Abstract
Calculations by the B3LYP density functional method with various basis sets and by the QCISD(T)/6-31G(d) ab initio method showed that the main pathway of monomolecular gas-phase decomposition of nitroethylene is that involving a cyclic intermediate, 4H-1,2-oxazete 2-oxide; the barrier of its formation (201.9, 203.9, and 216.5 kJ mol−1, as estimated by various methods) reasonably agrees with the experimental value (191.9 kJ mol−1). The barriers of alternative pathways of gas-phase decomposition of nitroethylene are considerably higher. The barriers of reactions involving radical cations are considerably lower than those of the similar reactions involving molecules. Among all the considered pathways of nitroethylene decomposition, bimolecular pathways are the most favorable energetically.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
REFERENCES
Nazin, G.M., Manelis, G.B., and Dubovitskii, D.F., Usp. Khim., 1968, vol. 37, no.8, p. 1443.
Nazin, G.M. and Manelis, G.B., Usp. Khim., 1994, vol. 63, no.4, p. 327.
Manelis, G.B., Nazin, G.M., Rubtsov, Yu.I., and Strunin, V.A., Termicheskoe razlozhenie i gorenie vzryvchatykh veshchestv i porokhov (Thermal Decomposition and Combustion of Explosives and Gunpowders), Moscow: Nauka, 1996. 223 s.
Khrapkovskii, G.M., Marchenko, G.N., and Shamov, A.G., Vliyanie molekulyarnoi struktury na kineticheskie parametry monomolekulyarnogo raspada C-i O-nitrosoedinenii (Influence of Molecular Structure on Kinetic Parameters of Monomolecular Decomposition of C-and O-Nitro Compounds), Kazan: FEN, 1997.
Dubikhin, V.V. and Nazin, G.M., Izv. Akad. Nauk SSSR, Ser. Khim., 1974, no. 4, p. 923.
Faustov, V.I., Shevelev, S.A., Anikin, N.A., and Yufit, S.S., Izv. Akad. Nauk SSSR, Ser. Khim., 1979, no. 11, p. 2800.
Shamov, A.G., Khrapkovskii, G.M., and Shamov, G.A., in Struktura i dinamika molekulyarnykh sistem (Structure and Dynamics of Molecular Systems), Ioshkar-Ola, 1998, issue 5, p. 85.
Khrapkovskii, G.M., Shamov, A.G., Shamov, G.A., and Shlyapochnikov, V.A., Zh. Org. Khim., 1999, vol. 35, no.6, p. 891.
Politzer, P., Concha, M.C., Grice, M.E., Murray, J.S., Lane, P., and Habibollazadeh, D., J. Mol. Struct. (THEOCHEM), 1998, vol. 452, no.10, p. 75.
Gindulyte, A., Massa, L., Huang, L., and Karle, J., J. Phys. Chem. A, 1999, vol. 103, no.50, p. 11 040.
Shamov, A.G. and Khrapkovskii, G.M., in Struktura i dinamika molekulyarnykh sistem (Structure and Dynamics of Molecular Systems), Kazan, 1999, issue 6, p. 347.
Shamov, A.G. and Khrapkovskii, G.M., in Struktura i dinamika molekulyarnykh sistem (Structure and Dynamics of Molecular Systems), Kazan, 1999, issue 6, p. 351.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Gill, P.M.W., Johnson, B.G., Robb, M.A., Cheeseman, J.R., Keith, T.A., Petersson, G.A., Montgomery, J.A., Raghavachari, K., Al-Laham, M.A., Zakrzewski, V.G., Ortiz, J.V., Foresman, J.B., Cioslowski, J., Stefanov, B.B., Nanayakkara, A., Challacombe, M., Peng, C.Y., Ayala, P.Y., Chen, W., Wong, M.W., Andres, J.L., Replogle, E.S., Gomperts, R., Martin, R.L., Fox, D.J., Binkley, J.S., Defrees, D.J., Baker, J., Stewart, J.P., Head-Gordon, M., Gonzalez, C., and Pople, J.A., GAUSSIAN 94, Pittsburgh: Gaussian, 1995.
