Zhao Chongyang, Ma Xinyou, Wu Xiangyu, Thomsen Ditte L, Bierbaum Veronica M, Xie Jing
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
J Phys Chem Lett. 2021 Aug 5;12(30):7134-7139. doi: 10.1021/acs.jpclett.1c01665. Epub 2021 Jul 23.
Direct dynamics simulation of singly hydrated peroxide ion reacting with CHCl reveals a new product channel that forms CHOH + Cl + HOOH, besides the traditional channel that forms CHOOH + Cl + HO. This finding shows that singly hydrated peroxide ion behaves as a dual nucleophile through proton transfer between HOO(HO) and HO(HOOH). Trajectory analysis attributes the occurrence of the thermodynamically and kinetically unfavored HO-induced pathway to the entrance channel dynamics, where extensive proton transfer occurs within the deep well of the prereaction complex. This study represents the first example of a single solvent molecule altering the nucleophile in a gas-phase ion-molecule nucleophilic substitution reaction, in addition to reducing the reactivity and affecting the dynamics, signifying the importance of dynamical effects of solvent molecules.
单水合过氧离子与CHCl反应的直接动力学模拟揭示了一个新的产物通道，该通道除了形成CHOOOH + Cl + HO的传统通道外，还会形成CHOH + Cl + HOOH。这一发现表明，单水合过氧离子通过HOO(HO)和HO(HOOH)之间的质子转移表现为双亲核试剂。轨迹分析将热力学和动力学上不利的HO诱导途径的出现归因于入口通道动力学，在预反应复合物的深阱内发生了广泛的质子转移。这项研究代表了气相离子-分子亲核取代反应中单个溶剂分子改变亲核试剂的首个例子，此外还降低了反应活性并影响了动力学，这表明溶剂分子动力学效应的重要性。
Zotero 插件