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The Calculation of directly bonded 13C-H and 13C-13C coupling constants using delocalized molecular orbital theory

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Abstract

The Pople-Santry theory of coupling in σ-electron systems lias been applied to directly bonded CH and CC coupling constants. Calculations on normal hydrocarbons, e.g. CH4, C2H6, C2H4, C2H2, show that the theory can give a satisfactory explanation of such coupling constants, although the values are sensitive to the parameters used in the calculation. The theory has been applied with varying success to the larger hydrocarbons methylacetylene, butadiene and benzene, and to the strained molecules cyclopropane and ferrocene. No difficulty arises in applying the theory to hetero-atomic systems (pyridine and pyrimidine) and the results are quite satisfactory.

Zusammenfassung

Die Pople-Santry Theory über Koppelung in σ-Elektronensystemen wurde auf CH und CC Koppelungskonstanten direkt gebundener Atome angewandt. Rechnungen für einfache Kohlenwasserstoffe, z. B. CH4, C2H6, C2H4, C2H2 zeigen, daß die Theorie eine zufriedenstellende Erklärung solcher Koppelungskonstanten geben kann, obwohl die Werte empfindlich von den in der Rechnung benutzten Parametern abhängen. Die Theorie wurde mit unterschiedlichem Erfolg auf die größeren Kohlenwasserstoffe Methylazetylen, Butadien und Benzol und auf die gespannten Moleküle Cyclopropan und Ferrocen angewandt. Bei Anwendung der Theorie auf Systeme mit Heteroatomen (Pyridin und Pyrimidin) entsteht keine Schwierigkeit und die Ergebnisse sind zufriedenstellend.

Résumé

La théorie de Pople et Santry sur le couplage dans les systèmes σ d'électrons a été appliquée aux constantes de couplage CH et CC entre atomes liés. Les calcules pour quelques simples hydrocarbures, par example CH4, C2H6, C2H4, C2H2, montrent que la théorie explique satisfaisamment ces constantes, bien que les valeurs dépendent sensiblement des paramètres du calcul. La théorie a été appliquée avec succès variable aux hydrocarbures plus grandes: methylacetylene, butadiene et benzène et aux molecules tendues: cyclopropane et ferrocène. Des systèmes à hétéroatomes (pyridine et pyrimidine) ne prêtent pas de difficultés, et les résultats sont satisfaisants.

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References

  1. Bent, H. A.: Chem. Reviews. 61, 275 (1961).

    Google Scholar 

  2. Certain, P. R., V. S. Watts, and J. H. Goldstein: Theoret. chim. Acta 2, 324 (1964).

    Google Scholar 

  3. Dischler, B.: Z. f. Naturforsch. 19a, 887 (1964).

    Google Scholar 

  4. Douglas, A. W.: J. chem. Physics. 40, 2413 (1964), and refs. given there.

    Google Scholar 

  5. e.g. see Frei, K., and H. J. Bernstein: J. chem. Physics 38, 1216 (1963).

    Google Scholar 

  6. Gutowsky, H. S., and C. Juan: J. chem. Physics. 37, 2198 (1962).

    Google Scholar 

  7. Jones, M. E., K. Hedberg, and V. Schomaker: J. Amer. chem. Soc. 77, 5278 (1955).

    Google Scholar 

  8. Lennard-Jones, Sir J.: Proc. Roy. Soc. A 198, 1, 14 (1949).

    Google Scholar 

  9. Lowdin, P.-O.: Phys. Rev. 90, 120 (1952).

    Google Scholar 

  10. Lynden-Bell, R. M., and N. Sheppard: Proc. Roy. Soc. A 269, 385 (1962).

    Google Scholar 

  11. Malinowsky, E. R.: J. Amer. chem. Soc. 83, 4479 (1961). However, see [4].

    Google Scholar 

  12. —, L. Z. Pollar, and J. P. Larmann: ibid.|J. Amer. chem. Soc. 84, 2649 (1962).

    Google Scholar 

  13. McConnel, H. M.: J. chem. Physics. 24, 460 (1956).

    Google Scholar 

  14. Mislow, K.: Tetr. Lett. 1415 (1964), and refs. given there.

  15. Muller, N, and D. E. Pritchard: J. chem. Physics. 31, 768, 1471 (1959).

    Google Scholar 

  16. ibid 36, 359 (1962).

    Google Scholar 

  17. Pople, J. A., and D. P. Santry: Molecular Physics. 7, 269 (1963).

    Google Scholar 

  18. ibid 8, 1 (1964).

    Google Scholar 

  19. —, and A. A. Bothner-By: J. chem. Physics. 42, 1339 (1965).

    Google Scholar 

  20. Randić, M., and Z. Maksić: Theoret. chim. Acta 3, 59 (1965).

    Google Scholar 

  21. Reddy, G. S., R. T. Hobgood, and J. H. Goldstein: J. Amer. chem. Soc. 84, 336 (1962).

    Google Scholar 

  22. Shoolery, J. N.: J. chem. Physics. 31, 1427 (1959).

    Google Scholar 

  23. Sutton, L. E.: Tables of interatomic distances, Chem. Soc. Spec. Publ. 11 (1958).

  24. Wheatley, P. J.: Acta Cryst. 13, 80 (1960).

    Google Scholar 

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Authors and Affiliations

  1. The Chemical Laboratory, The University of Sussex, England

    F. B. van Duijneveldt, V. M. S. Gil & J. N. Murrell

  2. Organisch Chemisch Laboratorium, University of Utrecht, UK

    F. B. van Duijneveldt

  3. Department of Chemistry, University of Coimbra, Portugal

    V. M. S. Gil

Authors
  1. F. B. van Duijneveldt
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  2. V. M. S. Gil
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  3. J. N. Murrell
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van Duijneveldt, F.B., Gil, V.M.S. & Murrell, J.N. The Calculation of directly bonded 13C-H and 13C-13C coupling constants using delocalized molecular orbital theory. Theoret. Chim. Acta 4, 85–93 (1966). https://doi.org/10.1007/BF00526013

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