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Abstract:

Theoretical and experimental studies on 3J C2H6eq NMR spin - spin coupling constants in both the 2-X-4-t-butyl-cyclohexanone (X = H, CH 3, F, Cl, and Br) and in their alcohol derivatives series are reported. Results thus found are rationalized in terms of the transmission of the Fermi contact contribution to such couplings. To this end, dependencies of 3J C2H6eq couplings versus the C 2 - C 1 - C 6 angle are compared in both series for equatorial and axial X orientations. The main trend is described in terms of the rear lobes interaction. Besides, for X = halogen atom in equatorial orientation a rather strong interaction between oxygen and halogen lone pairs is observed, and its influence on 3J C2H6eq couplings is discussed and rationalized in terms of different Fermi contact transmission pathways. (Figure presented) © 2011 American Chemical Society.

Registro:

Documento: Artículo
Título:Stereochemical dependence of 3J CH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives
Autor:Favaro, D.C.; Ducati, L.C.; Dos Santos, F.P.; Contreras, R.H.; Tormena, C.F.
Filiación:Chemistry Institute, State University of Campinas, Caixa Postal 6154, 13084-971 Campinas SP, Brazil
Department of Physics, FCEyN, University of Buenos Aires, Buenos Aires, Argentina
Palabras clave:Alcohol derivatives; Coupling constants; Experimental studies; Fermi contact; Halogen atoms; Lone pair; Spin coupling constants; Strong interaction; Bromine; Chlorine; Couplings
Año:2011
Volumen:115
Número:50
Página de inicio:14539
Página de fin:14545
DOI: http://dx.doi.org/10.1021/jp2083456
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_v115_n50_p14539_Favaro

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Citas:

---------- APA ----------
Favaro, D.C., Ducati, L.C., Dos Santos, F.P., Contreras, R.H. & Tormena, C.F. (2011) . Stereochemical dependence of 3J CH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives. Journal of Physical Chemistry A, 115(50), 14539-14545.
http://dx.doi.org/10.1021/jp2083456
---------- CHICAGO ----------
Favaro, D.C., Ducati, L.C., Dos Santos, F.P., Contreras, R.H., Tormena, C.F. "Stereochemical dependence of 3J CH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives" . Journal of Physical Chemistry A 115, no. 50 (2011) : 14539-14545.
http://dx.doi.org/10.1021/jp2083456
---------- MLA ----------
Favaro, D.C., Ducati, L.C., Dos Santos, F.P., Contreras, R.H., Tormena, C.F. "Stereochemical dependence of 3J CH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives" . Journal of Physical Chemistry A, vol. 115, no. 50, 2011, pp. 14539-14545.
http://dx.doi.org/10.1021/jp2083456
---------- VANCOUVER ----------
Favaro, D.C., Ducati, L.C., Dos Santos, F.P., Contreras, R.H., Tormena, C.F. Stereochemical dependence of 3J CH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives. J Phys Chem A. 2011;115(50):14539-14545.
http://dx.doi.org/10.1021/jp2083456