Structural Chemistry

, Volume 19, Issue 2, pp 191–198 | Cite as

Proton transfer in C-halogen pyrazole cyclamers. A theoretical study

Original Research

Abstract

Four monomers and twelve pyrazole cyclamers unsubstituted or bearing fluoro, chloro, or bromo substituents at positions 3 and 5 have been studied at the B3LYP/6-31+G** theoretical level. Two mechanisms of proton transfer, stepwise and synchronous, have been studied for dimers, trimers, and tetramers. Even though some values of the barriers have not been determined, the set of values of energies and geometries provide useful insights about the dynamics of NH-pyrazoles in the solid state.

Keywords

Pyrazole DFT Tautomerism Proton transfer 

References

  1. 1.
    Cammers A, Parkin S (2004) Cryst Eng Commun 6:168Google Scholar
  2. 2.
    Etter MC, Parker DL, Ruberu SR, Panunto TW, Britton DJ (1990) J Incl Phenom Macrocycl Chem 8:395CrossRefGoogle Scholar
  3. 3.
    (a) Etter MC (1990) Acc Chem Res 23:120; (b) Etter MC, MacDonald J, Bernstein J (1990) Acta Crystallogr B46:256Google Scholar
  4. 4.
    (a) Bernstein J, Etter MC, Leiserowitz L (1994) The role of hydrogen bonding in molecular assemblies. In: Dunitz JD, Burgi HB (eds) Structure correlations, Vol 2. VCH, Weinheim, pp 431–507; (b) Bernstein J, Davis RE, Shimoni L, Chang NL (1995) Angew Chem Int Ed Engl 34:1555Google Scholar
  5. 5.
    López C, Claramunt RM, García MA, Pinilla E, Torres MR, Alkorta I, Elguero J (2007) Cryst Growth Des 7:1176CrossRefGoogle Scholar
  6. 6.
    Haghiri A, Lerner HW, Wagner M, Bats JW 2002 Acta Crystallogr E58:o1378Google Scholar
  7. 7.
    CSD ver. 5.28 (updated January & May 2007): Allen FH (2002) Acta Crystallogr B58:380; Allen FH, Motherwell WDS (2002) Acta Crystallogr B58:407Google Scholar
  8. 8.
    (a) Becke AD (1988) Phys Rev A 38:3098; (b) Becke AD (1993) J Chem Phys 98:5648; (c) Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785Google Scholar
  9. 9.
    (a) Hehre WJ, Ditchfield R, Pople JA (1972) J Chem Phys 56:2257; (b) Clark T, Chandrasekar J, Schleyer PvR (1983) J Comput Chem 4:294Google Scholar
  10. 10.
    Gaussian 03, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adao C, Jaramill, J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA. Gaussian, Inc., Pittsburgh PA, 2003Google Scholar
  11. 11.
    Bader RFW (1990) Atoms in molecules: a quantum theory. Clarendon Press, Oxford; Biegler-König FW, Bader RFW, Tang TH (1982) J Comput Chem 3:317Google Scholar
  12. 12.
    Klein O, Aguilar-Parrilla F, López JM, Jagerovic N, Elguero J, Limbach HH (2004) J Am Chem Soc 126:11718CrossRefGoogle Scholar
  13. 13.
    (a) Elguero J, Marzin C, Katritzky AR, Linda P (1976) The tautomerism of heterocycles. Academic Press, New York, p 655; (b) Minkin VI, Garnosvskii AD, Elguero J, Katritzky AR, Denisko OV (2000) Adv Heterocycl Chem 76:157Google Scholar
  14. 14.
    Huheey JE (1983) Inorganic chemistry. Harper & Row, New YorkGoogle Scholar
  15. 15.
    Foces-Foces C, Alkorta I, Elguero J (2000) Acta Crystallogr Sect B 56:1018CrossRefGoogle Scholar
  16. 16.
    Alkorta I, Elguero J, Foces-Foces C, Infantes L (2006) Arkivoc ii:15Google Scholar
  17. 17.
    (a) Kubinyi H (1995) In: Wolff ME (ed) Burger’s medicinal chemistry and drug discovery, Vol 1. Wiley, New York, p 497; (b) Selassie CD (2003) In: Abraham DJ (ed) Burger’s medicinal chemistry and drug discovery, Vol 1. Wiley, Hoboken, pp 19–23Google Scholar
  18. 18.
    Paz JLG, Elguero J, Foces-Foces C, Llamas-Saiz AL, Aguilar-Parrilla F, Klein O, Limbach HH (1997) J Chem Soc Perkin Trans 2:101Google Scholar
  19. 19.
    Pauling L (1947) J Am Chem Soc 69:542CrossRefGoogle Scholar
  20. 20.
    Brown ID (1992) Acta Crystallogr B 48:553CrossRefGoogle Scholar
  21. 21.
    Ramos M, Alkorta I, Elguero J, Golubev NS, Denisov GS, Benedict H, Limbach HH (1997) J Phys Chem A 101:9791CrossRefGoogle Scholar
  22. 22.
    Alkorta I, Elguero J (1999) Struct Chem 10:157CrossRefGoogle Scholar
  23. 23.
    Alkorta I, Picazo O, Elguero J (2004) Tetrahedron-Asymmetry 15:1391CrossRefGoogle Scholar
  24. 24.
    Picazo O, Alkorta I, Elguero J (2003) J Org Chem 68:7485CrossRefGoogle Scholar
  25. 25.
    Sánchez M, Provasi PF, Aucar GA, Alkorta I, Elguero J (2005) J Phys Chem B 109:18189CrossRefGoogle Scholar
  26. 26.
    Espinosa E, Alkorta I, Elguero J, Molins E (2002) J Chem Phys 117:5529CrossRefGoogle Scholar
  27. 27.
    Stride JA, Jayasooriya UA, Zanotti JM, Kahn R (2006) New J Chem 30:425CrossRefGoogle Scholar
  28. 28.
    Castaneda JP, Denisov GS, Kucherov SYu, Schreiber VM, Shurukhina AV (2003) J Mol Struct 660:25CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  1. 1.Instituto de Química Médica (C.S.I.C.)MadridSpain

Personalised recommendations