Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

Citation: OROZCO-VALENCIA Ulises, GÁZQUEZ José L., VELA Alberto. Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis[J]. Acta Physico-Chimica Sinica, 2018, 34(6): 692-698. doi: 10.3866/PKU.WHXB201801121 shu

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

1.
Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, Colonia San Pedro Zacatenco, Ciudad de México, 07360, México
2.
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340, México

通讯作者: VELAAlberto, avela@cinvestav.mx

基金项目:
UOV was supported in part by Conacyt through a doctoral fellowship. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867

摘要: A global and local charge transfer partitioning model, based on the cornerstone theory developed by Robert G. Parr and Robert G. Pearson, which introduces two charge transfer channels (one for accepting electrons (electrophilic) and another for donating (nucleophilic)), is applied to the reaction of a set of indoles with 4, 6-dinitrobenzofuroxan. The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles, i.e., the indoles under consideration transfer electrons to 4, 6-dinitrobenzofuroxan. Evaluating the reactivity descriptors with exchange-correlation functionals including exact exchange (global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals; however, the trends are preserved. Comparing the trend obtained with the number of electrons donated by the indoles, and predicted by the partitioning model, with that observed experimentally based on the measured rate constants, we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4, 6-dinitrobenzofuroxan. This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species; therefore, it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting. The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions, and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve, reaching an optimal correlation, which in the present case indicates keeping three atoms from the indoles and two from 4, 6-dinitrobenzofuroxan. The atoms selected by this procedure provide valuable information about the local reactivity of the indoles. We further show that this information about the most reactive atoms on each reactant, combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants, allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.

关键词:

English

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

1.
Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, Colonia San Pedro Zacatenco, Ciudad de México, 07360, México
2.
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340, México

Corresponding author: VELA Alberto, avela@cinvestav.mx

Received Date: 24 November 2017
Accepted Date: 05 January 2018
Revised Date: 29 December 2017
Available Online: 15 June 2018
Fund Project:
UOV was supported in part by Conacyt through a doctoral fellowship. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867

Abstract: A global and local charge transfer partitioning model, based on the cornerstone theory developed by Robert G. Parr and Robert G. Pearson, which introduces two charge transfer channels (one for accepting electrons (electrophilic) and another for donating (nucleophilic)), is applied to the reaction of a set of indoles with 4, 6-dinitrobenzofuroxan. The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles, i.e., the indoles under consideration transfer electrons to 4, 6-dinitrobenzofuroxan. Evaluating the reactivity descriptors with exchange-correlation functionals including exact exchange (global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals; however, the trends are preserved. Comparing the trend obtained with the number of electrons donated by the indoles, and predicted by the partitioning model, with that observed experimentally based on the measured rate constants, we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4, 6-dinitrobenzofuroxan. This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species; therefore, it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting. The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions, and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve, reaching an optimal correlation, which in the present case indicates keeping three atoms from the indoles and two from 4, 6-dinitrobenzofuroxan. The atoms selected by this procedure provide valuable information about the local reactivity of the indoles. We further show that this information about the most reactive atoms on each reactant, combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants, allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.

Key words:

