对“应用量子化学计算理解溶剂对CH3O−/CH3S−亲核性的影响”的思考与拓展

doi:10.3866/PKU.DXHX202211018

Abstract

Abstract:

Herein we comment on and discuss the article mentioned in the title, "Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ 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_N2) reactions. We have added visualization examples to demonstrate the different properties of nucleophiles CH₃O⁻ and CH₃S⁻, 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.

Key words: Bimolecular nucleophilic substitution (S_N2) reaction, Solvent effect, Quantum chemistry calculation, Frontier molecular orbital theory, Visualization

Zhexuan Song, Yang Hu, Xiangyu Wu, Jing Xie. Comment and Improvement on "Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations"[J].University Chemistry, 2023, 38(9): 280-286.

Figures/Tables 4

References 15

1	邢其毅; 裴伟伟; 徐瑞秋; 裴坚. 基础有机化学, 第4版北京: 北京大学出版社, 2016, 242- 247.
2	K. 彼得∙C. 福尔哈特, 尼尔∙E. 肖尔. 有机化学: 结构与功能. 第8版. 戴立信, 席振峰, 罗三中, 等译. 北京: 化学工业出版社, 2020: 248–254.
3	Chabinyc M. L. ; Craig S. L. ; Regan C. K. ; Brauman J. I. Science 1998, 279, 1882. doi: 10.1126/science.279.5358.1882
4	Mikosch J. ; Trippel S. ; Eichhorn C. ; Otto R. ; Lourderaj U. ; Zhang J. ; Hase W. ; Weidemüller M. ; Wester R. Science 2008, 319, 183. doi: 10.1126/science.1150238
5	Xie J. ; Hase W. L. Science 2016, 352, 32. doi: 10.1126/science.aaf5172
6	Regan C. K. ; Craig S. L. ; Brauman J. I. Science 2002, 295, 2245. doi: 10.1126/science.1068849
7	朱荣秀; 王小莫; 郭今心; 张冬菊. 大学化学, 2023, 38 (2), 271.
8	Xie J. ; Sun R. ; Siebert M. R. ; Otto R. ; Wester R. ; Hase W. L. J. Phys. Chem. A 2013, 117, 7162. doi: 10.1021/jp4008027
9	Wu X. ; Zhao C. ; Xie J. ChemPhysChem 2022, 23, e202200285. doi: 10.1002/cphc.202200285
10	Ji X. ; Zhao C. ; Xie J. Phys. Chem. Chem. Phys. 2021, 23, 6349. doi: 10.1039/D0CP06299E
11	Hansen T. ; Roozee J. C. ; Bickelhaupt F. M. ; Hamlin T. A. J. Org. Chem. 2021, 87, 1805.
12	Zhao Y. ; Truhlar D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x
13	Marenich A. V. ; Cramer C. J. ; Truhlar D. G. J. Phys. Chem. B 2009, 113, 6378. doi: 10.1021/jp810292n
14	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; et al. Gaussian 09, Revision D. 01; Gaussian, Inc. : Wallingford, CT, USA, 2013.
15	NIST Chemistry WebBook. [2022-11-03]. https://webbook.nist.gov

类型	溶剂	ε	ΔG_O^‡	G_{sol, react.}	G_{sol, TS}	ΔG_{sol, O}	ΔG_S^‡	G_{sol, react.}	G_{sol, TS}	ΔG_{sol, S}	ΔΔG_{sol, S-O}	ΔΔG_S-O^‡
气相		1	−16.4	–	–	–	13.6	–	–	–	0.0	30.0
非质子	氯仿	4.7113	46.9	−239.8	−176.5	63.3	66.9	−226.0	−172.6	53.3	−10.0	20.0
	丙酮	20.493	55.7	−276.6	−204.6	72.0	77.1	−269.7	−206.2	63.5	−8.5	21.4
	乙腈	35.688	61.1	−284.6	−207.2	77.5	78.4	−274.0	−209.2	64.8	−12.7	17.3
质子溶剂	苯硫酚	4.2728	45.0	−223.9	−162.5	61.4	65.0	−216.2	−164.8	51.4	−10.0	20.0
	乙醇	24.852	84.4	−330.3	−229.6	100.8	76.8	−271.4	−208.2	63.2	−37.6	−7.6
	甲醇	32.613	89.9	−343.4	−237.1	106.2	77.4	−273.5	−209.7	63.8	−42.4	−12.5
	水	78.355	94.2	−340.1	−229.5	110.6	77.1	−258.7	−195.2	63.5	−47.1	−17.1

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Comment and Improvement on "Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations"

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Comment and Improvement on "Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations"