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Quantum chemical studies on electrophilic addition

III. Reaction of hydroxonium ion with ethylene. Acid catalysed ring opening of epoxides

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Abstract

The geometries of the 2-hydroxyethyl and isomeric oxiranium cations have been fully optimized using ab initio molecular orbital calculations employing the split valence shell 4-31G basis set. These species are possible intermediates in both the electrophilic addition of OH⊕ to ethylene and in the acid catalysed ring opening of oxirane. The optimized structures were then used to compute more accurate wave functions using Dunning's double-zeta basis set, and with this large basis set the bridged oxiranium ion was found to be the more stable by 7.2 kcal/mole. The barrier to interconversion of these two C2H4OH⊕ ions was computed to be 25.0 kcal/mole above the oxiranium ion.

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References

  1. Roberts, I., Kimball, G. E.: J. Am. Chem. Soc. 59, 947 (1937)

    Google Scholar 

  2. Lucas, H. J., Gould, C. W.: J. Am. Chem. Soc. 63, 2541 (1941)

    Google Scholar 

  3. Fahey, R. C., Shubert, C.: J. Am. Chem. Soc. 91, 1477 (1965)

    Google Scholar 

  4. Bartlett, P. D.: Rec. Chem. Prog. 11, 47 (1950)

    Google Scholar 

  5. Koskikallio, J., Whalley E.: Trans. Faraday Soc. 55, 815 (1959)

    Google Scholar 

  6. Long, F. A., Pritchard, J. G., Stafford, F. E.: J. Am. Chem. Soc. 79, 2362 (1957)

    Google Scholar 

  7. Laidler, K. J.: Chemical kinetics, second ed., p. 509. New York: McGraw Hill Book Co. 1965

    Google Scholar 

  8. Lambert, J. B., Johnson, D. H.: J. Am. Chem. Soc. 90, 1349 (1968)

    Google Scholar 

  9. Meerwein, H.: Angew. Chem. 67, 374 (1955)

    Google Scholar 

  10. Klages, F., Jung, H. A.: Chem. Ber. 92, 3757 (1965)

    Google Scholar 

  11. Perst, H.: Oxonium ions in organic chemistry. Weinheim: Verlag Chemie, New York: Academic Press 1971

    Google Scholar 

  12. Hopkinson, A. C., Lien, M. H., Yates, K., Csizmadia, I. G.: Theoret. Chim. Acta (Berl.) 38, 21 (1975)

    Google Scholar 

  13. Hopkinson, A. C., Lien, M. H., Yates, K., Csizmadia, I. G.: Theoret. Chim. Acta (Berl.) 44, 385 (1977)

    Google Scholar 

  14. Ditchfield, R., Hehre, W. J., Pople, J. A.: J. Chem. Phys. 54, 724 (1971)

    Google Scholar 

  15. Hehre, W. J., Lathan, W. A.: J. Am. Chem. Soc. 56, 5255 (1972)

    Google Scholar 

  16. Hehre, W. J., Lathan, W. A., Ditchfield, R., Newton, M. D., Pople, J. A.: GAUSSIAN 70, Quantum Chemistry Program Exchange No. 236, Indiana University, Bloomington, Indiana

  17. Dunning, T.: J. Chem. Phys. 53, 2823 (1970)

    Google Scholar 

  18. Duke, A. J.: Chem. Phys. Letters 10, 631 (1971)

    Google Scholar 

  19. POLYATOM (Version 2), Quantum Chemistry Program Exchange No. 199, Indiana University, Bloomington, Indiana

  20. Cunningham, G. L., Boyd, A. W., Myers, R. J., Gwinn, W. D., LeVan, W. I.: J. Chem. Phys. 19, 676 (1951)

    Google Scholar 

  21. Hehre, W. J., Stewart, R. F., Pople, J. A.: J. Chem. Phys. 51, 2657 (1969)

    Google Scholar 

  22. Hehre, W. J., Ditchfield, R., Stewart, R. F., Pople, J. A.: J. Chem. Phys. 52, 2191 (1970)

    Google Scholar 

  23. Lathan, W. A., Radom, L., Hariharan, P. C., Hehre, W. J., Pople, J. A.: Topics Current Chem. 40, 1 (1973)

    Google Scholar 

  24. Imanov, L. M., Kadzhar, Ch. O.: Izv. Akad. Nauk. Azerb. SSR, Ser. Fiz.-Mat. i Tekhn. Nauk. 1962, Nos. 55-8; Chem. Abs.: 58, 3011d (1963)

  25. Radom, L., Pople, J. A., Schleyer, P. v. R.: J. Am. Chem. Soc. 94, 5935 (1972)

    Google Scholar 

  26. Hoffman, R., Radom, L., Pople, J. A., Schleyer, P. v. R., Hehre, W. J., Salem, L.: J. Am. Chem. Soc. 94, 6221 (1972)

    Google Scholar 

  27. Radom, L., Hehre, W. J., Pople, J. A.: J. Am. Chem. Soc. 94, 2371 (1972)

    Google Scholar 

  28. Hehre, W. J., Hiberty, P. C.: J. Am. Chem. Soc. 96, 2665 (1974)

    Google Scholar 

  29. Pauling, L.: The nature of the chemical bond, third ed., p. 260. Cornell University Press 1960

  30. Gordon, J. W., Schmid, G. H., Csizmadia, I. G.: J. Chem. Soc. Perk. Trans. II, 1722 (1975)

    Google Scholar 

  31. Csizmadia, I. G., Bernardi, F., Lucchini, V., Modena, G.: J. Chem. Soc. Perk. Trans. II, 542 (1977)

    Google Scholar 

  32. Hariharan, D. C., Lathan, W. A., Pople, J. A.: Chem. Phys. Letters 14, 385 (1972)

    Google Scholar 

  33. Weber, J., McLean, A. D.: J. Am. Chem. Soc. 98, 875 (1976)

    Google Scholar 

  34. Csizmadia, I. G.: Progr. Theoret. Org. Chem. 1, 249 (1976)

    Google Scholar 

  35. Mezey, P. G.: Chem. Phys. Letters 47, 70 (1977)

    Google Scholar 

  36. Csizmadia, I. G., Theodorakopoulos, G., Schlegel, H. B., Whangbo, M. H., Wolfe, S.: Can. J. Chem. 55, 986 (1977)

    Google Scholar 

  37. Collis, M. J., Merrall, G. T.: Chem. Ind. (London), 711 (1964)

  38. Smith, L.: Z. Physik. Chem. 92, 739 (1918)

    Google Scholar 

  39. Smith, L., Skyle, S.: Acta Chem. Scand. 4, 39 (1950); 5, 1415 (1951)

    Google Scholar 

  40. de la Mare, P. B. D., Pritchard, J. G.: J. Chem. Soc. 3910 (1954)

  41. Traynham, J. G., Pascual, O. S.: Tetrahedron 7, 165 (1959)

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, York University, 4700 Keele Street, M3J 1P3, Downsview, Ontario, Canada

    Alan C. Hopkinson & Min H. Lien

  2. Department of Chemistry, University of Toronto, 80 St. George Street, M5S 1A1, Toronto, Ontario, Canada

    Imre G. Csizmadia & Keith Yates

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  1. Alan C. Hopkinson
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  2. Min H. Lien
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  3. Imre G. Csizmadia
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  4. Keith Yates
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Hopkinson, A.C., Lien, M.H., Csizmadia, I.G. et al. Quantum chemical studies on electrophilic addition. Theoret. Chim. Acta 47, 97–109 (1978). https://doi.org/10.1007/BF00547747

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  • DOI: https://doi.org/10.1007/BF00547747

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