Abstract
DFT calculations at the B3LYP/6-311++G(d,p) computational level have been carried out on three tautomeric pairs of 3-mercapto-1,2-azoles (pyrazoles, isoxazoles, and isothiazoles) to study the effect of halogen bonds (XBs) on the position of the equilibrium. As halogen bond donors, we have selected Br2, Cl2, BrCl, ClF and BrF and compare them with HF as a hydrogen bond donor. Several linear relationships were found between binding energies of different halogen bond donors. The main conclusion of this study is that the XB inverts the tautomeric equilibrium while an HB does not.
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Elguero J, Marzin C, Katritzky AR, Linda P (1976) The tautomerism of heterocycles. Academic Press, New York, NY
Minkin VI, Garnovskii AD, Elguero J, Katritzky AR, Denisko OV (2000) Adv Heterocycl Chem 76:157–323
O’Connell MJ, Ramsay CG, Steel PJ (1985) Aust J Chem 38:401–409
Kyrychenko A, Stepanenko Y, Waluk J (2000) J Phys Chem A 104:9542–9555
Alkorta I, Elguero J (2002) J Org Chem 67:1515–1519
Alkorta I, Elguero J (2009) How aromaticity affects the chemical and physicochemical properties of heterocycles: a computational approach. In: Krygowski TM, Cyránski MK (eds) Aromaticity in heterocyclic compounds, Topics in Heterocyclic Chemistry (Series Ed Gupta RR), vol 19. Springer, Berlin, Heidelberg
Nagy PI (2014) Int J Mol Sci 15:19562–19633
Metrangolo P, Resnati G (2001) Chem Eur J 7:2511–2519
Legon AC (2008) Struct Bond 126:17–64
Alkorta I, Blanco F, Solimannejad M, Elguero J (2008) J Phys Chem A 112:10856–10863
El-Sheshtawy HS, Salman HMA, El-Kemary M (2015) Spectrochim Acta Part A 137:442–449
Auffinger P, Hays FA, Ho PS (2004) PNAS 101:16789–16794
Katritzky AR, Hall CD, El-Gendy BEM, Draghici B (2010) J Comput Aided Mol Des 24:475–484
Scholfield MR, Vander Zanden CM, Carter M, Ho PS (2013) Protein Sci 22:139–152
Alkorta I, Rozas I, Elguero J (1998) J Phys Chem A 102:9278–9285
Alkorta I, Blanco F, Elguero J (2009) Struct Chem 20:63–71
Arriau J, Elguero J (1981) An Quim 77:105–111
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, KitaoO, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision D.01. Gaussian, Wallingford
Parr RG, Yang W (1989) Density-functional theory of atoms and molecules. Oxford University Press, New York, NY
Bartolotti LJ, Fluchichk K (1996) An introduction to density functional theory. In: Lipkowitz KB, Boyds DB (eds) Reviews in computational chemistry, vol 7. VCH, New York, NY
Kohn W, Becke AD, Parr RG (1996) J Phys Chem 100:12974–12980
Ziegler T (1991) Chem Rev 91:651–667
Tian L, Feiwu C (2012) J Comp Chem 33:580–592
Jmol: An open-source java viewer for chemical structures in 3D, version 130. http://www.jmolorg/. Accessed 26 Sept 2013
Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899–926
Glendening ED, Badenhoop JK, Reed AE, Carpenter JE, Bohmann JA, Morales CM, Landis CR, Weinhold F (2013) NBO-6; Theoretical Chemistry Institute. University of Wisconsin, Madisn, WI
Popelier PL (2000) Atoms in molecules: an introduction. Prentice Hall, London
Bader RFW (1990) Atoms in molecules: a quantum theory. Oxford University Press, Oxford
Keith TA (2013) AIMAll (Version 13.10.19) TK Gristmill Software, Overland Park KS, USA. http://aim.tkgristmill.com. Accessed 4 July 2013
Politzer P, Lane P, Concha MC, Ma Y, Murray JS (2007) J Mol Model 13:305–311
Kalescky R, Zou W, Kraka E, Cremer D (2014) J Phys Chem A 118:1948–1963
Knop O, Boyd RJ, Choi SC (1988) J Am Chem Soc 110:7299–7301
Alkorta I, Elguero J (2004) Struct Chem 15:117–120
Alkorta I, Solimannejad M, Provasi P, Elguero J (2007) J Phys Chem A 111:7154–7161
Mata I, Alkorta I, Molins E, Espinosa E (2010) Chem Eur J 16:2442–2452
Rozas I, Alkorta I, Elguero J (2000) J Am Chem Soc 122:11154–11161
Antonov L (ed) (2014) Tautomerism methods and theories. Wiley-VCH, Weinheim
Lipkowitz KB, Boyd DB (eds) (1991) Reviews in computational chemistry, vol 2. Wiley-VCH, New York, NY
Katritzky AR, Hall CD, El-Gendy BEDM, Draghici B (2010) J Comput Aided Mol Des 24:475–484
Metrangolo P, Resnati G (eds) (2008) Halogen bonding, fundamentals and applications, structure and bonding, vol 126. Springer, Berlin Heidelberg
Scholfield MR, Vander Zanden CM, Carter M, Ho PS (2013) Protein Sci 22:139–152
Acknowledgments
This work has been supported by the Spanish Ministerio de Economía y Competitividad (CTQ2012-35513-C02-02) and Comunidad Autónoma de Madrid (S2013/MIT-2841, Fotocarbon). Computer, storage, and other resources from the CTI (CSIC) are gratefully acknowledged. One of us (M.M.-L.) benefits from a contract from the Ministerio de Economía y Competitividad.
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Marta Marín-Luna was on leave from Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain.
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Marín-Luna, M., Alkorta, I. & Elguero, J. The influence of halogen bonds on tautomerism: the case of 3-mercapto-1,2-azoles (pyrazoles, isoxazoles, isothiazoles). Struct Chem 26, 639–645 (2015). https://doi.org/10.1007/s11224-015-0581-0
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DOI: https://doi.org/10.1007/s11224-015-0581-0