Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method  

ONIOM方法计算胺和二芳基碳正离子的亲核反应的速率常数

作　　者：张志平[1] 王晨[1] 傅尧[1] 郭庆祥[1] 

机构地区：[1]中国科学技术大学化学系,合肥230026

出　　处：《Chinese Journal of Chemical Physics》2010年第6期669-674,745,共7页化学物理学报（英文）

摘　　要：The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.

关 键 词：AMINE Diarylcarbenium ion Nucleophilic reaction Rate constant N-layered integrated molecule orbit and molecule mechanics 

分 类 号：O[理学]