Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (9): 2315-2321.DOI: 10.6023/cjoc201703010 Previous Articles     Next Articles



刘睿a, 钟向宏bb, 刘振宇b, 梁胜彪b, 朱红平a   

  1. a 厦门大学化学化工学院 固体表面物理化学国家重点实验室 厦门 361005;
    b 中国石油化工股份有限公司茂名分公司 茂名 525011
  • 收稿日期:2017-03-03 修回日期:2017-05-05 发布日期:2017-05-17
  • 通讯作者: 钟向宏, 朱红平;
  • 基金资助:


Selective Ethylene Oligomerization Catalyzed by the Chromium Complex Bearing N-Tetrahydrofurfuryl PNP Ligand

Liu Ruia, Zhong Xianghongb, Liu Zhenyub, Liang Shengbiaob, Zhu Hongpinga   

  1. a State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005;
    b Maoming Branch R & D Institute, SINOPEC, Maoming 525011
  • Received:2017-03-03 Revised:2017-05-05 Published:2017-05-17
  • Contact: 10.6023/cjoc201703010;
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21473142, 21673191) and the Innovative Research Team Program (No. IRT_14R31).

The N-tetrahydrofurfuryl diphoshinoamine (PNP) ligand (E) was synthesized by means of two-step salt elimination reactions where separation of the two kinds of the aminyl lithium salts for the respective reactions is necessary for obtaining a high yield of E. The ligand reacted with CrCl3(THF)3 and Cr(CO)6 to give P,P-chelation complexes[{Ph2PN(CH2OC4H7)-PPh2}CrCl2(μ-Cl)]2 (1) and[Ph2PN(CH2OC4H7)PPh2]Cr(CO)4 (2), respectively. Complexes E, 1 and 2 were characterized by spectroscopy and elemental analysis, of which complex 2 was further confirmed by X-ray crystallography. Upon activation with methylaluminoxane (MAO) or AlEt3, the catalyst systems including 1, 2, E/CrCl3(THF)3, E/Cr(acac)3 and E/CrCl2(THF)2 were investigated. The best catalytic activity was achieved by 15.9 kg (product)/g (Cr)·h in which a selectivity of 63.6% for 1-C8 was obtained.

Key words: chromium complexes, catalytic property, ethylene tri-/tetramerization, catalytic reaction conditions