Almatarneh Mansour H, Elayan Ismael A, Al-Sulaibi Mazen, Al Khawaldeh Ahmad, Saber Sedeeqa O W, Al-Qaralleh Mahmood, Altarawneh Mohammednoor
Department of Chemistry, University of Jordan, Amman 11942, Jordan.
Chemistry Department, Memorial University, St. John's, Newfoundland and Labrador A1B 3X7, Canada.
ACS Omega. 2019 Feb 14;4(2):3306-3313. doi: 10.1021/acsomega.8b02792. eCollection 2019 Feb 28.
A detailed computational study of the decomposition reaction mechanisms of -propylamine (-PA), -propylamine (-PA), and the cis-isomer of its protonated form (-HPA) has been carried out. Fourteen major pathways with their kinetic and thermodynamic parameters are reported. All reported reactions have been located with a concerted transition state, leading to significant products that agree with previous theoretical and experimental studies. Among six decomposition pathways of -PA, the formation of propene and NH is the significant one, kinetically and thermodynamically, with an activation energy barrier of 281 kJ mol. The production of two carbenes is found via two different transition states, where the reactions are thermodynamically controlled and reversible. Furthermore, five decomposition pathways of -PA have been considered where the formation of ethene, methylimine, and H is the most plausible one with an activation energy barrier of 334 kJ mol. The results show that the formation of propene and NH from the decomposition of -HPA is the most favorable reaction with an activation barrier of 184 kJ mol, that is, the lowest activation energy calculated for all decomposition pathways.
对正丙胺（n - PA）、异丙胺（i - PA）及其质子化形式的顺式异构体（i - HPA）的分解反应机理进行了详细的计算研究。报告了十四条主要反应途径及其动力学和热力学参数。所有报道的反应均通过协同过渡态定位，得到的主要产物与先前的理论和实验研究结果一致。在n - PA的六条分解途径中，从动力学和热力学角度来看，丙烯和NH的形成是主要途径，其活化能垒为281 kJ/mol。通过两种不同的过渡态发现了两种卡宾的生成，其中反应是热力学控制且可逆的。此外，还考虑了i - PA的五条分解途径，其中乙烯、甲亚胺和H的形成是最合理的途径，其活化能垒为334 kJ/mol。结果表明，i - HPA分解生成丙烯和NH是最有利的反应，活化能垒为184 kJ/mol，即所有分解途径计算得到的最低活化能。
