Open AccessEfficient and Recyclable RuCl 3 ⋅ 3H 2 O Catalyst Modified with Ionic Diphosphine for the Alkoxycarbonylation of Aryl Halides
Author(s) -
Zhou Qing,
Liu Lei,
Guo WenDi,
Liang WenYu,
Lu Yong,
Liu Ye
Publication year - 2019
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201800266
Subject(s) - halide , steric effects , ionic liquid , aryl , catalysis , chemistry , ionic bonding , selectivity , medicinal chemistry , organic chemistry , ion , alkyl
A series of ionic (mono‐/di‐)phosphines ( L2 , L4 , and L6 ) with structural similarity and their corresponding neutral counterparts ( L1 , L3 , and L5 ) were applied to modulate the catalytic performance of RuCl 3 ⋅ 3H 2 O. With the involvement of the ionic diphosphine ( L4 ), in which the two phosphino‐fragments were linked by butylene group, RuCl 3 ⋅ 3H 2 O with advantages of low cost, robustness, and good availability was found to be an efficient and recyclable catalyst for the alkoxycarbonylation of aryl halides. The L4 ‐based RuCl 3 ⋅ 3H 2 O system corresponded to the best conversion of PhI (96 %) along with 99 % selectivity to the target product of methyl benzoate as well as the good generality to alkoxycarbonylation of different aryl halides (ArX, X=I and Br) with alcohols MeOH, EtOH, i ‐PrOH and n ‐BuOH. The electronic and steric effects of the applied phosphines, which were analyzed by the 31 P NMR for 1 J 31 P‐ 77 Se 1 J measurement and single‐crystal X‐ray diffraction, were carefully co‐related to the performance RuCl 3 ⋅ 3H 2 O catalyst. In addition, the L4 ‐based RuCl 3 ⋅ 3H 2 O system could be recycled successfully for at least eight runs in the ionic liquid [Bmim]PF 6 .