新型铱配合物催化水作氢源的氢甲酰化反应  

Novel Ir-Complexes for Hydroformylation of Olefins with H_(2)O as the Hydrogen Source

作　　者：刘欢 林旭锋 杨妲 Liu Huan;Lin Xufeng;Yang Da(Department of Chemistry,College of Science,China University of Petroleum,Qingdao,Shandong 266580)

机构地区：[1]中国石油大学(华东)理学院化学系,山东青岛266580

出　　处：《有机化学》2021年第9期3571-3577,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21576291);山东省自然科学基金(No.ZR2014BM002);中国博士后科学基金(No.2019M662460);青岛市博士后基金(No.05TB2010001);自主创新科研计划(No.20CX06032A)资助项目.

摘　　要：基于不同电子和空间效应的膦配体L1~L4,合成了一系列新型铱配合物Ir-L1~Ir-L4,考察了配体在铱配合物催化水作氢源的氢甲酰化反应中的影响.研究表明,具有较强π-受电子能力的离子型双齿膦配体L4(1J31P-77Se=781 Hz)修饰的铱配合物可以同时促进水煤气变换反应和烯烃氢甲酰化反应:以Ir-L4配合物为催化剂,1-己烯的转化率高达93%,产物醛(直链醛和支链醛)的收率为93%,1-己烯加氢副产物己烷的收率小于1%,表明水作氢源几乎完全抑制了烯烃加氢副反应.此外,Ir-L4催化体系结合离子液体([MePh3P]Br)还可实现催化剂的回收循环5次.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 strongπ-accepting ability(1 J31P-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.

关 键 词：离子型膦配体 铱配合物 氢甲酰化反应 水煤气变换反应 

分 类 号：O641.4[理学—物理化学] O621.251[理学—化学]