How Does the Bent–Walsh Rule Work in Molecules of para-Disubstituted Benzene Derivatives? The Case of para-Nitrophenol and para-Nitrophenolate

• Autorzy: Krygowski T. M. , Szatyłowicz H.
• Języki publikacji: EN

Abstrakty

EN

DFT (B3LYP/6-311+G**) optimization of nitrobenzene, 4-nitrophenol and 4-nitrophenolate with the constraints for the rotating nitrogroup, with an interval of 15°, allowed us to show how the Bent–Walsh rule works in a whole range of variation of geometry in the vicinity of both substituted carbon atoms, C1 and C4. For scatter plots of geometry parameters in the vicinity of the C1 carbon atom the general view is in line with the Bent–Walsh rule. The relationship between the mean value of C1C2 and C1C6 bond lengths and the CO bond length has a negative slope, as expected. Two other dependences, this is the above mentioned bond lengths on C6–C1–C2 angle, have also rational slopes but present a relationship between two clusters, for 4-nitrophenol and 4-nitrophenolate, and within these clusters the slopes are opposite, due to the dominant resonance effect over the electronegativity one. In the case of scatter plots of geometry parameters in the vicinity of the C4 carbon atom the general view is again in line with the Bent–Walsh rule, but irregularities are of different shape: they result from strong interactions between oxygen atoms of the nitro group and both CH in ortho positions. These in - teractions become the strongest for planar conformation of the nitro group and decrease in strength with an in crease of the rotation angle. This results in a perturbation in the resonance/electronegativity blend leading to substantial deviations from linear dependences of the CN bond length vs. the mean value of C4C3 and C4C5 bond lengths, and the CN bond length vs. C3–C4–C5 angle.

Słowa kluczowe

EN

nitro group; substituent effect; electronegativity; Bent-Walsh rule; hydrogen bond

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2009
• Tom: Vol. 83, nr 5
• Strony: 787--797
• Opis fizyczny: Bibliogr. 33 poz., rys.

Twórcy

autor

Krygowski T. M.

autor

Szatyłowicz H.

• De partment of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland,

Bibliografia

• 1. Walsh A.D., Discuss. Faraday Soc, 2, 18 (1947).
• 2. Bent H.A., Chem. Rev., 61, 275 (1961).
• 3. Krygowski T.M., In: Structure and Reactivity, Liebman J.F. and Greenberg A., Eds.; VCH, Weinheim, 1988; Chapt. 6, pp. 231-254.
• 4. Domenicano A, Vaciago A. and Coulson CA., Acta Cryst., B31, 221 (1975).
• 5. Domenicano A, Vaciago A. and Coulson CA, Acta Cryst., B31, 1630 (1975).
• 6. Domenicano A. and Murray-Rust P, Tetrahedron Lett., 20,2283 (1979).
• 7. Campanelli A.R, Domenicano A. and Ramondo F.J., Phys. Chem. A, 107, 6429 (2003).
• 8. Grabowski S.J. and Krygowski T.M, Acta Cryst., C41, 1224 (1985).
• 9. Maurin J. and Krygowski T.M, Acta Cryst., C43, 64 (1987).
• 10. Krygowski T.M, Anulewicz R, Daniluk T. and Drapała T, Struct. Chem., 1, 371 (1990).
• 11. Maurin J. and Krygowski T.M, J. Mol. Struct., 158, 359 (1987).
• 12. Hohenberg P. and Kohn W, Phys. Rev., 136, B864 (1964).
• 13. Kohn W. and Sham L.J, Phys. Rev., 140, A1133 (1965).
• 14. Stephens P.J, Devlin F.J, Chabalowski C.F. and Frisch M.J, J. Phys. Chem., 98, 11623 (1994).
• 15. Becke A.D., J. Phys. Chem., 98, 1372 (1993).
• 16. Becke A.D., J. Chem. Phys., 98, 5648 (1993).
• 17. Lee C, Yang W. and Parr R.G, Phys. Rev. B, 37, 785 (1988).
• 18. Krishnan R, Binkley J.S, Seeger R. and Pople JA, J. Chem. Phys., 72, 650 (1980).
• 19. Frisch M.J, Trucks G.W, Schlegel H.B, Scuseria G.E., Robb M.A, Cheeseman J.R, Montgomery J.A. Jr., Vreven T, Kudin K.N, Burant J.C, Millam J.M., Iyengar S.S., Tomasi J., Barone V., Mennucci B., Cossi M, Scalmani G, RegaN, Petersson G.A, Nakatsuji H, HadaM, EharaM., ToyotaK, Fukuda R, Hasegawa J., Ishida M, Nakajima T, Honda Y, Kitao O., Nakai H., Kiene M, Li X, Knox J.E, Hratchian H.P., Cross J.B., Adamo C, Jaramillo J, Gomperts R., Stratmann R.E., Yazyev O., Austin A.J, Cammi R, Pomelli C, Ochterski J.W., Ayala P.Y, Morokuma K., Voth G.A., Salvador P, Dannenberg J.J, Zakrzewski V.G, Dapprich S, Daniels A.D., Strain M.C., Farkas O, Malick D.K, Rabuck A.D., Raghavachari K, Foresman J.B, Ortiz J.V, Cui Q, Baboul A.G., Clifford S., Cioslowski J, Stefanov B.B., Liu G, Liashenko A, Piskorz P, Komaromi I, Martin R.L, Fox D.J, Keith T, Al-Laham M.A, Peng C.Y., Nanayakkara A, Challacombe M, Gill P.M.W, Johnson B, Chen W., Wong M.W, Gonzalez C. and Pople J.A, Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
• 20. Dobrowolski M.A, Krygowski T.M. and Cyrański M.K., Coll. Czech. Chem. Comm., (2009) in press.
• 21. Boese R., Blaser D. and Krygowski T.M, Struct. Chem., 3, 363 (1992).
• 22. Irle S, Krygowski T.M, Niu J.E. and Schwarz W.H.E, J. Org. Chem., 60, 6744 (1995).
• 23. Exner O. and Krygowski T.M., Chem. Soc. Rev., 25, 71 (1996).
• 24. Hansch G, Leo A. and Taft R.W., Chem. Rev., 91, 165 (1991).
• 25. Stanger A., J. Am. Chem. Soc., 113, 8277 (1991).
• 26. Maksie Z.B, Eckert-Maksic M, Hodoscek M., Koch W. and Kovacek D, In: Molecules in Natural Science and Medicine, Maksie Z.B. and Eckert-Maksic M., Eds.; Ellis Horwood, Chichester, 1991; p. 334.
• 27. Krygowski T.M., Pindelska E, Cyrański M.K. and Haefelinger G., Chem. Phys. Lett., 359,158 (2002).
• 28. Szatyłowicz H. and Krygowski TM, Polish J. Chem., 78, 1719 (2004).
• 29. Krygowski TM, Zachara J.E. and Szatyłowicz H, J. Phys. Org. Chem., 18, 110 (2005).
• 30. Majerz I. and Koll A., Acta Cryst., B60, 406 (2004).
• 31. Kwiatkowska E, Majerz I. and Koll A., Chem. Phys. Lett., 398, 130 (2004).
• 32. Majerz L, Kwiatkowska E. and Koll A, J. Phys. Org. Chem., 18, 833 (2005).
• 33. Majerz I, Kwiatkowska E. and Koll A, J. Mol. Struc, 831, 106 (2007).