Abstract
A comparative Møller–Plesset perturbation theory-based study to analyze the substituent’s effect on the aromaticity and electronic properties of benzene, borazine and diazadiborine has been performed considering electron-donating groups (EDGs) such as –NH2 and –CH3 as well as electron-withdrawing groups (EWGs) such as –NO2 and –CF3 at various positions. The lowest energy structures of all monosubstituted rings follow the same trend of NICS values such that there is slight change in the aromaticity due to EDGs and EWGs. However, N-substituted borazine rings are more aromatic but less stable than B-substitution. More interestingly, the aromaticity of substituted diazadiborine rings increases with the increase in the energy of the isomers due to change in the position of substituent. Therefore, the aromaticity does not account for the relative stability of these species. The electronic properties of lowest energy isomers of benzene, borazine and diazadiborine are affected by the substituent in accordance with the aromaticity. For instance, the substitution of EDGs decreases and that of EWGs increases the ionization potential for all ring systems. The electronic properties of –NO2 (strong EDG)-substituted rings are particularly noticeable due to their large electrophilic index values and larger ionization potentials. This comprehensive report is intended to provide new insights into the energetics, aromaticity and related properties of substituted six-membered homocyclic as well as heterocyclic rings.
Similar content being viewed by others
References
Chiavarino B, Crestoni ME, Marzio AD, Fornarini S, Rosi M (1999) J Am Chem Soc 121:11204
Chiavarino B, Crestoni ME, Fornarini S (1999) J Am Chem Soc 121:2619
Kiran B, Phukan AK, Jemmis ED (2001) Inorg Chem 40:3615
Islas R, Chamorro E, Robles J, Heine T, Santos JC, Merino G (2007) Struct Chem 18:833
Timoshkin AY, Frenking G (2003) Inorg Chem 42:60
Fernandez I, Frenking G (2007) Faraday Discuss 135:403
Schleyer PVR, Jiao H, Hommes NJVE, Malkin VG, Malkina OL (1997) J Am Chem Soc 119:12669
Steiner E, Soncini A, Fowler PW (2006) J Phys Chem A 110:12882
Krygowski TM, Ejsmont K, Stepien BT, Cyranski MK, Poater J, Sola M (2004) J Org Chem 69:6634
Beachley OT Jr (1970) J Am Chem Soc 92:5372
Dunkin TR, Beachley OT Jr (1974) Inorg Chem 13:1768
Nelson JT, Pietro WJ (1989) Inorg Chem 28:544
Del Bene JE, Yanez M, Alkorta I, Elguero J (2009) J Chem Theory Comput 5:2239
Baranac-Stojanović M (2014) Chem Eur J 20:16558
Ghosh D, Periyasamy G, Pati SK (2011) Phys Chem Chem Phys 13:20627
Srivastava AK, Misra N (2015) New J Chem 39:2483
Srivastava AK, Misra N (2015) Chem Phys Lett 625:5
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 09, Revision B.01, Gaussian Inc., Wallingford CT (2010)
Becke AD (1988) Phys Rev A 38:3098
Lee C, Yang W, Parr RG (1988) Phys. Rev. B 37:785
Zhurko GA, Zhurko DA (2012) Chemcraft Version 1:7
Schleyer PVR, Maerker C, Dransfeld A, Jiao H, Hommes NJVE (1996) J Am Chem Soc 118:6317
Schleyer PVR, Jiao H (1996) Pure Appl Chem 68:209
Kohn W, Becke AD, Parr RG (1996) J Phys Chem 100:12974
Parr RG, Pearson RG (1983) J Am Chem Soc 105:7512
Parr RG, Szentpaly LV, Liu S (1999) J Am Chem Soc 121:1922
Chattaraj PK, Lee H, Parr RG (1991) J Am Chem Soc 113:1855
Brown HC, Okamoto Y (1958) J Am Chem Soc 80:4979
Baranac-Stojanović M (2013) J Phys Chem A 117:11540
Stasyuk OA, Szatylowicz H, Krygowski TM (2014) Org Biomol Chem 12:6476
Parthasarathi R, Subramanian V, Roy DR, Chattaraj PK (2004) Bioorg. Med. Chem. 12:5533
Acknowledgments
The author, A. K. Srivastava, wishes to acknowledge Council of Scientific and Industrial Research (CSIR), India, for Senior Research Fellowship (SRF) [Grant No. 09/107(0359)/2012-EMR-I].
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Srivastava, A.K., Pandey, S.K. & Misra, N. The aromaticity and electronic properties of monosubstituted benzene, borazine and diazadiborine rings: an ab initio MP2 study. Theor Chem Acc 135, 158 (2016). https://doi.org/10.1007/s00214-016-1918-5
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-016-1918-5