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Abstract:

The IPPP‐CLOPPA method is used to study the origin of the difference between exo‐exo and endo‐endo vicinal interproton couplings in norbornane and norbornene. The main pathway defining such couplings is found to be determined by the corresponding CH bonds and antibonds. For this reason they can be considered to be transmitted through space. Contributions from excitations involving MOs of bridge 7 and the CH endo and exo bonds and antibonds are found to be negligible in both compounds. Even though bridges 5–6 and 7 are not included in the coupling pathway, they influence the structure of endo and exo CH bonds, and thus cause the nonequivalence of endo‐endo and exo‐exo couplings. Results obtained with the NNBI method are compared to those of IPPP‐CLOPPA. Copyright © 1991 John Wiley & Sons, Inc.

Registro:

Documento: Artículo
Título:Exo‐exo and endo‐endo vicinal proton spin‐spin coupling constants in norbornane and norbornene. An IPPP‐CLOPPA analysis
Autor:Cavasotto, C.N.; Giribet, C.G.; de Azúa, M.C.R.; Contreras, R.H.
Filiación:Departamento de Física, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Buenos Aires, 1428, Argentina
Año:1991
Volumen:12
Número:2
Página de inicio:141
Página de fin:146
DOI: http://dx.doi.org/10.1002/jcc.540120202
Título revista:Journal of Computational Chemistry
Título revista abreviado:J. Comput. Chem.
ISSN:01928651
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01928651_v12_n2_p141_Cavasotto

Referencias:

