A DFT Study on the Stability and Aromaticity of Heterobenzenes Containing Group 15 Elements
Iulia Păuşescu
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Institute for Chemistry Timişoara of the Romanian Academy, 300223 Timişoara, România
Search for more papers by this authorCorresponding Author
Mihai Medeleanu
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Correspondence to: Mihai Medeleanu; e-mail: [email protected].Search for more papers by this authorMircea Ştefănescu
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Search for more papers by this authorFrancisc Peter
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Search for more papers by this authorRaluca Pop
Faculty of Pharmacy, University of Medicine and Pharmacy “Victor Babeş” Timişoara, 300041 Timişoara, România
Search for more papers by this authorIulia Păuşescu
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Institute for Chemistry Timişoara of the Romanian Academy, 300223 Timişoara, România
Search for more papers by this authorCorresponding Author
Mihai Medeleanu
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Correspondence to: Mihai Medeleanu; e-mail: [email protected].Search for more papers by this authorMircea Ştefănescu
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Search for more papers by this authorFrancisc Peter
Faculty of Industrial Chemistry and Environmental Engineering, University Politehnica of Timişoara, 300006 Timişoara, România
Search for more papers by this authorRaluca Pop
Faculty of Pharmacy, University of Medicine and Pharmacy “Victor Babeş” Timişoara, 300041 Timişoara, România
Search for more papers by this authorABSTRACT
The stability and aromaticity of 36 heterobenzenes containing group 15 elements were evaluated at the B3LYP/6-311+G(d,p) level of theory. Stability evaluation was performed based on the enthalpies of formation calculated from imaginary reactions and on the absolute hardness reactivity descriptor. The aromaticity was investigated by means of geometric (Bird, Harmonic Oscillator Model of Aromaticity (HOMA) indices), energetic (aromatic stabilization energy), and magnetic criteria (nucleus-independent chemical shifts [NICS] index). Also, within the conceptual density functional theory (DFT) theory, reactivity-based descriptors (highest occupied molecular orbital and lowest unoccupied molecular orbital [HOMO—LUMO] energy gap, absolute hardness, electrophilicity) were computed. The results led to the conclusion that all heterobenzenes exhibit aromatic character, which generally decreases from N to As containing compounds and from one to six substituted CH groups.
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REFERENCES
- 1De Proft, F.; Geerlings, P. Chem Rev 2001, 101, 1451–1464.
- 2Krygowski, T. M.; Cyrañski, M. K.; Czarnocki, Z.; Häfelinger, G.; Katritzky, A. R. Tetrahedron 2000, 56, 1783–1796.
- 3Krygowski, T. M.; Cyrañski, M. K. Chem Rev 2001, 101, 1385–1419.
- 4Katritzky, A. R.; Jug, K.; Oniciu, D. C. Chem Rev 2001, 101, 1421–1449.
- 5Pop, O. R.; Medeleanu, M.; Csunderlik, C.; Mracec, M. Rev Chim 2010, 61(5), 483–486.
- 6Pop, R.; Andoni, M.; Pãuşescu, I.; Medeleanu, M.; Rev Chim 2013, 64(9), 942–945.
- 7Pop, R.; Andoni, M.; van Staden, J.; Pãuşescu, I.; Medeleanu, M. Dig J Nanomater Bios 2013, 8(4), 1739–1750
- 8Dong, W.; Wang, H.; Ge, Q.; Wang, L. Struct Chem 2007, 18, 593–597.
- 9Saieswari, A.; Priyakumar, U. D.; Sastry, G. N. J Mol Struct (Theochem) 2003, 663, 145–148.
- 10Kassaee, M. Z.; Jalalimanesh, N.; Musavi, S. M. J Mol Struct (Theochem) 2007, 816, 153–160
- 11Omelchenko, I. V.; Shishkin, O. V.; Gorb, L.; Leszczynski, J.; Fias, S.; Bultinck, P. Phys Chem Chem Phys 2011, 13, 20356–20548.
