The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to C...The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).展开更多
基金Financial support from National Natural Science Foundation of China (22078336, U1662133, 21773158, 22008238)Innovation Academy for Green Manufacture, CAS (IAGM2020C13) is gratefully acknowledged
文摘The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).
