Theoretica chimica acta

, Volume 65, Issue 1, pp 65–76 | Cite as

Transformation matrices as tool to investigate the changes in the electronic structure of reacting molecules along the reaction coordinate

  • Gernot Frenking
  • Nikolaus Heinrich
Original Investigations

Abstract

The calculation of the transformation matrix between the molecular orbitals of the transition state and the educt provides detailed information on the alteration and interaction of the MO’s along the reaction coordinate. This is demonstrated for four different kinds of reactions: (a) Conrotatory ringopening of cyclobutene; (b) Addition of methylene to ethylene; (c) Nucleophilic substitution of CH3CN and CH3NC by CN; (d) 1,2 Rearrangement of methylcarbene to ethylene. MNDO has been employed for the calculations but any other method may be used as well.

Key words

Transformation matrix electronic structure of transition states orbital interaction reaction mechanism 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Fukui, K., Fujimoto, H.: Bull. Chem. Soc. Japan41, 1989 (1968)Google Scholar
  2. 2.
    Fukui, K., Fujimoto, H.: Bull. Chem. Soc. Japan42, 3399 (1969)Google Scholar
  3. 3.
    Fukui, K.: Theory of orientation and stereoselection. Berlin: Springer-Verlag, 1975Google Scholar
  4. 4.
    Fleming, I.: Frontier orbitals and organic chemical reactions. New York: Wiley, 1976Google Scholar
  5. 5.
    Berson, J. A., Salem, L.: J. Am. Chem. Soc.94, 8917 (1972)CrossRefGoogle Scholar
  6. 6.
    Epiotis, N. D.: Theory of organic reactions. Berlin: Springer-Verlag, 1978Google Scholar
  7. 7.
    Frenking, G.: J. Mol. Struct. THEOCHEM104, 233 (1983)CrossRefGoogle Scholar
  8. 8.
    Dewar, M. J. S., Thiel, W.: J. Am. Chem. Soc.99, 4899 (1977)CrossRefGoogle Scholar
  9. 9. a)
    McIver, Jr., J. W., Komornicki, A.: Chem. Phys. Letters10, 303 (1971);CrossRefGoogle Scholar
  10. 9. b)
    Poppinger, D.: Chem. Phys. Letters35, 550 (1975)CrossRefGoogle Scholar
  11. 10.
    Dewar, M. J. S., Kirschner, S.: J. Am. Chem. Soc.93, 4290 (1971)CrossRefGoogle Scholar
  12. 11.
    McIver, Jr., J. W., Komornicki, A.: J. Am. Chem. Soc.94, 2625 (1972)CrossRefGoogle Scholar
  13. 12.
    Stephenson, L. M., Brauman, J. I.: Acc. Chem. Res.7, 65 (1974)CrossRefGoogle Scholar
  14. 13.
    Dewar, M. J. S., Haselbach, E.: J. Am. Chem. Soc.92, 590 (1970)CrossRefGoogle Scholar
  15. 14.
    Ref. 4, p. 103f.Google Scholar
  16. 15. a)
    Rondan, N., Houk, K. N., Moss, R. A.: J. Am. Chem. Soc.102, 1770 (1980);CrossRefGoogle Scholar
  17. 15. b)
    Zurawski, B., Kutzelnigg, W.: J. Am. Chem. Soc.100, 2654 (1978)CrossRefGoogle Scholar
  18. 16. a)
    Bodor, N., Dewar, M. J. S., Wasson, J. S.: J. Am. Chem. Soc.94, 9095 (1972);CrossRefGoogle Scholar
  19. 16. b)
    Schoeller, W. W., Aktekin, N.: J. Chem. Soc. Chem. Comm. 20 (1982)Google Scholar
  20. 17.
    Frenking, G., Schwarz, H.: Z. Naturforsch.36b, 797 (1981)Google Scholar
  21. 18.
    Ref. 4, p. 96.Google Scholar
  22. 19.
    Fujimoto, H., Yamabe, S., Fukui, K.: Tetrahedron Letters 439 (1971)Google Scholar
  23. 20. a)
    Salem, L.: J. Am. Chem. Soc.90, 543 (1968);CrossRefGoogle Scholar
  24. 20. b)
    Klopman, G.: J. Am. Chem. Soc.90, 223 (1968);CrossRefGoogle Scholar
  25. 20. c)
    Pearson, R. G.: J. Am. Chem. Soc.85, 3533 (1963);CrossRefGoogle Scholar
  26. 20. d)
    Pearson, R., Songstad, J.: J. Am. Chem. Soc.89, 1827 (1967)CrossRefGoogle Scholar
  27. 21.
    Ref. 4, p. 40fGoogle Scholar
  28. 22.
    Jones, W. M.: Rearrangements in ground and excited states. P. deMayo (ed.), Vol. 1, Essay 3. New York: Academic Press, 1980Google Scholar
  29. 23.
    Altmann, J. A., Csizmadia, I. G., Yates, K.: J. Am. Chem. Soc.97, 5217 (1975)CrossRefGoogle Scholar
  30. 24.
    Frenking, G., Schmidt, J.: Tetrahedron, in pressGoogle Scholar
  31. 25.
    Hammond, G. S.: J. Am. Chem. Soc.77, 334 (1955)CrossRefGoogle Scholar
  32. 26.
    Raghavachari, K., Frisch, M.J., Pople, J. A., Schleyer, P. v. R.: Chem. Phys. Letters85, 145 (1982)CrossRefGoogle Scholar
  33. 27.
    Keller, E.: Chem. unserer Zeit14, 56 (1980)CrossRefGoogle Scholar
  34. 28.
    Jorgensen, W. L., Salem, L.: Orbitale organischer Moleküle. Weinheim: Verlag Chemie, 1974Google Scholar

Copyright information

© Springer-Verlag 1984

Authors and Affiliations

  • Gernot Frenking
    • 1
  • Nikolaus Heinrich
    • 1
  1. 1.Institut für Organische ChemieTechnische Universität BerlinBerlin 12

Personalised recommendations