Efficient and Recyclable RuCl3 ⋅ 3H2O Catalyst Modified with Ionic Diphosphine for the Alkoxycarbonylation of Aryl Halides |
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Authors: | Qing Zhou Lei Liu Wen-Di Guo Wen-Yu Liang Prof Yong Lu Prof Ye Liu |
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Institution: | Shanghai Key Laboratory of Green Chemistry & Chemical Processes, East China Normal University, 3663 North Zhongshan Road, 200062 Shanghai, China |
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Abstract: | 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 ⋅ 3H2O. With the involvement of the ionic diphosphine ( L4 ), in which the two phosphino-fragments were linked by butylene group, RuCl3 ⋅ 3H2O 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 ⋅ 3H2O 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 31P NMR for 1J31P-77Se1J measurement and single-crystal X-ray diffraction, were carefully co-related to the performance RuCl3 ⋅ 3H2O catalyst. In addition, the L4 -based RuCl3 ⋅ 3H2O system could be recycled successfully for at least eight runs in the ionic liquid Bmim]PF6. |
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Keywords: | Alkoxycarbonylation aryl halides ionic diphosphines Ru(III) complex catalyst recyclability |
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