NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects

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In this work a rationalization of the very large substituent effects on 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes is presented. The Fermi contact contribution to such couplings was calculated in a series of 13 X-derivatives within the DFT-B3LYP framework using the finite perturbation theory....

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Autores principales: Barone, Verónica, Peralta, Juan Ernesto, Contreras, Rubén Horacio
Publicado: 2001
Materias:
DFT
Fermi contact
Heavy atom effect
Hyperconjugative interactions
NBO
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01928651_v22_n14_p1615_Barone
http://hdl.handle.net/20.500.12110/paper_01928651_v22_n14_p1615_Barone
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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_01928651_v22_n14_p1615_Barone2023-06-08T15:19:58Z NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects Barone, Verónica Peralta, Juan Ernesto Contreras, Rubén Horacio DFT Fermi contact Heavy atom effect Hyperconjugative interactions NBO In this work a rationalization of the very large substituent effects on 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes is presented. The Fermi contact contribution to such couplings was calculated in a series of 13 X-derivatives within the DFT-B3LYP framework using the finite perturbation theory. Core electrons for atoms beyond the Second Row were taken into account using effective core potentials. Calculated couplings are in very good agreement with experimental values. The role played by hyperconjugative interactions involving bonds or antibonds belonging to the coupling pathway are studied using the NBO approach. Heavy atom contribution to substituent effects on 3J(C1,H3) couplings was estimated as small. This contrasts notably with trends observed in the corresponding 13C substituent chemical shifts, SCSs. The latter were estimated comparing for X = Cl, Br, I, SnMe3, calculated SCSs with their experimental values. Such estimations are in line with explicit calculations of the spin-orbit contribution reported in the literature for smaller compounds. © 2001 John Wiley & Sons, Inc. J Comput Chem. Fil:Barone, V. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Peralta, J.E. 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. 2001 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01928651_v22_n14_p1615_Barone http://hdl.handle.net/20.500.12110/paper_01928651_v22_n14_p1615_Barone
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic DFT
Fermi contact
Heavy atom effect
Hyperconjugative interactions
NBO
spellingShingle DFT
Fermi contact
Heavy atom effect
Hyperconjugative interactions
NBO
Barone, Verónica
Peralta, Juan Ernesto
Contreras, Rubén Horacio
NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects
topic_facet DFT
Fermi contact
Heavy atom effect
Hyperconjugative interactions
NBO
description In this work a rationalization of the very large substituent effects on 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes is presented. The Fermi contact contribution to such couplings was calculated in a series of 13 X-derivatives within the DFT-B3LYP framework using the finite perturbation theory. Core electrons for atoms beyond the Second Row were taken into account using effective core potentials. Calculated couplings are in very good agreement with experimental values. The role played by hyperconjugative interactions involving bonds or antibonds belonging to the coupling pathway are studied using the NBO approach. Heavy atom contribution to substituent effects on 3J(C1,H3) couplings was estimated as small. This contrasts notably with trends observed in the corresponding 13C substituent chemical shifts, SCSs. The latter were estimated comparing for X = Cl, Br, I, SnMe3, calculated SCSs with their experimental values. Such estimations are in line with explicit calculations of the spin-orbit contribution reported in the literature for smaller compounds. © 2001 John Wiley & Sons, Inc. J Comput Chem.
author Barone, Verónica
Peralta, Juan Ernesto
Contreras, Rubén Horacio
author_facet Barone, Verónica
Peralta, Juan Ernesto
Contreras, Rubén Horacio
author_sort Barone, Verónica
title NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects
title_short NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects
title_full NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects
title_fullStr NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects
title_full_unstemmed NMR 3J(C1,H3) couplings in 1-X-bicyclo[1.1.1]pentanes. FPT-DFT and NBO studies of hyperconjugative interactions and heavy atom substituent effects
title_sort nmr 3j(c1,h3) couplings in 1-x-bicyclo[1.1.1]pentanes. fpt-dft and nbo studies of hyperconjugative interactions and heavy atom substituent effects
publishDate 2001
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01928651_v22_n14_p1615_Barone
http://hdl.handle.net/20.500.12110/paper_01928651_v22_n14_p1615_Barone
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AT peraltajuanernesto nmr3jc1h3couplingsin1xbicyclo111pentanesfptdftandnbostudiesofhyperconjugativeinteractionsandheavyatomsubstituenteffects
AT contrerasrubenhoracio nmr3jc1h3couplingsin1xbicyclo111pentanesfptdftandnbostudiesofhyperconjugativeinteractionsandheavyatomsubstituenteffects
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