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Abstract:

All four isotropic contributions to the NMR fluorine-fluorine coupling constants (Fermi contact, FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO) have been calculated for 2,6-difluoropyridine, 2,4,6-trifluoropyridine, perfluoropyridine, and 2-Br-3,4,5,6,7,8-hexafluoroquinoline by means of density functional theory in combination with the rather modest 6-311G** basis set. Experimental values ranging from -20.3 to +45.8 Hz are semiquantitatively reproduced for three- to seven-bond couplings, suggesting that the different electronic effects responsible for the spin-spin interactions are adequately taken into account. In all cases, the relative importance of noncontact terms was examined. With few exceptions, the sum of the SD and PSO noncontact terms is larger than the FC contact contribution, even though in most cases the two noncontact values have opposite signs. The widespread assumption that the Fermi contact term dominates scalar spin-spin couplings in the case of light atoms would appear to be an oversimplification for JFF in polyfluorinated organic molecules. In addition, the CPU performance of the Fermi contact contribution calculated separately by the coupled-perturbed and the finite-perturbation methods was investigated showing the latter to be slightly more efficient.

Registro:

Documento: Artículo
Título:DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines
Autor:Barone, V.; Peralta, J.E.; Contreras, R.H.; Snyder, J.P.
Filiación:Departamento de Física, FCEyN, Universidad de Buenos Aires, Buenos Aires, Argentina
Department of Chemistry, Emory University, Atlanta, GA 30322, United States
Palabras clave:Density functional theory; Finite perturbation theory scheme; Fluorinated pyridines; Spin-spin coupling constants; Aromatic compounds; Chemical bonds; Fermi level; Magnetization; Molecular structure; Perturbation techniques; Probability density function; Fluorine compounds
Año:2002
Volumen:106
Número:23
Página de inicio:5607
Página de fin:5612
DOI: http://dx.doi.org/10.1021/jp020212d
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_v106_n23_p5607_Barone

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Citas:

---------- APA ----------
Barone, V., Peralta, J.E., Contreras, R.H. & Snyder, J.P. (2002) . DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines. Journal of Physical Chemistry A, 106(23), 5607-5612.
http://dx.doi.org/10.1021/jp020212d
---------- CHICAGO ----------
Barone, V., Peralta, J.E., Contreras, R.H., Snyder, J.P. "DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines" . Journal of Physical Chemistry A 106, no. 23 (2002) : 5607-5612.
http://dx.doi.org/10.1021/jp020212d
---------- MLA ----------
Barone, V., Peralta, J.E., Contreras, R.H., Snyder, J.P. "DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines" . Journal of Physical Chemistry A, vol. 106, no. 23, 2002, pp. 5607-5612.
http://dx.doi.org/10.1021/jp020212d
---------- VANCOUVER ----------
Barone, V., Peralta, J.E., Contreras, R.H., Snyder, J.P. DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines. J Phys Chem A. 2002;106(23):5607-5612.
http://dx.doi.org/10.1021/jp020212d