DOI QR코드

DOI QR Code

An ab initio Study on the Molecular Elimination Reactions of Methacrylonitrile

  • Oh, Chang-Young (Department of Chemistry and Research Institute for Basic Sciences, Kangwon National University) ;
  • Park, Tae-Jun (Department of Chemistry, Dongguk University) ;
  • Kim, Hong-Lae (Department of Chemistry and Research Institute for Basic Sciences, Kangwon National University)
  • Published : 2005.08.20

Abstract

Ab initio quantum chemical molecular orbital calculations have been performed for the unimolecular decomposition of methacrylonitrile ($CH_3C(CN)=CH_2$), especially for HCN and $H_2$ molecular elimination channels. Structures and energies of the reactants, products, and relevant species along the individual reaction pathways were determined by MP2 gradient optimization and MP4 single point energy calculations. Direct four-center elimination of HCN and three-center elimination of H2 channels were identified. In addition, H or CN migration followed by HCN or H2 elimination channels via the methylcyanoethylidene intermediate was also identified. Unlike the case of crotonitrile previously studied, in which the dominant decomposition process was the direct three-center elimination of HCN, the most important reaction pathway should be the direct threecenter elimination of $H_2$ in the case of methacrylonitrile.

Keywords

References

  1. Balko, B. A.; Zhang, J.; Lee, Y. T. J. Chem. Phys. 1992, 97, 935 https://doi.org/10.1063/1.463196
  2. Cromwell, E. F.; Stolow, A.; Vrakking, M. J. J.; Lee, Y. T. J. Chem. Phys. 1992, 97, 4029 https://doi.org/10.1063/1.462942
  3. Jensen, J. H.; Morokuma, K.; Gordon, M. S. J. Chem. Phys. 1994, 100, 1981 https://doi.org/10.1063/1.466550
  4. Reilly, P. T. A.; Xie, Y.; Gordon, R. J. Chem. Phys. Lett. 1991, 178, 511 https://doi.org/10.1016/0009-2614(91)87011-Y
  5. Mo, Y.; Tonokura, K.; Matsumi, Y.; Kawasaki, M.; Sato, S.; Arikawa, T.; Reilly, P. T. A.; Xie, Y.; Yang, Y.; Huang, Y.; Gordon, R. J. J. Chem. Phys. 1992, 97, 4815 https://doi.org/10.1063/1.463836
  6. He, G.; Yang, Y.; Huang, Y.; Gordon, R. J. J. Phys. Chem. 1993, 97, 2186 https://doi.org/10.1021/j100112a020
  7. Tonokura, K.; Daniels, L. B.; Suzuki, T.; Yamashita, K. J. Phys. Chem. 1997, 101, 7754 https://doi.org/10.1021/jp971595w
  8. Blank, D. A.; Sun, W.; Suits, A. G.; Lee, Y. T.; North, S. W.; Hall, G. E. J. Chem. Phys. 1998, 108, 5414 https://doi.org/10.1063/1.475930
  9. Riehl, J. F.; Morokuma, K. J. Chem. Phys. 1994, 100, 8976 https://doi.org/10.1063/1.466702
  10. Riehl, J. F.; Musaev, D.; Morokuma, K. J. Chem. Phys. 1994, 101, 5942 https://doi.org/10.1063/1.467311
  11. North, S. W.; Hall, G. E. Chem. Phys. Lett. 1996, 263, 148 https://doi.org/10.1016/S0009-2614(96)01191-8
  12. Blank, D. A.; Suits, A. G.; Lee, Y. T.; North, S. W.; Hall, G. E. J. Chem. Phys. 1998, 108, 5784 https://doi.org/10.1063/1.475989
  13. Derecskei-Kovacs, A.; North, S. W. J. Chem. Phys. 1999, 110, 2862 https://doi.org/10.1063/1.477929
  14. Oh, C. Y.; Shin, S. K.; Kim, H. L.; Park, C. R. Chem. Phys. Lett. 2001, 342, 27 https://doi.org/10.1016/S0009-2614(01)00557-7
  15. Li, R.; Derecskei-Kovacs, A.; North, S. W. Chem. Phys. 2000, 254, 309 https://doi.org/10.1016/S0301-0104(00)00050-1
  16. Oh, C. Y.; Shin, S. K.; Kim, H. L.; Park, C. R. J. Phys. Chem. A 2003, 107, 4333 https://doi.org/10.1021/jp0221183
  17. Oh, C. Y.; Kim, H. L. J. Chem. Phys. Submitted for publication
  18. 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.; Perdersen, 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.; Nagayakkara, A.; Gonzales, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98; Gaussian Inc.: Pittsburgh, PA, 1998
  19. Gallo, M. M.; Hamilton, T. P.; Schaefer III, H. F. J. Am. Chem. Soc. 1990, 112, 8714 https://doi.org/10.1021/ja00180a011

Cited by

  1. Photodissociation Dynamics of Cyanamide at 212 nm vol.28, pp.9, 2005, https://doi.org/10.5012/bkcs.2007.28.9.1485
  2. Physical Chemistry Research Articles Published in the Bulletin of the Korean Chemical Society: 2003-2007 vol.29, pp.2, 2008, https://doi.org/10.5012/bkcs.2008.29.2.450