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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Publicado:	2004
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:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v108_n38_p7762_Tormena 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	paper:paper_10895639_v108_n38_p7762_Tormena
record_format	dspace
spelling	paper:paper_10895639_v108_n38_p7762_Tormena2023-06-08T16:06:19Z Anomeric effect on geminal and vicinal JHH NMR coupling constants 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. 2004 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v108_n38_p7762_Tormena 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 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.
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
publishDate	2004
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v108_n38_p7762_Tormena http://hdl.handle.net/20.500.12110/paper_10895639_v108_n38_p7762_Tormena
_version_	1768543573158920192

Anomeric effect on geminal and vicinal JHH NMR coupling constants

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