1. [1]
  Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules, Revised ed.; Oxford University Press: New York, NY, USA, 1994.
2. [2]
  Chermette, H. J. Comput. Chem. 1999, 20, 129. doi: 10.1002/(Sici)1096-987x(19990115)20:1 < 129::Aid-Jcc13 > 3.0.Co; 2-A
3. [3]
  Geerlings, P.; De Proft, F.; Langenaeker, W. Chem. Rev. 2003, 103, 1793. doi: 10.1021/cr990029p
4. [4]
  Gázquez, J. L. J. Mex. Chem. Soc. 2008, 52, 3.
5. [5]
  Liu, S. B. Acta Phys. -Chim. Sin. 2009, 25, 590. doi: 10.3866/Pku.Whxb20090332
6. [6]
  Chattaraj, P. K.; Sarkar, U.; Roy, D. R. Chem. Rev. 2006, 106, 2065. doi: 10.1021/cr040109f
7. [7]
  Chattaraj, P. K.; Roy, D. R. Chem. Rev. 2007, 107, PR46. doi: 10.1021/cr078014b
8. [8]
  Chattaraj, P. K.; Giri, S.; Duley, S. Chem. Rev. 2011, 111, PR43. doi: 10.1021/cr100149p
9. [9]
  Pearson, R. G. Coord. Chem. Rev. 1990, 100, 403. doi: 10.1016/0010-8545(90)85016-l
10. [10]
  Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512. doi: 10.1021/Ja00364a005
11. [11]
  Pearson, R. G. Inorg. Chem. 1988, 27, 734. doi: 10.1021/ic00277a030
12. [12]
  Pearson, R. G. J. Org. Chem. 1989, 54, 1423. doi: 10.1021/jo00267a034
13. [13]
  Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry; University Science Books: Sausalito, CA, USA, 2005.
14. [14]
  Ayers, P. W.; Anderson, J. S. M.; Bartolotti, L. J. Int. J. Quantum Chem. 2005, 101, 520. doi: 10.1002/qua.20307
15. [15]
  Roos, G.; Geerlings, P.; Messens, J. J. Phys. Chem. B 2009, 113, 13465. doi: 10.1021/jp9034584
16. [16]
  Orozco-Valencia, A. U.; Gazquez, J. L.; Vela, A. J. Phys. Chem. A 2017, 121, 4019. doi: 10.1021/acs.jpca.7b01765
17. [17]
  Orozco-Valencia, U.; Gazquez, J. L.; Vela, A. J. Mol. Model. 2017, 23, 207. doi: 10.1007/s00894-017-3368-y
18. [18]
  Lakhdar, S.; Westermaier, M.; Terrier, F.; Goumont, R.; Boubaker, T.; Ofial, A. R.; Mayr, H. J. Org. Chem. 2006, 71, 9088. doi: 10.1021/jo0614339
19. [19]
  Parr, R. G.; Yang, W. T. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036
20. [20]
  Berkowitz, M. J. Am. Chem. Soc. 1987, 109, 4823. doi: 10.1021/ja00250a012
21. [21]
  Yang, W.; Mortier, W. J. J. Am. Chem. Soc. 1986, 108, 5708. doi: 10.1021/ja00279a008
22. [22]
  Fuentealba, P.; Perez, P.; Contreras, R. J. Chem. Phys. 2000, 113, 2544. doi: 10.1063/1.1305879
23. [23]
  Ayers, P. W.; Morrison, R. C.; Roy, R. K. J. Chem. Phys. 2002, 116, 8731. doi: 10.1063/1.1467338
24. [24]
  Bultinck, P.; Fias, S.; Van Alsenoy, C.; Ayers, P. W.; Carbo-Dorca, R. J. Chem. Phys. 2007, 127, 034102. doi: 10.1063/1.2749518
25. [25]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al. Gaussian 09, Revision D.01; Gaussian Inc.: Wallingford, CT, USA, 2009. http://www.oalib.com/references/9060914
26. [26]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865
27. [27]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1997, 78, 1396. doi: 10.1103/PhysRevLett.78.1396
28. [28]
  Hirshfeld, F. L. Theor. Chim. Acta 1977, 44, 129. doi: 10.1007/bf00549096
29. [29]
  Humphrey, W.; Dalke, A.; Schulten, K. J. Mol. Graphics Modell. 1996, 14, 33. doi: 10.1016/0263-7855(96)00018-5
30. [30]
  Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x
31. [31]
  Terrier, F.; Pouet, M. J.; Halle, J. C.; Hunt, S.; Jones, J. R.; Buncel, E. J. Chem. Soc., Perkin Trans. 2 1993, 1665. doi: 10.1039/p29930001665
32. [32]
  Domingo, L. R.; Perez, P. Org. Biomol. Chem. 2011, 9, 7168. doi: 10.1039/c1ob05856h

扫一扫看文章

计量

PDF下载量: 6
文章访问数: 349
HTML全文浏览量: 19

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

通讯作者: VELAAlberto, avela@cinvestav.mx

English

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

Corresponding author: VELA Alberto, avela@cinvestav.mx

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

通讯作者: VELAAlberto, avela@cinvestav.mx

English

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

Corresponding author: VELA Alberto, avela@cinvestav.mx

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs