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Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method
张志平,王晨,傅尧*,郭庆祥*
Author NameAffiliationE-mail
张志平 Department of Chemistry, University of Science and Technology of China, Hefei 230026, China  
王晨 Department of Chemistry, University of Science and Technology of China, Hefei 230026, China  
傅尧* Department of Chemistry, University of Science and Technology of China, Hefei 230026, China fuyao@ustc.edu.cn 
郭庆祥* Department of Chemistry, University of Science and Technology of China, Hefei 230026, China qxguo@ustc.edu.cn 
Abstract:
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 exam-ined. 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.
Key words:  Amine, Diarylcarbenium ion, Nucleophilic reaction, Rate constant, N-layered integrated molecule orbit and molecule mechanics
FundProject:
ONIOM方法计算胺和二芳基碳正离子的亲核反应的速率常数
Zhi-ping Zhang,Chen Wang,Yao Fu*,Qing-xiang Guo*
摘要:
利用第一性原理计算了胺和二芳基碳正离子的亲核反应的速率常数. 研究不同的溶剂化模型(PCM、CPCM和COSMORS)、不同类型的原子半径(UA0、UAKS、UAHF、Bondi和UFF)、以及一些单点能计算方法(B3LYP、B3P86、B3PW91、BHANDH、BMKPBEPBE、M06、MP2和ONIOM)在计算这类速率常数时的表现.通过比较速率常数的实验值和计算值,发现ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))//B3LYP/6-31G(d)/PCM/UFF方法表现最好. 该方法随后被用于计算更多的胺和二芳基碳正离子的亲核反应的速率常数. 65个反应的速率常数的实验值和计算值之间表现出了相当好的相关性,这表明该方法适用于计算胺二芳基碳正离子的亲核反应的速率常数.
关键词:  胺,二芳基碳正离子,亲核反应,速率常数, ONIOM
DOI:10.1088/1674-0068/23/06/669-674
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