高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (10): 1683.

• 论文 • 上一篇    下一篇

茂钛配合物-纳米氢化钠双组分高活性加氢催化剂的研究

范荫恒2, 廖世健1, 徐筠1, 钱廷龙3, 黄吉玲3   

  1. 1. 辽宁师范大学化学系, 大连 116029;
    2. 中国科学院大连化学物理研究所, 大连 116023;
    3. 华东理工大学应用化学研究所, 上海 200237
  • 收稿日期:1996-08-27 出版日期:1997-10-24 发布日期:1997-10-24
  • 通讯作者: 廖世健
  • 作者简介:范荫恒, 男, 50岁, 副教授.
  • 基金资助:

    国家自然科学基金;中国科学院上海有机化学研究所金属有机开放实验室资助

Highly Active Hydrogenation Catalysts from Titanocenes and Sodium Hydride of Nanometric Size

FAN Yin-Heng2, LIAO Shi-Jian1, XU Jun1, QIAN Yan-Long3, HUANG Ji-Ling3   

  1. 1. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023;
    2. Department of Chemistry, Liaoning Normal University, Dalian 116029;
    3. Institute of Applied Chemistry, East China University of Science and Technology, Shanghai 200237
  • Received:1996-08-27 Online:1997-10-24 Published:1997-10-24

摘要: 提出了带有不同取代基的茂钛配合物与纳米氢化钠(NaH*)组成的高活性加氢催化剂.在常温常压下,取代茂钛配合物(这里有图片)<19971027-1.gif> TiCL2NaH*对I-己烯的加氢反应有极高的初始活性,TOFmax达到110mol H2/(molTi·s)催化转换数达到22200molH2(molTi)该催化体系对底物有明显的专一选择性,只有端烯烃才能发生加氢反应,且无异构化副反应发生.纳米氢化钠的助剂作用是该催化体系高活性的关键因素.

关键词: 取代茂钛配合物, 纳米氢化钠, 催化加氢, 烯烃

Abstract: The hydrogenation of 1-hexene was catalyzed by titanocene with varioussubstituted groups in combination with nanometric sodium hydride. When the steric hindrance ofthe substituted group on the cyclopentadienyl ring is relatively small, the titanium complexgives high initial catalytic activity but poor stability, whereas when the steric hindrance islarge (for instance, five-membered ring or six-membered ring), the titanium complex giveslower initial catalytic acitivty but better stabilty. At normal temperature and pressure, amaximum turnover frequency(TOFmax) of H2/(mol Ti·s) and a turnover(TO) of22200 mol H2/(mol Ti) were obtained by using bis [(1'-ethyl)cyclohexyl-cyclopentadiTiCl2/NaH*as catalyst. Only the terminal olefin could be hydrogenated by using this kind ofcatalytic system. Isomerization of olefins did not occur in the course of hydrogenation. It isthe key factor that the nanometric NaH*was used as the cocatalyst in the reaction. Thecombination of titanocenes with commercial sodium hydride which was synthesized at hightemperatures did not display any catalytic activity for the hydrogenation of 1-hexene.

Key words: Titanocenes, Nanometric sodium hydride, Catalytic hydrogenation, Olefins

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