Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (9): 3571-3577.DOI: 10.6023/cjoc202104025 Previous Articles     Next Articles



刘欢, 林旭锋*(), 杨妲*()   

  1. 中国石油大学(华东)理学院化学系 山东青岛 266580
  • 收稿日期:2021-04-12 修回日期:2021-05-25 发布日期:2021-07-12
  • 通讯作者: 林旭锋, 杨妲
  • 基金资助:
    国家自然科学基金(21576291); 山东省自然科学基金(ZR2014BM002); 中国博士后科学基金(2019M662460); 青岛市博士后基金(05TB2010001); 自主创新科研计划(20CX06032A)

Novel Ir-Complexes for Hydroformylation of Olefins with H2O as the Hydrogen Source

Huan Liu, Xufeng Lin(), Da Yang()   

  1. Department of Chemistry, College of Science, China University of Petroleum, Qingdao, Shandong 266580
  • Received:2021-04-12 Revised:2021-05-25 Published:2021-07-12
  • Contact: Xufeng Lin, Da Yang
  • Supported by:
    National Natural Science Foundation of China(21576291); Natural Science Foundation of Shandong Province(ZR2014BM002); China Postdoctoral Science Foundation(2019M662460); Postdoctoral Applied Research Project of Qingdao City(05TB2010001); Fundamental Research Funds for the Central Universities(20CX06032A)

A series of novel Ir-complexes, namely Ir-L1, Ir-L2, Ir-L3 and Ir-L4, where L1~L4 represent phosphine ligands having different electronic and steric effects, were synthesized in this work. Then the effect of the as-synthesized phosphine ligands on the performance of the Ir(I)-complexes catalysts was investigated for the hydroformylation reaction using H2O as the hydrogen source. It was found that the Ir-complex modified by the ionic bi-dentate phosphines L4 with a strong π-accepting ability (1J31P-77Se =781 Hz) can effectively promote water gas shift reaction (WGSR) and hydroformylation of olefins at the same time. As a result, a 1-hexene conversion of 93% was obtained, and the total yields of the target (linear and branched) aldehydes were up to 93% when using the Ir-L4 catalyst. Meanwhile, the yield of hexane from the hydrogenation of 1-hexene was less than 1%, showing that the side reaction of olefin hydrogenation can be almost completely inhibited when using H2O as the hydrogen source. Moreover, by using the ionic liquid of [MePh3P]Br as the solvent, Ir-L4 catalyst can be efficiently recovered for at least 5 times.

Key words: ionic phosphines, iridium complexes, hydroformylation, water gas shift reaction