caa a22 4500 605487766 CHVBK 20210128100452.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00214-015-1634-6 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1634-6 Theoretical studies on the aminolysis mechanism of propylene carbonate with ammonia [Elektronische Daten] [Rong Chen, Xiaoling Luo, Guoming Liang] The possible mechanisms of the aminolysis reaction of propylene carbonate with ammonia were investigated by computational techniques. Optimized structures for all the stationary points were examined by employing the B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) methods. The uncatalyzed, base-catalyzed and acid-catalyzed aminolysis reactions were taken into account. Two possible mechanisms of the concerted process and the addition/elimination stepwise pathway are investigated, and the first stages of the stepwise mechanism for all pathways are the rate-limiting processes. The results indicate that the concerted process of non-catalyzed aminolysis has lower energy barrier in comparison with the stepwise mechanism. Concerning the base-catalyzed and acid-catalyzed aminolysis, the neutral stepwise pathway is more favorable than the concerted mechanism and the energy barriers of all steps are lower than those of the uncatalyzed aminolysis. The solvent effect by a polarized continuum model does not significantly change the conclusion. Springer-Verlag Berlin Heidelberg, 2015 Aminolysis of ester nationallicence Propylene carbonate nationallicence Catalytic role nationallicence Mechanism nationallicence PCM model nationallicence Chen Rong College of Chemistry, Chongqing Normal University, 401331, Chongqing, China aut Luo Xiaoling College of Chemistry, Chongqing Normal University, 401331, Chongqing, China aut Liang Guoming College of Chemistry, Chongqing Normal University, 401331, Chongqing, China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-12 1432-881X 134:3<1 2015 134 214 https://doi.org/10.1007/s00214-015-1634-6 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1634-6 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Chen Rong College of Chemistry, Chongqing Normal University, 401331, Chongqing, China aut NATIONALLICENCE 700 1- Luo Xiaoling College of Chemistry, Chongqing Normal University, 401331, Chongqing, China aut NATIONALLICENCE 700 1- Liang Guoming College of Chemistry, Chongqing Normal University, 401331, Chongqing, China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-12 1432-881X 134:3<1 2015 134 214