Structural Chemistry

, Volume 18, Issue 6, pp 797–805

Substitution effects in phenyl and N-pyrrole derivatives along the periodic table

Original Paper

Abstract

A theoretical study of the monosubstitution effects of all the atoms of the second and third row of the periodic table on the phenyl and pyrrole rings has been carried out by means of B3LYP/6-31 + G(d,p) DFT calculations. The geometric and electronic properties, calculated using the Atoms In Molecules methodology, have been analyzed. Some of the results have been rationalized based on the electronegativity of the substituents. In addition, the different parameters obtained have been compared with different aromaticity indexes (HOMA, NICS, and ASE), as well as with Taft’s σ0R parameter.

Keywords

Benzene Pyrrole Substituent effects Aromaticity AIM 

References

  1. 1.
    Minkin VI, Glukhovtsev MN, Simkin BY (1994) Aromaticity and antiaromaticity. John Wiley & Sons, Inc., New YorkGoogle Scholar
  2. 2.
    Krygowski TM, Stepien BT (2005) Chem Rev 105:3482CrossRefGoogle Scholar
  3. 3.
    Krygowski TM, Dobrowolski MA, Zborowski K, Cyranski MK (2006) J Phys Org Chem 19:889CrossRefGoogle Scholar
  4. 4.
    Krygowski TM, Ejsmont K, Stepien BT, Cyranski MK, Poater J, Sola M (2004) J Org Chem 69:6634CrossRefGoogle Scholar
  5. 5.
    Matito E, Solà M, Salvador P, Duran M (2007) Faraday Discuss 135:325CrossRefGoogle Scholar
  6. 6.
    Fernandez I, Frenking G (2007) Faraday Discuss 135:403CrossRefGoogle Scholar
  7. 7.
    Alonso M, Herradón B (2007) Chem Eur J 13:3913CrossRefGoogle Scholar
  8. 8.
    Giambiagi M, de Giambiagi MS, Silva CDD, de Figueiredo AP (2000) Phys Chem Chem Phys 2:3381CrossRefGoogle Scholar
  9. 9.
    Juselius J, Sundholm D (1999) Phys Chem Chem Phys 1:3429CrossRefGoogle Scholar
  10. 10.
    Kovacevic B, Baric D, Maksic ZB, Muller T (2004) Chemphyschem 5:1352CrossRefGoogle Scholar
  11. 11.
    Mó O, Yañéz M, Llamas-Saiz AL, Foces-Foces C, Elguero J (1995) Tetrahedron 51:7045CrossRefGoogle Scholar
  12. 12.
    Begtrup M, Balle T, Claramunt RM, Sanz D, Jiménez JA, Mó O, Yañéz M, Elguero J (1998) Theochem-J Mol Struc 453:255CrossRefGoogle Scholar
  13. 13.
    Becke AD (1993) J Chem Phys 98:5648CrossRefGoogle Scholar
  14. 14.
    Lee CT, Yang WT, Parr RG (1988) Phys Rev B 37:785CrossRefGoogle Scholar
  15. 15.
    Hariharan PC, Pople JA (1973) Theor Chim Acta 28:213CrossRefGoogle Scholar
  16. 16.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JJA, 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, Bakken V, Adamo C, Jaramillo 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 (2003) Gaussian-03. Gaussian, Inc., Wallingford CTGoogle Scholar
  17. 17.
    Bader RFW (1990) Atoms in molecules: a quantum theory. Clarendon Press, OxfordGoogle Scholar
  18. 18.
    Biegler-König FW, Bader RFW, Tang TH (1982) J Comput Chem 3:317CrossRefGoogle Scholar
  19. 19.
