Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes

A series of 23 bridgehead-substituted bicyclo[1.1.1]pentanes were synthesized and the 3J(C1-H) coupling constants determined from their proton-coupled 13C NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exe...

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Publicado: 1996
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v9_n3_p168_Della
http://hdl.handle.net/20.500.12110/paper_08943230_v9_n3_p168_Della
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_08943230_v9_n3_p168_Della2023-06-08T15:47:49Z Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes A series of 23 bridgehead-substituted bicyclo[1.1.1]pentanes were synthesized and the 3J(C1-H) coupling constants determined from their proton-coupled 13C NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give 3J(C1-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a second-row element. © 1996 by John Wiley & Sons, Ltd. 1996 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v9_n3_p168_Della http://hdl.handle.net/20.500.12110/paper_08943230_v9_n3_p168_Della
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description A series of 23 bridgehead-substituted bicyclo[1.1.1]pentanes were synthesized and the 3J(C1-H) coupling constants determined from their proton-coupled 13C NMR spectra. It was found that the values of the couplings are strongly dependent upon the type of substituent present, with powerful effects exerted by the halogens in particular. The IPPP-CLOPPA-INDO theoretical approach, which was employed to provide a measure of the extent of through-bond versus through-space transmission of coupling information, was found to give 3J(C1-H) values in good agreement with experimental data. Empirical substituent parameter regressions were performed and found to be consistent with the CLOPPA description of the increase in both the through-bond and through-space contributions to the coupling. The substituent parameter regressional analyses also demonstrated that electronegativity effects play a predominant role in determining the magnitude of the couplings, particularly in those substrates in which the substituent is attached to the ring system by a second-row element. © 1996 by John Wiley & Sons, Ltd.
title Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
spellingShingle Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
title_short Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
title_full Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
title_fullStr Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
title_full_unstemmed Experimental and theoretical study of substituent effects on3J(13Cl-1H) coupling constants in 1-X-bicyclo[1.1.1]pentanes
title_sort experimental and theoretical study of substituent effects on3j(13cl-1h) coupling constants in 1-x-bicyclo[1.1.1]pentanes
publishDate 1996
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v9_n3_p168_Della
http://hdl.handle.net/20.500.12110/paper_08943230_v9_n3_p168_Della
_version_ 1768543662798536704

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