原子与分子物理学报2017，Vol.34Issue(6)：1011-1016,6.DOI:10.3969/j.issn.1000-0364.2017.06.005
FeCl3催化2-(1-丙炔基)-2'-乙酰基联苯环化反应的机理研究
Theoretical investigation on the mechanism of FeCl3-catalyzed cyclization reaction of 2-(1-propinyl) -2' -acetyl biphenyl
摘要
Abstract
Density functional theory (DFT) with B3LYP function was employed to study the mechanism of 2-(1-propinyl) -2' -acetylbiphenyl intramolecular cyclization reaction. The calculation results show that the re-action can occur through both the four-membered and the eight-membered ring pathways with FeCl3 catalyst or without catalyst. Under the two conditions, the rate determining steps of the two pathways are the processes of the formations of the four-membered ring intermediate and the eight-membered ring intermediate, respectively. Without the catalyst, the difference of the energy barriers of the rate determining steps of the two pathways of the reaction is only 6. 8 kJ · mol-1 , which exhibits that the two pathways are competitive. Under the existence of FeCl3 catalyst, the energy barrier of the rate determining step of the four-membered ring pathway is reduced to 137. 52 kJ·mol-1 ,which is 57. 4 kJ·mol-1 lower than that of the energy barrier of the eight-membered ring pathway. The low energy barrier shows clearly that the reaction catalyzed by FeCl3 occurs mainly through the four-membered ring pathway. Besides, the energy barrier of the rate determining step of the four-membered ring pathway with FeCl3 is 114. 23 kJ·mol-1 lower than that of the reaction without catalyst. These differences indi-cate that FeCl3 is an efficient catalyst which can increase the reaction rate and moderate the reaction condition.关键词
反应机理/FeCl3/密度泛函理论/菲衍生物/过渡金属Key words
Reaction mechanism/FeCl3/Density functional theory/Phenanthrene derivative/Transitional metal分类
化学化工引用本文复制引用
刘晓,朱元强,景亚,曹宁..FeCl3催化2-(1-丙炔基)-2'-乙酰基联苯环化反应的机理研究[J].原子与分子物理学报,2017,34(6):1011-1016,6.基金项目
油气藏地质及开发工程国家重点实验室开放基金资助项目(PLN1124) （PLN1124）