  • Musher, J.I., The N.M.R. spectra of some bicyclo [2.2.1] heptanols (1963) Molecular Physics, 6, p. 93
  • Laszlo, P., von Ragué Schleyer, P., (1964) J. Am. Chem. Soc., 86, p. 1171
  • Subramanian, P.M., Emerson, M.T., Le Bel, N.A., (1965) J. Org. Chem., 30, p. 2624
  • Marchand, A.P., Marchand, N.W., Segre, A.L., (1969) Tetrahedron Lett., 59, p. 5207
  • Anet, F.A.L., Lee, H.H., Sudmeier, J.L., (1967) J. Am. Chem. Soc., 89, p. 4431
  • Karplus, M., (1959) J. Chem. Phys., 30, p. 11
  • (1963) J. Am. Chem. Soc., 85, p. 2870
  • Marshall, J.L., Walter, S.R., Barfield, M., Marchand, A.P., Marchand, N.W., Segre, A.L., (1976) Tetrahedron, 32, p. 537
  • Barfield, M., Dean, A.M., Fallick, C.J., Spear, R.J., Sternhell, S., Westerman, P.W., (1975) J. Am. Chem. Soc., 97, p. 1482
  • Barfield, M., (1980) J. Am. Chem. Soc., 102, p. 1
  • de Leeuw, F.A.A.M., van Beuzekom, A.A., Altona, C., Through-Space effects on vicinal proton spin-spin coupling constants mediated via hetero atoms: Nonequivalence of cis couplings in five-membered rings (1983) Journal of Computational Chemistry, 4, p. 438
  • Engelmann, A.R., Contreras, R.H., Transmission mechanisms of spin-spin coupling constants within theCHF approximation: Their study using inner projections of the polarization propagator (1983) International Journal of Quantum Chemistry, 23, p. 1033
  • Diz, A.C., Giribet, C.G., Contreras, R.H., The use of localized molecular orbitals and the polarization propagator to identify transmission mechanisms in nuclear spin-spin couplings (1990) International Journal of Quantum Chemistry, 37, p. 663. , M.C. Ruiz de Azúa
  • Ruiz de Azúa, M.C., Diz, A.C., Giribet, C.G., Contreras, R.H., Rae, I.D., (1986) Int. J. Quant. Chem., 20 S, p. 585
  • Aucar, G.A., Giribet, C.G., Ruiz de Azúa, M.C., Diz, A.C., Contreras, R.H., (1988) J. Mol. Struct. (Theochem), 164, p. 1
  • Rae, I.D., Staffa, A., Diz, A.C., Giribet, C.G., Ruiz de Azúa, M.C., Contreras, R.H., Through-Space Transmission of19F-13C Coupling Via an Intermediate Bond. An Experimental and Theoretical Study (1987) Australian Journal of Chemistry, 40, p. 1923
  • Contreras, R.H., Ruiz de Azúa, M.C., Giribet, C.G., (1986) Magnetic Resonance in Chemistry, 24, p. 675
  • Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., Ruiz de Azúa, M.C., Contreras, R.H., (1990) J. Mol. Struct. (Theochem), 205, p. 63
  • Contreras, R.H., Scuseria, G.E., Theoretical additivity in multipath13C,1H coupling constants (1984) Organic Magnetic Resonance, 22, p. 411
  • Linderberg, J., Öhrn, Y., (1973) Propagators in Quantum Chemistry, , Academic Press, London, Chap. 7
  • Oddershede, J., (1978) Advances in Quantum Chemistry, 11. , P. O. Löwdin, Academic Press, New York
  • Verwoerd, W., (1979) Chem. Phys., 44, p. 151
  • Pople, J.A., Beveridge, D.L., (1970) Approximate Molecular Orbital Theory, , McGraw‐Hill, New York, Chap. 4
  • Archirel, P., Barbier, C., (1978) J. Chem. Phys., 75, p. 1003
  • Chiang, J.F., Wilcox, C.F., Jr., Bauer, S.H., (1968) J. Am. Chem. Soc., 90, p. 3149
  • Chiang, J.F., Chiang, R., Lu, K.C., Sung, E.‐M., Harmony, M.D., (1977) J. Mol. Struct., 41, p. 67
  • Wiberg, K.B., (1985) J. Org. Chem., 50, p. 5285
  • Bremer, M., Schötz, K., von Ragué Schleyer, P., Fleischer, U., Schindler, M., Kutzelnigg, W., Koch, W., Pulay, P., The 7-Norbornadienyl Cation: An NMR/IGLO Validation of its ab initio Structure (1989) Angewandte Chemie International Edition in English, 28, p. 1042
  • A print out of the 6‐31G* optimized geometries of norbornane and norbornene is gratefully acknowledged to Prof. Paul von Ragué Schleyer

Citas:

---------- APA ----------
Cavasotto, C.N., Giribet, C.G., de Azúa, M.C.R. & Contreras, R.H. (1991) . Exo‐exo and endo‐endo vicinal proton spin‐spin coupling constants in norbornane and norbornene. An IPPP‐CLOPPA analysis. Journal of Computational Chemistry, 12(2), 141-146.
http://dx.doi.org/10.1002/jcc.540120202
---------- CHICAGO ----------
Cavasotto, C.N., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H. "Exo‐exo and endo‐endo vicinal proton spin‐spin coupling constants in norbornane and norbornene. An IPPP‐CLOPPA analysis" . Journal of Computational Chemistry 12, no. 2 (1991) : 141-146.
http://dx.doi.org/10.1002/jcc.540120202
---------- MLA ----------
Cavasotto, C.N., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H. "Exo‐exo and endo‐endo vicinal proton spin‐spin coupling constants in norbornane and norbornene. An IPPP‐CLOPPA analysis" . Journal of Computational Chemistry, vol. 12, no. 2, 1991, pp. 141-146.
http://dx.doi.org/10.1002/jcc.540120202
---------- VANCOUVER ----------
Cavasotto, C.N., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H. Exo‐exo and endo‐endo vicinal proton spin‐spin coupling constants in norbornane and norbornene. An IPPP‐CLOPPA analysis. J. Comput. Chem. 1991;12(2):141-146.
http://dx.doi.org/10.1002/jcc.540120202