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Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (8): 883-905.DOI: 10.6023/A14060434 Previous Articles     Next Articles

Review

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
  • 投稿日期:2014-06-03 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 Published:2014-07-07

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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