Becke, A.D., J. Chem. Phys., 1993, vol. 98, no.2, p. 1372.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A., Stratmann R.E., Burant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Gonzalez, C., Challacombe, M., Gill, P.M.W., Johnson, B.G., Chen, W., Wong, M.W., Andres, J.L., Head-Gordon, M., Replogle, E.S., and Pople, J.A., GAUSSIAN 98, Rev. A.1, Pittsburgh: Gaussian, 1998.
Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, no.209, p. 221.
Peng, C. and Schlegel, H.B., Israel J. Chem., 1993, vol. 33, p. 449.
Baker, J., J. Comput. Chem., 1986, vol. 7, no.4, p. 385.
Foresman, J.B. and Frisch, A., Exploring Chemistry with Electronic Structure Methods, Pittsburgh: Gaussian, 1996, p. 188.
Khrapkovskii, G.M., Chachkov, D.V., and Shamov, A.G., in Struktura i dinamika molekulyarnykh sistem (Structure and Dynamics of Molecular Systems), Kazan, 1999, issue 6, p. 358.
Dubikhin, V.V., Nazin, G.M., and Manelis, G.B., Izv. Akad. Nauk SSSR, Ser. Khim., 1974, no. 6, p. 1345.
Khrapkovskii, G.M., Shamov, A.G., and Shamov, G.A., in Svoistva veshchestv i stroenie molekul (Properties of Substances and Molecular Structure), Tver: Tversk. Gos. Univ., 1998, p. 41.
Dewar, M.J.S., Ritchie, J.P., and Alster, J., J. Org. Chem., 1985, vol. 50, no.7, p. 1031.
Khrapkovskii, G.M., Shamov, A.G., Shamov, G.A., and Slyapochnikov, V.A., Mendeleev Commun., 1997, no. 5, p. 169.
Khrapkovskii, G.M., Nikolaeva, E.V., Chachkov, D.V., and Shamov, A.G., Zh. Obshch. Khim., 2004, vol. 74, no.6, p. 983.
Gurvich, L.V., Karachevtsev, G.V., Kondrat’ev, V.N., Lebedev, Yu.A., Medvedev, V.A., Potapov, V.K., and Khodeev, Yu.S., Energiya razryva khimicheskikh svyazei. Potentsialy ionizatsii i srodstvo k elektronu (Dissociation Energies of Chemical Bonds. Ionization Potentials and Electron Affinities), Moscow: Nauka, 1974.
Khrapkovskii, G.M., Shamov, A.G., Shamov, G.A., Nikolaeva, E.V., and Chachkov, D.V., Khim. Komp’yut. Model., Butlerovsk. Soobshch., 2002, no. 6, p. 17.
Kinstle, T.H. and Stam, J.G., J. Org. Chem., 1970, vol. 35, no.6, p. 1771.
Wiser, K. and Berndt, A., Angew. Chem., 1975, vol. 87, no.2, p. 72.
Wiser, K. and Berndt, A., Angew. Chem., 1975, vol. 87, no.2, p. 73.
Shamov, A.G. and Khrapkovskii, G.M., Mendeleev Commun., 2001, no. 4, p. 163.
Shamov, A.G., Nikolaeva, E.V., and Khrapkovskii, G.M., in Struktura i dinamika molekulyarnykh sistem (Structure and Dynamics of Molecular Systems), Kazan, 2002, issue 9, part 2, p. 277.
Egsgaard, H. and Carlsen, L., Org. Mass Spectrom., 1989, vol. 24, no.9, p. 1031.
Nikolaeva, E.V., Shamov, A.G., and Khrapkovskii, G.M., in Struktura i dinamika molekulyarnykh sistem (Structure and Dynamics of Molecular Systems), Ioshkar-Ola, 2001, issue 8, part 2, p. 190.
JAGUAR 4.1, Portland: Schrödinger, 2000.
Author information
Authors and Affiliations
Additional information
Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1327–1342.
Original Russian Text Copyright © 2004 by Shamov, Nikolaeva, Khrapkovskii.
Rights and permissions
About this article
Cite this article
Shamov, A.G., Nikolaeva, E.V. & Khrapkovskii, G.M. Mechanism of gas-phase decomposition of nitroethylene: A theoretical study. Russ J Gen Chem 74, 1227–1242 (2004). https://doi.org/10.1007/s11176-005-0144-y
Received:
Issue Date:
DOI: https://doi.org/10.1007/s11176-005-0144-y