Anomeric effect on geminal and vicinal JHH NMR coupling constants

Trends for geminal (2JHH) and vicinal ( 3JHH) nuclear magnetic resonance indirect spin-spin coupling constants, SSCCs, for 2-methylthiirane (5) and 2-methyloxirane (6) are studied both from experimental and theoretical points of view to determine the influence of hyperconjugative interactions on the...

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Autores principales: Tormena, C.F., Rittner, R., Contreras, R.H., Peralta, J.E.
Formato: JOUR
Materias:
Chemical bonds
Diamagnetism
Dielectric properties
Molecular structure
Nuclear magnetic resonance spectroscopy
Paramagnetism
Protons
Anomeric effect
Coupling constant
Diamagnetic spin
Spin-spin coupling
Isomers
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_10895639_v108_n38_p7762_Tormena
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_10895639_v108_n38_p7762_Tormena
record_format dspace
spelling todo:paper_10895639_v108_n38_p7762_Tormena2023-10-03T16:04:32Z Anomeric effect on geminal and vicinal JHH NMR coupling constants Tormena, C.F. Rittner, R. Contreras, R.H. Peralta, J.E. Chemical bonds Diamagnetism Dielectric properties Molecular structure Nuclear magnetic resonance spectroscopy Paramagnetism Protons Anomeric effect Coupling constant Diamagnetic spin Spin-spin coupling Isomers Trends for geminal (2JHH) and vicinal ( 3JHH) nuclear magnetic resonance indirect spin-spin coupling constants, SSCCs, for 2-methylthiirane (5) and 2-methyloxirane (6) are studied both from experimental and theoretical points of view to determine the influence of hyperconjugative interactions on these couplings. These two analogous compounds were chosen because it was expected that they exhibit quite different anomeric effects. Hyperconjugative interactions are investigated using the "natural bond orbital" method. Coupling constants are calculated within the density functional theory including all four scalar contributions, that is, the Fermi contact, the spin-dipolar, and the paramagnetic and diamagnetic spin-orbital contributions. Solvent dielectric effects are taken into account using Tomasi's polarizable continuum model. Results for geminal couplings are consistent with linear correlations connecting 2J HH with the coupling pathway occupation numbers taken from the literature. The present analysis suggests that both 2JHH and 3JHH coupling constants are sensitive probes to gauge the anomeric effect, as well as other hyperconjugative interactions. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_10895639_v108_n38_p7762_Tormena
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Chemical bonds
Diamagnetism
Dielectric properties
Molecular structure
Nuclear magnetic resonance spectroscopy
Paramagnetism
Protons
Anomeric effect
Coupling constant
Diamagnetic spin
Spin-spin coupling
Isomers
spellingShingle Chemical bonds
Diamagnetism
Dielectric properties
Molecular structure
Nuclear magnetic resonance spectroscopy
Paramagnetism
Protons
Anomeric effect
Coupling constant
Diamagnetic spin
Spin-spin coupling
Isomers
Tormena, C.F.
Rittner, R.
Contreras, R.H.
Peralta, J.E.
Anomeric effect on geminal and vicinal JHH NMR coupling constants
topic_facet Chemical bonds
Diamagnetism
Dielectric properties
Molecular structure
Nuclear magnetic resonance spectroscopy
Paramagnetism
Protons
Anomeric effect
Coupling constant
Diamagnetic spin
Spin-spin coupling
Isomers
description Trends for geminal (2JHH) and vicinal ( 3JHH) nuclear magnetic resonance indirect spin-spin coupling constants, SSCCs, for 2-methylthiirane (5) and 2-methyloxirane (6) are studied both from experimental and theoretical points of view to determine the influence of hyperconjugative interactions on these couplings. These two analogous compounds were chosen because it was expected that they exhibit quite different anomeric effects. Hyperconjugative interactions are investigated using the "natural bond orbital" method. Coupling constants are calculated within the density functional theory including all four scalar contributions, that is, the Fermi contact, the spin-dipolar, and the paramagnetic and diamagnetic spin-orbital contributions. Solvent dielectric effects are taken into account using Tomasi's polarizable continuum model. Results for geminal couplings are consistent with linear correlations connecting 2J HH with the coupling pathway occupation numbers taken from the literature. The present analysis suggests that both 2JHH and 3JHH coupling constants are sensitive probes to gauge the anomeric effect, as well as other hyperconjugative interactions.
format JOUR
author Tormena, C.F.
Rittner, R.
Contreras, R.H.
Peralta, J.E.
author_facet Tormena, C.F.
Rittner, R.
Contreras, R.H.
Peralta, J.E.
author_sort Tormena, C.F.
title Anomeric effect on geminal and vicinal JHH NMR coupling constants
title_short Anomeric effect on geminal and vicinal JHH NMR coupling constants
title_full Anomeric effect on geminal and vicinal JHH NMR coupling constants
title_fullStr Anomeric effect on geminal and vicinal JHH NMR coupling constants
title_full_unstemmed Anomeric effect on geminal and vicinal JHH NMR coupling constants
title_sort anomeric effect on geminal and vicinal jhh nmr coupling constants
url http://hdl.handle.net/20.500.12110/paper_10895639_v108_n38_p7762_Tormena
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AT rittnerr anomericeffectongeminalandvicinaljhhnmrcouplingconstants
AT contrerasrh anomericeffectongeminalandvicinaljhhnmrcouplingconstants
AT peraltaje anomericeffectongeminalandvicinaljhhnmrcouplingconstants
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