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

Corresponding author: VELA Alberto, avela@cinvestav.mx
Received Date: 24 November 2017
Revised Date: 29 December 2017
Accepted Date: 5 January 2018
Available Online: 12 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

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.
- Chemical reactivity,
- Conceptual DFT,
- Charge transfer,
- Nucleophilicity,
- Indoles, Transition state prediction
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 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 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 doi: 10.3866/Pku.Whxb20090332
6. [6]
  Chattaraj, P. K.; Sarkar, U.; Roy, D. R. Chem. Rev. 2006, 106, 2065. doi: 10.1021/cr040109f doi: 10.1021/cr040109f
7. [7]
  Chattaraj, P. K.; Roy, D. R. Chem. Rev. 2007, 107, PR46. doi: 10.1021/cr078014b doi: 10.1021/cr078014b
8. [8]
  Chattaraj, P. K.; Giri, S.; Duley, S. Chem. Rev. 2011, 111, PR43. doi: 10.1021/cr100149p doi: 10.1021/cr100149p
9. [9]
  Pearson, R. G. Coord. Chem. Rev. 1990, 100, 403. doi: 10.1016/0010-8545(90)85016-l 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 doi: 10.1021/Ja00364a005
11. [11]
  Pearson, R. G. Inorg. Chem. 1988, 27, 734. doi: 10.1021/ic00277a030 doi: 10.1021/ic00277a030
12. [12]
  Pearson, R. G. J. Org. Chem. 1989, 54, 1423. doi: 10.1021/jo00267a034 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 doi: 10.1002/qua.20307
15. [15]
  Roos, G.; Geerlings, P.; Messens, J. J. Phys. Chem. B 2009, 113, 13465. doi: 10.1021/jp9034584 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 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 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 doi: 10.1021/jo0614339
19. [19]
  Parr, R. G.; Yang, W. T. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036 doi: 10.1021/ja00326a036
20. [20]
  Berkowitz, M. J. Am. Chem. Soc. 1987, 109, 4823. doi: 10.1021/ja00250a012 doi: 10.1021/ja00250a012
21. [21]
  Yang, W.; Mortier, W. J. J. Am. Chem. Soc. 1986, 108, 5708. doi: 10.1021/ja00279a008 doi: 10.1021/ja00279a008
22. [22]
  Fuentealba, P.; Perez, P.; Contreras, R. J. Chem. Phys. 2000, 113, 2544. doi: 10.1063/1.1305879 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 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 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.
26. [26]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.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 doi: 10.1103/PhysRevLett.78.1396
28. [28]
  Hirshfeld, F. L. Theor. Chim. Acta 1977, 44, 129. doi: 10.1007/bf00549096 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 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 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 doi: 10.1039/p29930001665
32. [32]
  Domingo, L. R.; Perez, P. Org. Biomol. Chem. 2011, 9, 7168. doi: 10.1039/c1ob05856h doi: 10.1039/c1ob05856h
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1.
沈阳化工大学材料科学与工程学院沈阳 110142