对“应用量子化学计算理解溶剂对CH_(3)O^(-)/CH_(3)S^(-)亲核性的影响”的思考与拓展

Comment and Improvement on“Understanding the Effect of Solvents on the Nucleophilicity of CH_(3)O−/CH_(3)S−Using Quantum Chemical Calculations”

本文对近期发表于本刊的论文(题目中所示)展开讨论,结合近期溶剂化作用的科研进展,以期更全面地运用量子化学理解溶剂化效应对离子-分子型亲核取代S_(N)2反应的影响。我们增加了可视化图像展示亲核试剂CH_(3)O^(-)/CH_(3)S^(-)的差异,对比气、液相反应势能曲线揭示溶剂化降低亲核性的本质,并且考虑了不同类型的溶剂,使用物理意义明确的前线分子轨道模型阐释溶剂化效应。我们希望通过本文的有益探讨,完善该计算化学辅助有机化学的教学案例。

Herein we comment on and discuss the article mentioned in the title,“Understanding the Effect of Solvents on the Nucleophilicity of CH_(3)O^(−)/CH_(3)S^(−)Using Quantum Chemical Calculations”,which was published in this journal.By implementing the recent advances in solvent effect,we intend to use quantum chemistry to improve the understanding of students towards solvent effect on ion-molecular nucleophilic substitution(S_(N)2)reactions.We have added visualization examples to demonstrate the different properties of nucleophiles CH_(3)O^(−)and CH_(3)S^(−),uncovered the nature of how solvation weakens the nucleophilicity through comparing the potential energy profiles in gas and liquid phases,considered different types of solvents,and employed frontier molecular orbital model to illustrate the solvation effect.We anticipate the work herein can improve this teaching case as a model for organic chemistry assisted by computational chemistry.