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Abstract:

Long-range 4JHH couplings in 1,3-dithiane derivatives are rationalized in terms of the effects of hyperconjugative interactions involving the S=0 group. Theoretical and experimental studies of 4JHH couplings were carried out in 1,3-dithiane-l-oxide (2), cw-l,3-dithiane-l,3-dioxide (3), l,3-dithiane-l,l,3-trioxide (4), and 1,3-dithiane-1,1,3,3-tetraoxide (5) compounds. Hyperconjugative interactions were studied with the natural bond orbital, NBO, method. Hyperconjugative interactions involving the LP O, oxygen lone pair and σ*C2-S1 and σ*S1-C6 antibonding orbitals yield an increase of 4JHeq-Heq couplings. Long-range 4JHax-Hax couplings were also observed between hydrogen atoms in axial orientation, which are rationalized as originating in hyperconjugative interactions involving the bonding σC6-h axand antibonding σ*S=O orbitals. The symmetry for orbital interactions is possible only when the S=0 group is in the axial orientation. © 2009 American Chemical Society.

Registro:

Documento: Artículo
Título:Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane
Autor:Gauze, G.F.; Basso, E.A.; Contreras, R.H.; Tormena, C.F.
Filiación:Departamento de Química, Universidade Estadual de Maringá, CEP-87020-900, Maringá, Brazil
Department of Physics, FCEyN, University of Buenos Aires and CONICET, Buenos Aires, Argentina
Department of Organic Chemistry, Chemistry Institute, University of Campinas, UNICAMP, P.O. Box 6154, CEP: 13084-971 Campinas, Brazil
Palabras clave:3 dioxides; Anti bondings; Antibonding orbitals; Axial orientations; Experimental studies; Hydrogen atoms; Hyperconjugative interactions; Lone pairs; Natural bond orbitals; Nmr couplings; Orbital interactions; Orbitals; Sulfur oxidations; Transmission mechanisms; Hydrogen; Oxygen; Sulfur; Sulfur compounds; Couplings
Año:2009
Volumen:113
Número:11
Página de inicio:2647
Página de fin:2651
DOI: http://dx.doi.org/10.1021/jp810981z
Título revista:Journal of Physical Chemistry A
Título revista abreviado:J Phys Chem A
ISSN:10895639
CODEN:JPCAF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v113_n11_p2647_Gauze

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Citas:

---------- APA ----------
Gauze, G.F., Basso, E.A., Contreras, R.H. & Tormena, C.F. (2009) . Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane. Journal of Physical Chemistry A, 113(11), 2647-2651.
http://dx.doi.org/10.1021/jp810981z
---------- CHICAGO ----------
Gauze, G.F., Basso, E.A., Contreras, R.H., Tormena, C.F. "Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane" . Journal of Physical Chemistry A 113, no. 11 (2009) : 2647-2651.
http://dx.doi.org/10.1021/jp810981z
---------- MLA ----------
Gauze, G.F., Basso, E.A., Contreras, R.H., Tormena, C.F. "Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane" . Journal of Physical Chemistry A, vol. 113, no. 11, 2009, pp. 2647-2651.
http://dx.doi.org/10.1021/jp810981z
---------- VANCOUVER ----------
Gauze, G.F., Basso, E.A., Contreras, R.H., Tormena, C.F. Effect of sulfur oxidation on the transmission mechanism of4JHH NMR coupling constants in 1,3-dithiane. J Phys Chem A. 2009;113(11):2647-2651.
http://dx.doi.org/10.1021/jp810981z