare-earth organometallic complex, the chemistry of rare-earth organometallic complexes has had a great advance during the past sixty years. A variety of Cp containing rare-earth metal complexes, including mono-Cp, bis-Cp, and tri-Cp complexes, have been synthesized. Variation of the size of substituent on Cp ring, introducing the nitrogen or oxygen containing pendant arm to Cp ring or using ansa bis-Cp ligands make the synthesis and stabilization of these three types of rare-earth metal Cp complexes available. The Cp related ligands, such as indenyl and fluorenyl, also have been applied for the rare-earth organometallic complexes. From 1990's, there was a tendency to explore the rare-earth organometallic complexes with ancillary ligands beyond Cp and its derivatives in order to search for more efficient rare-earth metal catalysts. Non-Cp ligands, such as biphenolates, β-diketiminates, amidinates, guanidinates, etc. have been introduced into the chemistry of rare-earth organometallic complexes, and a larger number of non-Cp rare-earth organometallic complexes have been synthesized and characterized. The application of non-cyclopentadienyl ligands not only resulted in the rare-earth organometallic complexes with new structural features, but also the catalysts with high activity and high selectivity for the polymer synthesis and organic synthesis. The rare-earth organometallic complexes catalyze homo- and co-polymerization of olefins as well as specific polymerization of dienes and polar monomers. The discovery of the catalytic system composed of the neutral rare-earth metal dialkyls/borate enables to synthesize some interesting polymers which are difficult to be prepared by using other catalytic system. The rare-earth organometallic complexes are also able to catalyze some important organic reactions, such as hydroamination, hydrophosphinylation, and hydroalkoxylation, etc. Different from the late-translation metal catalyzed organic reactions, most of the rare-earth metal catalyzed ones do not involve oxidative addition and reductive elimination steps. The review describes some important developments of the chemistry of rare-earth organometallic complexes in the past sixty years.

Key words: rare-earth organometallic complex, lanthanocene, ligand design, synthesis, catalysis