    Alkorta I, Picazo O (2005) Arkivoc ix:305Google Scholar
  20. 20.
    Krygowski TM, Cyranski MK, Czarnocki Z, Hafelinger G, Katritzky AR (2000) Tetrahedron 56:1783CrossRefGoogle Scholar
  21. 21.
    Schleyer PvR, Jiao HJ (1996) Pure Appl Chem 68:209CrossRefGoogle Scholar
  22. 22.
    Krygowski TM (1993) J Chem Inf Comp Sci 33:70Google Scholar
  23. 23.
    Schleyer PvR, Maerker C, Dransfeld A, Jiao HJ, Hommes NJRV (1996) J Am Chem Soc 118:6317CrossRefGoogle Scholar
  24. 24.
    Schleyer PvR, Manoharan M, Wang ZX, Kiran B, Jiao HJ, Puchta R, Hommes NJRV (2001) Org Lett 3:2465CrossRefGoogle Scholar
  25. 25.
    Corminboeuf C, Heine T, Seifert G, Schleyer PV, Weber J (2004) Phys Chem Chem Phys 6:273CrossRefGoogle Scholar
  26. 26.
    Hehre WJ, Radom L, Schleyer PVR, Pople JA (1986) Ab initio molecular orbital theory. John Wiley & Sons, New YorkGoogle Scholar
  27. 27.
    Tamagawa K, Iijima T, Kimura M (1976) J Mol Struct 30:243CrossRefGoogle Scholar
  28. 28.
    Amirebrahimi V, Choplin A, Demaison J, Roussy G (1981) J Mol Spectrosc 89:42CrossRefGoogle Scholar
  29. 29.
    Lister DG, Tyler JK, Hog JH, Larsen NW (1974) J Mol Struct 23:253CrossRefGoogle Scholar
  30. 30.
    Larsen NW (1979) J Mol Struct 51:175CrossRefGoogle Scholar
  31. 31.
    Doraiswamy S, Sharma SD (1983) J Mol Struct 102:81CrossRefGoogle Scholar
  32. 32.
    Keidel FA, Bauer SH (1956) J Chem Phys 25:1218CrossRefGoogle Scholar
  33. 33.
    Naumov VA, Tafipol’skii MA, Samdal S (2003) Russ J Gen Chem 73:896CrossRefGoogle Scholar
  34. 34.
    Cradock S, Muir JM, Rankin DWH (1990) J Mol Struct 220:205CrossRefGoogle Scholar
  35. 35.
    Nygaard L, Nielsen JT, Kirchhei J, Maltesen G, Rastrupa J, Sorensen GO (1969) J Mol Struct 3:491CrossRefGoogle Scholar
  36. 36.
    Huber S, Ha TK, Bauder A (1997) J Mol Struct 413:93CrossRefGoogle Scholar
  37. 37.
    Glidewell C, Robiette AG, Sheldrick GM (1971) J Mol Struct 9:476CrossRefGoogle Scholar
  38. 38.
    Alkorta I, Barrios L, Rozas I, Elguero J (2000) J Mol Struc-Theochem 496:131CrossRefGoogle Scholar
  39. 39.
    Alkorta I, Rozas I, Elguero J (1998) J Mol Struc-Theochem 452:227CrossRefGoogle Scholar
  40. 40.
    Alkorta I, Rozas I, Elguero J (1998) Struct Chem 9:243CrossRefGoogle Scholar
  41. 41.
    Howard ST, Krygowski TM (1997) Can J Chem 75:1174CrossRefGoogle Scholar
  42. 42.
    Pauling L (1945) The nature of chemical bond. Cornell University Press, Ithaca, New YorkGoogle Scholar
  43. 43.
    Bromilow J, Brownlee RTC, Lopez VO, Taft RW (1979) J Org Chem 44:4766CrossRefGoogle Scholar
  44. 44.
    Hansch C, Leo A, Hoekman D (1995) Exploring QSAR. American Chemical SocietyGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Krzysztof Zborowski
    • 1
  • Ibon Alkorta
    • 2
  • José Elguero
    • 2
  1. 1.Faculty of ChemistryJagiellonian UniversityKrakowPoland
  2. 2.Instituto de Química Médica (C.S.I.C.)MadridSpain

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