Efficient and Recyclable RuCl 3 ⋅ 3H 2 O Catalyst Modified with Ionic Diphosphine for the Alkoxycarbonylation of Aryl Halides.

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 RuCl3  ⋅ 3H2 O. With the involvement of the ionic diphosphine ( L4 ), in which the two phosphino-fragments were linked by butylene group, RuCl3  ⋅ 3H2 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 RuCl3  ⋅ 3H2 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 RuCl3  ⋅ 3H2 O catalyst. In addition, the L4 -based RuCl3  ⋅ 3H2 O system could be recycled successfully for at least eight runs in the ionic liquid [Bmim]PF6 .