文献类型：期刊文献

英文题名：Highly selective ethylene trimerization catalyzed by half-sandwich indenyl titanium complexes with pendant arene groups and MAO

作者：Zhang, Yanlu[1];Ma, Haiyan[1];Huang, Jiling[1]

机构：[1]E China Univ Sci & Technol, Lab Organometall Chem, Shanghai 200237, Peoples R China

年份：2013

卷号：373

起止页码：85

外文期刊名：JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL

收录：;EI(收录号：20131916311310);WOS:【SCI-EXPANDED(收录号:WOS:000319242800012)】；

基金：This work is subsidized by the National Basic Research Program of China (2005CB623801), National Natural Science Foundation of China (20774027, 21274041), and Key Project of Chinese Ministry of Education (109064). All the financial supports are gratefully acknowledged.

语种：英文

外文关键词：Titanium; Indenyl; Pendant arene; Ethylene; Trimerization

摘要：A series of half-sandwich indenyl titanium complexes [Ind-(bridge)-Ar]TiCl3 (C1-C9) bearing pendant arene group on indenyl ring have been synthesized and used for the catalytic ethylene trimerization to 1-hexene in the presence of MAO. The molecular structures of complexes C3 [Ind-C(cydo-C5H10)-Ph]TiCl3 and C5 [Ind-C(cyclo-C5H10)-(p-MePh)]TiCl3 have been established by single-crystal X-ray diffraction study. No intramolecular coordination interaction between the arene moiety and the titanium center could be observed in the solid state of these complexes. At 0 degrees C and 0.8 MPa of ethylene pressure, upon activation with MAO, C3 possesses the highest activity of 1968 kg of 1-hexene/(mol-Tih) and the overall selectivity of 95.9% by mass for 1-hexene, and is also more active than the corresponding cyclopentadienyl analog [Cp-C(cyclo-C5H10)-Ph]TiCl3 (C10) under the identical conditions. The substituents of various steric and electronic effects on the pendant arene group and the bridge unit between the indenyl and this arene group exert great influence on the activity and selectivity of these indenyl titanium complexes for ethylene trimerization to 1-hexene. Similar to cyclopentadienyl analogs, upon activation with MAO the resultant indenyl catalytic systems also show great sensitivity to the temperature. With the increase of the reaction temperature, both the activity and selectivity of 1-hexene declined. (C) 2013 Elsevier B.V. All rights reserved.