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

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, V., Peralta, J.E., Contreras, R.H.
Formato: JOUR
Materias:
DFT
Fermi contact
Heavy atom effect
Hyperconjugative interactions
NBO
Acceso en línea: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 todo:paper_01928651_v22_n14_p1615_Barone2023-10-03T15:09:07Z 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, V. Peralta, J.E. Contreras, R.H. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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, V.
Peralta, J.E.
Contreras, R.H.
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.
format JOUR
author Barone, V.
Peralta, J.E.
Contreras, R.H.
author_facet Barone, V.
Peralta, J.E.
Contreras, R.H.
author_sort Barone, V.
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
url http://hdl.handle.net/20.500.12110/paper_01928651_v22_n14_p1615_Barone
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AT peraltaje nmr3jc1h3couplingsin1xbicyclo111pentanesfptdftandnbostudiesofhyperconjugativeinteractionsandheavyatomsubstituenteffects
AT contrerasrh nmr3jc1h3couplingsin1xbicyclo111pentanesfptdftandnbostudiesofhyperconjugativeinteractionsandheavyatomsubstituenteffects
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