Artículos de revistas
Anomeric Effect On Geminal And Vicinal Jhh Nmr Coupling Constants
Registro en:
Journal Of Physical Chemistry A. , v. 108, n. 38, p. 7762 - 7768, 2004.
10895639
10.1021/jp047226z
2-s2.0-4944229277
Autor
Tormena C.F.
Rittner R.
Contreras R.H.
Peralta J.E.
Institución
Resumen
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. 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