Abstract
The enthalpy and activation energy of reactions involving attack by MeO •2 and MeO •2 on CH2 groups of 2-butyl nitrite and 2-nitrosobutane have been calculated by quantum chemical methods. The abstraction of a hydrogen atom is accompanied, in the former case, by concerted N–O bond breaking and, in the latter case, by concerted C–N bond breaking, resulting in NO• formation. On the basis of the results obtained, an algorithm has been developed within the intersecting parabolas model for calculating the enthalpies, activation energies, and rate constants of these types of reactions involving alkyl, alkoxyl, aminyl, peroxyl, phenoxyl, thiyl, and hydroxyl radicals.
Similar content being viewed by others
References
Nekrasov, B.V., Osnovy obshchei khimii (Fundamentals of General Chemistry), Moscow: Khimiya, 1973.
Atkinson, R., Baulch, D.L., Cox, R.A., Hampson, R.F., Kerr, J.A., and Troe, J., J. Phys. Chem. Ref. Data, 1992, vol. 41, p. 1125.
Fontecave, M. and Pierre, J.L., Bull. Soc. Chim. Fr., 1994, vol. 131, p. 620.
Korth, H.G., Sustmann, R., Thater, C., Butler, A.R., and Ingold, K.U., J. Biol. Chem., 1994, vol. 269, p. 17776.
Denisov, E.T. and Shestakov, A.F., Russ. Chem. Bull., 2012, vol. 61, no. 1, p. 12.
Denisov, E.T. and Shestakov, A.F., Kinet. Catal., 2013, vol. 54, no. 1, p. 17.
Denisov, E.T., Russ. Chem. Bull., 2013, vol. 62, no. 7, p. 1533.
Denisov, E.T., Kinet. Catal., 2015, vol. 56, no. 1, p. 56.
Denisov, E.T. and Shestakov, A.F., Russ. J. Phys. Chem. A, 2015, vol. 89, no. 8, p. 1343.
Denisov, E.T. and Tumanov, V.E., Russ. Chem. Rev., 2005, vol. 74, no. 9, p. 825.
Luo, Y.-R., Handbook of Bond Dissociation Energies in Organic Compounds, Boca Raton, Fla.: CRC, 2003.
Denisov, E.T. and Denisova, T.G., Handbook of Antioxidants: Bond Dissociation Energies, Rate Constants, Activation Energies and Enthalpies of Reactions, Boca Raton, Fla.: CRC, 2000.
Lide, D., Handbook of Chemistry and Physics, Boca Raton, Fla.: CRC, 2007–2008.
NIST Standard Reference Database 19A: Positive Ion Energetics, Version 2.02, Gaithersburg, Md.: National Inst. of Standards and Technology, 1994.
Perdew, J.P., Burke, K., and Ernzerhof, M., Phys. Rev. Lett., 1996, vol. 77, p. 3865.
Ustynyuk, Yu.A. and Laikov, D.N., Russ. Chem. Bull., 2005, vol. 54, no. 3, p. 820.
Revision, D., Wallingford, Conn.: Gaussian Inc., 2013.
Hirshfeld, F.L., Theor. Chim. Acta, 1977, vol. 44, p. 129.
Denisov, E.T., Russ. Chem. Rev., 1997, vol. 66, no. 10, p. 859.
Denisov, E.T., in General Aspects of the Chemistry of Radicals, Alfassi, Z.B, Ed., New York: Wiley, 1999, p. 79.
Aleksandrov, I.V., Teor. Eksp. Khim., 1976, vol. 12, no. 3, p. 299.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © E.T. Denisov, A.F. Shestakov, N.S. Emel’yanova, 2016, published in Kinetika i Kataliz, 2016, Vol. 57, No. 3, pp. 297–307.
Rights and permissions
About this article
Cite this article
Denisov, E.T., Shestakov, A.F. & Emel’yanova, N.S. Free-radical abstraction reactions with concerted fragmentation and NO formation. Kinet Catal 57, 297–307 (2016). https://doi.org/10.1134/S0023158416030046
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0023158416030046