- 12Wang, Y.; Wu, J. I. C.; Li, Q.; von Ragué Schleyer, P. Org Lett 2010, 12(21), 4824–4827.
- 13 Gaussian 09, Revision B.01, 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.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida., M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakaim, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J., Gaussian, Inc.: Wallingford CT, 2010.
- 14Chesnut, D. B.; Moore, K. D., J Comput Chem 1985, 10, 648–659.
- 15Lu, T.; Chen, F. J Comp Chem 2012, 33, 580–592.
- 16Wolinski, K.; Hinto, J. F.; Pulay, P. J Am Chem Soc 1990, 112, 8251–8260.
- 17Bird, C. W. Tetrahedron 1985, 41, 1409–1414.
- 18Krygowski, T. M.; Cyrañski, M. K. Tetrahedron 1996, 52, 10255–10264.
- 19Krygowski, T. M.; Cyrañski, M. K. Tetrahedron 1996, 52, 1713–1722.
- 20Cyrañski, M. K. Chem Rev 2005, 105, 3773–3811.
- 21Shaik, S. S.; Shurki, A.; Danovich, D.; Hiberty, P. C., Chem Rev 2001, 101, 1501–1540.
- 22Williams, C. I.; Whitehead, M. A. J Mol Struct Theochem 1997, 393, 9–24.
- 23Yu, J.; Sumathi, R.; Green, Jr., W. H. J Am Chem Soc 2004, 126(39), 12685–12700.
- 24Shobe, D. S. J. Phys Chem A 2005, 109, 9118–9122.
- 25Fabian, J.; Lewars, E. Can J Chem 2004, 82, 50–69.
- 26Cyranski, M. K.; Schleyer, P. v. R.; Krygowski, T. M.; Jiao, H.; Hohlneicher, G. Tetrahedron 2003, 59, 1657–1665.
- 27Krygowski, T. M.; Cyranski, M. K., Chem Rev 2001, 101, 1385–1419.
- 28Fernández, I.; Frenking, G., Faraday Discuss 2007, 135, 403–421.
- 29Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. J. J Am Chem Soc 1996, 118, 6317–6318.
- 30Nyulaszi, L.; Benko, Z. In Aromatic Phosphorus Heterocycles in Topics in Heterocyclic Chemistry: Aromaticity in Heterocyclic Compounds; T. M. Krygowski, M. K. Cyranski, (Eds.); Springer-Verlag: Berlin, 2009.
- 31Wang, Y.; Wu, J. I. C.; Li, Q.; Schleyer, P. v. R. Org Lett 2010, 12(21), 4824–4827.
- 32Roy, D. R.; Bultinck, P.; Subramanian, V.; Chattaraj, P. K. J Mol Struct Theochem 2008, 854, 35–39.
- 33De Proft, F.; Geerlings, P. Phys Chem Chem Phys 2004, 6, 242–248.
- 34Chamizo, J. A.; Morgado, J.; Sosa, O. Organometallics 1993, 12, 5005–5007.
- 35Bultinck, P.; Rafat, M.; Ponec, R.; Van Gheluwe, B.; Carbo-Dorca, R.; Popelier, P. J Phys Chem A 2006, 110, 7642–7648.
- 36Ponec, R.; Bultinck, P.; Gallegos Saliner, A. J Phys Chem A 2005, 109, 6606–6609.
- 37Matito, E.; Sola, M.; Salvador, P.; Duran, M. Faraday Discus 2007, 135, 325–345.
- 38Sola, M.; Feixas, F.; Jimenez-Halla, J. O. C.; Matito, E.; Poater, J. Symmetry 2010, 2, 1156–1179.
- 39Poater, J.; Fradera, X.; Duran, M.; Sola, M. Chemistry 2003, 9(2), 400–406.
- 40Poater, J.; Fradera, X.; Duran, M.; Solà, M. Chem Eur J 2003, 9, 1113–1122.
- 41Poater, J.; Garcia-Cruz, I.; Illas, F.; Sola, M. Phys Chem Chem Phys 2004, 6, 314–318.
