有机化学 ›› 2001, Vol. 21 ›› Issue (11): 1040-1045. 上一篇    下一篇

研究论文

由富烯配体合成茂金属化合物的研究

白生弟;魏学红;原欣亮;刘滇生   

  1. 山西大学化学系.太原(030006)
  • 发布日期:2001-11-25

Study on synthesizing metallocenes from fulvenes

Bai Shengdi;Wei Xuehong;Yuan Xinliang;Liu Diansheng   

  1. Shanxi Univ., Dept of Chem.Taiyuan(030006)
  • Published:2001-11-25

报道了一系列富烯包括烷基取代富烯、6-氨基富烯和具有稠环结构的6-氨基苯并富烯经由去氢或加成反应合成取代二茂金属络合物;(1-二甲氨基)乙烯基环戊二烯基锂与过渡金属的络合反应在一定条件下可以发生分子内碳碳偶联及二甲基胺的消除反应,得到丙烯桥联茂金属化合物,从推导的反应历程提出该反应的反应机理;尚合成了两个新的外消旋手性化合物。

关键词: 富烯, 去氢, 加成反应, 稠环化合物, 配体, 合成, 金属茂络合物, 氨基, 环戊二烯基

Fulvenes are one of the most important starting materials for synthesizing metallocenes. Reported here is a study on synthesis of metallocenes from a series of fulvenes (including alkylfulvenes, 6- aminofulvenes and 6-aminobenzofulvenes) via deprotonation or addition reaction. When treating 6-dimethylamino-6-methylfulvene with ZrCl4, it was found that an intramolecular C-C coupling and a NMe2H elimination reaction occurred leading to the formation of a novel allyl-bridged metallocene. The mechanism is discussed in detail. The chiral complexes were also synthesized from 6-dimethylamino-6- methylbenzofulvene and 1-methyl-2- cyclopentadienenylpyrrolidine.

Key words: FULVENE, ADDITION REACTION, FUSED RING COMPOUNDS, LIGANDS, SYNTHESIS, METALLOCENES, AMINO GROUP, CYCLOPENTADIENYL GROUP

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