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Contreras, R.H.; Esteban, Á.L.; Díez, E.; Della, E.W.; Lochert, I.J.; Dos Santos, F.P.; Tormena, C.F. "Experimental and theoretical study of hyperconjugative interaction effects on NMR1JCH scalar couplings" (2006) Journal of Physical Chemistry A. 110(12):4266-4275
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Abstract:

Hyperconjugative and electrostatic interactions effects on 1JCH spin-spin coupling constants (SSCCs) are critically studied from both theoretical and experimental points of view. A qualitative model is used to predict how the former affect such SSCCs, while electrostatic interactions are modeled with a point charge placed in the vicinity of the corresponding σCH bond. Hyperconjugative interactions are calculated using the "natural bond orbital" approach, and using the point-charge model, it is shown how intertwined are both types of interactions. Several members of the series 1-X-bicyclo[1.1.1]pentane and 1-X-3- methylbicyclo[1.1.1]pentane are chosen as model compounds for measuring 1JCH SSCCs; in some of them were performed also DFT-SSCC calculations. The strained cage substrate in these series defines strong σ-hyperconjugative interactions, making these compounds excellent examples to verify the qualitative model presented in this work. It is verified that (a) hyperconjugative interactions from the σCH bond or into the σ*CH antibond containing the coupling nuclei yield a decrease of the corresponding 1JCH SSCC and (b) hyperconjugative interactions from other bonds involving the coupling C nucleus yield an increase of that 1JCH SSCC. © 2006 American Chemical Society.

Registro:

Documento: Artículo
Título:Experimental and theoretical study of hyperconjugative interaction effects on NMR1JCH scalar couplings
Autor:Contreras, R.H.; Esteban, Á.L.; Díez, E.; Della, E.W.; Lochert, I.J.; Dos Santos, F.P.; Tormena, C.F.
Filiación:Departamento de Física, FCEyN, CONICET (C1428EHA), Buenos Aires, Argentina
Departamento de Química Física, Universidad de Alicante, Apartado 99, E-03080 Alicante, Spain
Departamento de Química Física Aplicada, Facultad de Ciencias, C2, Universidad Autónoma de Madrid, E-28049 Madrid, Spain
Department of Chemistry, Flinders University, Bedford Park, SA 5108, Australia
Departamento de Química, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Avenue Bandeirantes 3900, 14040-901, Ribeirao Preto, Sao Paulo, Brazil
Defense Science and Technology Organization, Weapons Systems Division, P.O. Box 1500, Salisbury, SA 5108, Australia
Palabras clave:Chemical bonds; Electric charge; Electrostatics; Mathematical models; Nuclear magnetic resonance; Nuclear physics; Hyperconjugation; Nucleus; Point charge; Scalar couplings; Molecular physics
Año:2006
Volumen:110
Número:12
Página de inicio:4266
Página de fin:4275
DOI: http://dx.doi.org/10.1021/jp0555201
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_v110_n12_p4266_Contreras

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Citas:

---------- APA ----------
Contreras, R.H., Esteban, Á.L., Díez, E., Della, E.W., Lochert, I.J., Dos Santos, F.P. & Tormena, C.F. (2006) . Experimental and theoretical study of hyperconjugative interaction effects on NMR1JCH scalar couplings. Journal of Physical Chemistry A, 110(12), 4266-4275.
http://dx.doi.org/10.1021/jp0555201
---------- CHICAGO ----------
Contreras, R.H., Esteban, Á.L., Díez, E., Della, E.W., Lochert, I.J., Dos Santos, F.P., et al. "Experimental and theoretical study of hyperconjugative interaction effects on NMR1JCH scalar couplings" . Journal of Physical Chemistry A 110, no. 12 (2006) : 4266-4275.
http://dx.doi.org/10.1021/jp0555201
---------- MLA ----------
Contreras, R.H., Esteban, Á.L., Díez, E., Della, E.W., Lochert, I.J., Dos Santos, F.P., et al. "Experimental and theoretical study of hyperconjugative interaction effects on NMR1JCH scalar couplings" . Journal of Physical Chemistry A, vol. 110, no. 12, 2006, pp. 4266-4275.
http://dx.doi.org/10.1021/jp0555201
---------- VANCOUVER ----------
Contreras, R.H., Esteban, Á.L., Díez, E., Della, E.W., Lochert, I.J., Dos Santos, F.P., et al. Experimental and theoretical study of hyperconjugative interaction effects on NMR1JCH scalar couplings. J Phys Chem A. 2006;110(12):4266-4275.
http://dx.doi.org/10.1021/jp0555201