A Trade-off between Solvation and Collision Activation in Steering Competing E2 and S_(N)2 Dynamics  

作　　者：Hongyi Wang Xu Liu Siwei Zhao Gang Fu Wenqing Zhen Li Yang Jiaxu Zhang 

机构地区：[1]State Key Laboratory of Urban Water Resource and Environment,MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage,School of Chemistry and Chemical Engineering,Harbin Institute of Technology,Harbin 150001,P.R.China [2]College of Chemistry,Liaoning University,Shenyang 110036,P.R.China

出　　处：《Precision Chemistry》2024年第1期40-48,共9页精准化学（英文）

基　　金：supported by the State Key Lab of Urban Water Resource and Environment of Harbin Institute of Technology(No.ES202303);the National Natural Science Foundation of China(No.22203039).

摘　　要：The prototypical E2 elimination and SN2 sub-stitution reactions between microsolvated fluoride and ethyl bromide show unexpected dynamic behaviors in mechanistic evolution driven by solvation and collision activation.Considering the steric effects,the gas-phase selectivity favors an E2 pathway barely dependent on collision energies.Remarkably,base solvation steers the reaction in an effective way toward substitution at a near-thermal energy,whereas the governing high-energy events retain elimination.Chemical dynamics simulations reproduce exper-imental findings and uncover a crucial solute-solvent coupling in determining such competing processes.Interestingly,collision activation can tune the underlying atomistic dynamics essentially in the reactant entrance channel and cause a mechanism shift.These features for the ubiquitous competing E2/SN2 dynamics remain quite unknown,providing unique insight into reaction selectivity for complex chemical networks.

关 键 词：E2/S_(N)2 Competition Atomistic Dynamics Reaction Mechanisms MICROSOLVATION Collision Activation 

分 类 号：O62[理学—有机化学]