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Zaccari, D.; Barone, V.; Peralta, J.E.; Contreras, R.H.; Taurian, O.E.; Díez, E.; Esteban, A. "Solvent effects on nuclear magnetic resonance 2J(C,Hf) and 1J(C,Hf) spin-spin coupling constantsinacetaldehyde" (2003) International Journal of Molecular Sciences. 4(3):93-106
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Abstract:

The known solvent dependence of 1J(Cc,Hf and 2J(C1,Hf) couplings in acetaldehyde is studied from a theoretical viewpoint based on the density functional theory approach where the dielectric solvent effect is taken into account with the polarizable continuum model. The four terms of scalar couplings, Fermi contact, paramagnetic spin orbital, diamagnetic spin orbital and spin dipolar, are calculated but the solvent effect analysis is restricted to the first term since for both couplings it is by far the dominant contribution. Experimental trends of Δ1J(Cc,Hf) and Δ 2J(C1,Hf) Vs ε (the solvent dielectric constant) are correctly reproduced although they are somewhat underestimated. Specific interactions between solute and solvent molecules are studied for dimethylsulfoxide, DMSO, solutions considering two different one-to-one molecular complexes between acetaldehyde and DMSO. They are determined by interactions of type C=O-H-C and S=O-H-C, and the effects of such interactions on 1J(Cc,Hf) and 2J(C 1,Hf) couplings are analyzed. Even though only in a semiquantitative way, it is shown that the effect of such interactions on the solvent effects, of Δ1J(Cc,Hf) and Δ2J(C1,Hf), tend to improve the agreement between calculated and experimental values. These results seem to indicate that a continuum dielectric model has not enough flexibility for describing quantitatively solvent effects on spin-spin couplings. Apparently, even for relatively weak hydrogen bonding, the contribution from "direct" interactions is of the same order of magnitude as the "dielectric" effect.

Registro:

Documento: Artículo
Título:Solvent effects on nuclear magnetic resonance 2J(C,Hf) and 1J(C,Hf) spin-spin coupling constantsinacetaldehyde
Autor:Zaccari, D.; Barone, V.; Peralta, J.E.; Contreras, R.H.; Taurian, O.E.; Díez, E.; Esteban, A.
Filiación:Departamento de Quimica y Fisica, FCEF-QyN Univ. Nac. de Rio Cuarto, Ruta Nac. 36, Km 601, (5800) Río Cuarto, Argentina
Departamento de Física, Univ. de Buenos Aires and CONICET, Ciudad Universitaria, (1428), Buenos Aires, Argentina
Depto. de Quimica Fisica Aplicada, Facultad de Ciencias C2, Univ. Autónoma de Madrid, E-28049, Madrid, Spain
Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Alicante, E-03080 Alicante, Spain
Palabras clave:Density functional theory; Natural J coupling; Solvent effect; Spin-spin couplings; acetaldehyde; benzaldehyde; dimethyl sulfoxide; salicylaldehyde; article; complex formation; density functional theory; dielectric constant; electron spin resonance; hydrogen bond; molecular interaction; nuclear magnetic resonance; solvation; solvent effect
Año:2003
Volumen:4
Número:3
Página de inicio:93
Página de fin:106
DOI: http://dx.doi.org/10.3390/i4030093
Título revista:International Journal of Molecular Sciences
Título revista abreviado:Int. J. Mol. Sci.
ISSN:14220067
CAS:acetaldehyde, 75-07-0; benzaldehyde, 100-52-7; dimethyl sulfoxide, 67-68-5; salicylaldehyde, 90-02-8
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14220067_v4_n3_p93_Zaccari

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Citas:

---------- APA ----------
Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurian, O.E., Díez, E. & Esteban, A. (2003) . Solvent effects on nuclear magnetic resonance 2J(C,Hf) and 1J(C,Hf) spin-spin coupling constantsinacetaldehyde. International Journal of Molecular Sciences, 4(3), 93-106.
http://dx.doi.org/10.3390/i4030093
---------- CHICAGO ----------
Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurian, O.E., Díez, E., et al. "Solvent effects on nuclear magnetic resonance 2J(C,Hf) and 1J(C,Hf) spin-spin coupling constantsinacetaldehyde" . International Journal of Molecular Sciences 4, no. 3 (2003) : 93-106.
http://dx.doi.org/10.3390/i4030093
---------- MLA ----------
Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurian, O.E., Díez, E., et al. "Solvent effects on nuclear magnetic resonance 2J(C,Hf) and 1J(C,Hf) spin-spin coupling constantsinacetaldehyde" . International Journal of Molecular Sciences, vol. 4, no. 3, 2003, pp. 93-106.
http://dx.doi.org/10.3390/i4030093
---------- VANCOUVER ----------
Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurian, O.E., Díez, E., et al. Solvent effects on nuclear magnetic resonance 2J(C,Hf) and 1J(C,Hf) spin-spin coupling constantsinacetaldehyde. Int. J. Mol. Sci. 2003;4(3):93-106.
http://dx.doi.org/10.3390/i4030093