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Abstract:

The through-space transmission of couplings involving bridgehead carbon atoms in substituted 1-X-bicycloalkanes (X = H, F, CH3) was analysed theoretically with a modified version of the IPPP-INDO method. The through-space components are further decomposed into a sum of individual "coupling pathways", each of which involves two occupied and two vacant localized orbitals. The relative importance of these orbitals indicates which are the most important bonds and antibonding orbitals defining the transmission mechanisms. In this way, it is shown that the main trends of the through-space component of j(C1-H) (where H is the proton bonded to the remaining bridgehead carbon atom CH) and J(C1-CH) are directly related to the amplitude of the CH-H bonding orbital on C1. The decrease in the through-space values when going from bicyclopentane to bicyclooctane is thus explained by the decrease in this amplitude as the C1-CH distance increases. The dependence of J(C1-H) on the substituent X can also be explained by the effect of X on the CH-H bond. The through-space IPPP results are found to be quite different from those obtained using the NNBI approach, showing that both methods are based on different grounds. © 1990.

Registro:

Documento: Artículo
Título:Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms
Autor:Aucar, G.A.; Zunino, V.; Ferraro, M.B.; Giribet, C.G.; De Azúa, M.C.R.; Contreras, R.H.
Filiación:Departamento de Fisica, Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, 3400 CorrientesArgentina
Universidad Nacional de Luján, 6700 LujánArgentina
Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, UBA, Ciudad Universitaria, Pab. 1, 1428 Buenos AiresArgentina
Año:1990
Volumen:205
Número:C
Página de inicio:63
Página de fin:77
DOI: http://dx.doi.org/10.1016/0166-1280(90)85107-X
Título revista:Journal of Molecular Structure: THEOCHEM
Título revista abreviado:J. Mol. Struct. THEOCHEM
ISSN:01661280
CODEN:THEOD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v205_nC_p63_Aucar

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Citas:

---------- APA ----------
Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., De Azúa, M.C.R. & Contreras, R.H. (1990) . Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms. Journal of Molecular Structure: THEOCHEM, 205(C), 63-77.
http://dx.doi.org/10.1016/0166-1280(90)85107-X
---------- CHICAGO ----------
Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., De Azúa, M.C.R., Contreras, R.H. "Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms" . Journal of Molecular Structure: THEOCHEM 205, no. C (1990) : 63-77.
http://dx.doi.org/10.1016/0166-1280(90)85107-X
---------- MLA ----------
Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., De Azúa, M.C.R., Contreras, R.H. "Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms" . Journal of Molecular Structure: THEOCHEM, vol. 205, no. C, 1990, pp. 63-77.
http://dx.doi.org/10.1016/0166-1280(90)85107-X
---------- VANCOUVER ----------
Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., De Azúa, M.C.R., Contreras, R.H. Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms. J. Mol. Struct. THEOCHEM. 1990;205(C):63-77.
http://dx.doi.org/10.1016/0166-1280(90)85107-X