Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms

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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 path...

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Autores principales: Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., De Azúa, M.C.R., Contreras, R.H.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_01661280_v205_nC_p63_Aucar
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_01661280_v205_nC_p63_Aucar2023-10-03T15:03:13Z Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms Aucar, G.A. Zunino, V. Ferraro, M.B. Giribet, C.G. De Azúa, M.C.R. Contreras, R.H. 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. Fil:Aucar, G.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Zunino, V. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Ferraro, M.B. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Giribet, C.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_01661280_v205_nC_p63_Aucar
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description 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.
format JOUR
author Aucar, G.A.
Zunino, V.
Ferraro, M.B.
Giribet, C.G.
De Azúa, M.C.R.
Contreras, R.H.
spellingShingle 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
author_facet Aucar, G.A.
Zunino, V.
Ferraro, M.B.
Giribet, C.G.
De Azúa, M.C.R.
Contreras, R.H.
author_sort Aucar, G.A.
title Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms
title_short Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms
title_full Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms
title_fullStr Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms
title_full_unstemmed Analysis of multipath transmission of spin-spin coupling constants in 1-X-bicycloalkanes. Part I. The through-space transmission via the bridgehead carbon atoms
title_sort analysis of multipath transmission of spin-spin coupling constants in 1-x-bicycloalkanes. part i. the through-space transmission via the bridgehead carbon atoms
url http://hdl.handle.net/20.500.12110/paper_01661280_v205_nC_p63_Aucar
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