有机化学 ›› 2014, Vol. 34 ›› Issue (4): 821-828.DOI: 10.6023/cjoc201310047 上一篇    下一篇

研究简报

茚环3-位手性基团取代的桥联二茚锆络合物合成及表征

赵睿国a,b, 马海燕a   

  1. a 华东理工大学金属有机化学研究室 上海 200237;
    b 内蒙古大学化学化工学院 呼和浩特 010021
  • 收稿日期:2013-10-29 修回日期:2013-12-10 出版日期:2014-04-25 发布日期:2013-12-27
  • 通讯作者: 马海燕 E-mail:haiyanma@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 20774027,21274041)和中央高校基本科研业务费(No. WK1214048)资助项目.

Synthesis and Characterization of ansa-Bis(3-chiral groupsubstituted indenyl) Zirconium Complexes

Zhao Ruiguoa,b, Ma Haiyana   

  1. a Laboratory of Organometallic Chemistry, East China University of Science and Technology, Shanghai 200237;
    b School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021
  • Received:2013-10-29 Revised:2013-12-10 Online:2014-04-25 Published:2013-12-27
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 20774027, 21274041) and the Fundamental Research Funds for the Central Universities (No. WK1214048).

将(+)-新孟基和(+)-异莰基引入茚环结构中,合成得到三个茚环3-位手性基团取代的桥联二茚配体化合物1a3a. 利用这些配体化合物的二锂盐与四氯化锆反应,最终分离得到两个C2-对称的亚乙基桥联取代二茚锆络合物2b3b,相应具类内消旋结构、C1-对称的锆络合物2c3c未能分离得到纯品. 所有配体化合物和络合物均通过1H NMR、13C NMR、元素分析(或HRMS)的鉴定. 对络合物2c进一步用X射线单晶衍射测定了晶体结构. 2c属正交晶系,其空间群为P2(1)2(1)2(1),晶胞参数a=10.946(4) Å,b=13.377(4) Å,c=24.294(8) Å,α=β=γ=90°,Mr=694.94,V=3557(2) Å3Dc=1.298 g/cm3Z=4,F(000)=1464,μ=0.486 mm-1R=0.0296,wR=0.0683 [I>2sI)].

关键词: 手性基团取代茚, 桥联二茚配体, 茚锆络合物, 合成, 晶体结构

Ethylene or methylene bridged bis(indenyl) compounds 1a3a bearing chiral substituent have been obtained by introducing (+)-neomenthyl or (+)-isocamphyl to the 3-position of indenyl ring. Two C2-symmetric ethylene bridged bis(indenyl) zirconium complexes 2b and 3b have been isolated readily from the reaction of the dilithium salts of these compounds with zirconium tetrachloride. The purification of corresponding meso-like, C1-symmetric complexes 2c and 3c was however not successful. All of the proligand compounds and zirconium complexes have been characterized by 1H NMR, 13C NMR spectra and elemental analysis (or HRMS). The molecular structure of 2c was further determined by X-ray single crystal diffraction analysis. The crystal of 2c belongs to orthorhombic, space group P2(1)2(1)2(1) with cell parameters a=10.946(4) Å, b=13.377(4) Å, c=24.294(8) Å, α=β=γ=90°, Mr=694.94, V=3557(2) Å3, Dc=1.298 g/cm3, Z=4, F(000)=1464, μ=0.486 mm-1, R=0.0296 and wR=0.0683 [I>2s(I)].

Key words: chiral group substituted indene, bridged bis(indenyl) ligand, zirconium complex, synthesis, crystal structure