应用量子化学计算理解溶剂对CH3O−/CH3S−亲核性的影响

doi:10.3866/PKU.DXHX202206035

大学化学 >> 2023, Vol. 38 >> Issue (2): 271-276.doi: 10.3866/PKU.DXHX202206035

应用量子化学计算理解溶剂对CH₃O⁻/CH₃S⁻亲核性的影响

朱荣秀(), 王小莫, 郭今心, 张冬菊()

山东大学化学与化工学院, 济南 250100

收稿日期:2022-06-13 录用日期:2022-08-19 发布日期:2022-08-26
通讯作者: 朱荣秀,张冬菊 E-mail:rxzhu@sdu.edu.cn;zhangdj@sdu.edu.cn
基金资助:
山东大学教育教学改革研究项目(2022Y072);山东大学教育教学改革研究项目(2022Y076)

Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations

Rongxiu Zhu(), Xiaomo Wang, Jinxin Guo, Dongju Zhang()

School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China

Received:2022-06-13 Accepted:2022-08-19 Published:2022-08-26
Contact: Rongxiu Zhu, Dongju Zhang E-mail:rxzhu@sdu.edu.cn;zhangdj@sdu.edu.cn

摘要/Abstract

摘要：

溶剂对亲核试剂亲核性的影响是有机化学课程中的重要教学内容。本文以CH₃O⁻/CH₃S⁻与CH₃Cl的双分子亲核取代反应为例，设计了一个计算化学与有机化学相结合的教学案例，通过量子化学计算直观地描述了反应的分子机理，获得了反应的热力学和动力学信息，据此分析了溶剂对亲核试剂亲核性的影响，给出了表征亲核能力的亲核指数。

关键词: 亲核性, 双分子亲核取代, 溶剂效应, 密度泛函理论计算

Abstract:

The effect of solvents on the nucleophilicity of nucleophiles is an important teaching topic in organic chemistry. Considering the bimolecular nucleophilic substitution (S_N2) reaction between methoxide (CH₃O⁻) and thiomethoxide (CH₃S⁻) anions with chloroform (CH₃Cl) as a representative example, this paper designs a teaching case for integrating computational chemistry into the organic chemistry curriculum. By performing quantum chemical calculations, we determined the reaction mechanism, obtained the thermodynamic and kinetic information of the reactions, and investigated the effect of solvents on the properties of nucleophiles. Polar protic solvents, such as methanol and water, and polar aprotic solvents, such as acetone, acetonitrile, and chloroform, were analyzed. The nucleophilic index was also calculated to evaluate the nucleophilic reactivities of CH₃O⁻ and CH₃S⁻.

Key words: Nucleophilicity, S_N2 reaction, Solvent effect, DFT calculations

朱荣秀, 王小莫, 郭今心, 张冬菊. 应用量子化学计算理解溶剂对CH₃O⁻/CH₃S⁻亲核性的影响[J]. 大学化学, 2023, 38(2): 271-276.

Rongxiu Zhu, Xiaomo Wang, Jinxin Guo, Dongju Zhang. Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations[J]. University Chemistry, 2023, 38(2): 271-276.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.3866/PKU.DXHX202206035

https://www.dxhx.pku.edu.cn/CN/Y2023/V38/I2/271

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参考文献 10

1	Xie J. ; Hase W. L. Science 2016, 352, 32. doi: 10.1126/science.aaf5172
2	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.
3	胡春. 有机化学, 第2版北京: 中国医药科技出版社, 2013, 209- 220.
4	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.
5	Zhao Y. ; Truhlar D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x
6	Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F. NBO 5.0; Theoretical Chemistry Institute, University of Wisconsin: Madison, WI, USA, 2001.
7	Raghavachari K. ; Trucks G. W. ; Pople J. A. ; Head-Gordon M. Chem. Phys. Lett. 1989, 157, 479. doi: 10.1016/S0009-2614(89)87395-6
8	Zhuo L. G. ; Liao W. ; Yu Z. X. Asian J. Org. Chem. 2012, 1, 336. doi: 10.1002/ajoc.201200103
9	Domingo L. R. ; Perez P. Org. Biomol. Chem. 2011, 9, 7168. doi: 10.1039/c1ob05856h
10	Szabó I. ; Csaszar A. G. ; Czakó G. Chem. Sci. 2013, 4, 4362. doi: 10.1039/c3sc52157e

势能面各驻点	极性非质子溶剂						极性质子溶剂
	氯仿		丙酮		乙腈		甲醇		水
	CH₃O⁻	CH₃S⁻	CH₃O⁻	CH₃S⁻	CH₃O⁻	CH₃S⁻	CH₃O⁻	CH₃S⁻	CH₃O⁻	CH₃S⁻
孤立反应物	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0
IM0	20.5	25.8	25.7	27.3	25.9	25.6	31.7	27.6	24.5	25.7
TS0	25.3	27.7	30.9	28.6	31.8	33.1	30.0	33.7	33.2	34.2
IM1	23.9	26.4	29.5	27.6	32.1	26.9	332.6	26.7	32.1	26.2
TS1	50.5	65.5	58.7	75.6	60.4	77.1	87.6	76.0	89.4	76.4
IM2	−155.8	−109.2	−165.9	−111.4	−162.8	−112.7	−107.0	−112.0	−101.5	−111.7
产物+Cl⁻	−178.0	−129.4	−187.6	−131.6	−184.2	−131.5	−127.8	−131.9	−121.2	−130.4

溶剂模型	亲核试剂	溶剂	HOMO能级/eV	N/eV	溶剂模型	亲核试剂	溶剂	HOMO能级/eV	N/eV
隐含溶剂(SMD)	CH₃O⁻	H₂O	−7.28	4.18	隐含+ 显含溶剂	CH₃O⁻	H₂O	−10.17	1.29
	CH₃O⁻	CH₃OH	−7.13	4.36		CH₃O⁻	CH₃OH	−9.86	1.63
	CH₃S⁻	H₂O	−5.85	5.60		CH₃S⁻	H₂O	−7.58	3.88
	CH₃S⁻	CH₃OH	−5.76	5.73		CH₃S⁻	CH₃OH	−7.50	4.00

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应用量子化学计算理解溶剂对CH₃O⁻/CH₃S⁻亲核性的影响

Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations

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