Artículo
Rae, I.D.; Staffa, A.; Diz, A.C.; Giribet, C.G.; de Azúa, M.C.R.; Contreras, R.H. "Through-space transmission of 19F-13C coupling via an intermediate bond. An experimental and theoretical study" (1987) Australian Journal of Chemistry. 40(12):1923-1940
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Abstract:
In order to obtain a deeper insight into the title effect, several compounds with an F atom very close to a C-H of a nearby functional group were synthesized and the relevant couplings measured. The most conspicuous case was that of 8-fluoro-2-hydroxynaphthalene-l-carbaldehyde where a close proximity between the F and H atoms is the result of fluorine-oxygen repulsion and the formation of an intramolecular hydrogen bond between the hydroxyl and carbonyl groups. The experimental four-bond J(F, CHO) coupling is 26·2 Hz. A compound very similar to this one, but without the OH group, was chosen on which to perform a polarization propagator analysis of the through-space (ts) coupling pathways, at the rpa-indo level. The expression for the ts coupling in terms of the projected polarization propagator and perturbators was numerically analysed. It is found that this coupling is completely dominated by a ts component of the Fermi contact (fc) term, the main features of which are: (i) It decays exponentially with the F-H distance; (ii) Its main contribution comes from an electron excitation involving the F lone-pair, the C-H bond of the CHO moiety and its corresponding antibonding orbital; (iii) The π-type lone-pair does not contribute to the ts coupling pathway of the FC term. © 1987 ASEG.
Registro:
| Documento: | Artículo |
| Título: | Through-space transmission of 19F-13C coupling via an intermediate bond. An experimental and theoretical study |
| Autor: | Rae, I.D.; Staffa, A.; Diz, A.C.; Giribet, C.G.; de Azúa, M.C.R.; Contreras, R.H. |
| Filiación: | Department of Chemistry, Monash University, Clayton, VIC, 3168, Australia Departamento de Fisica, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 1, Buenos Aires, 1428, Argentina CONICET, Argentina |
| Año: | 1987 |
| Volumen: | 40 |
| Número: | 12 |
| Página de inicio: | 1923 |
| Página de fin: | 1940 |
| DOI: | http://dx.doi.org/10.1071/CH9871923 |
| Título revista: | Australian Journal of Chemistry |
| Título revista abreviado: | Aust. J. Chem. |
| ISSN: | 00049425 |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00049425_v40_n12_p1923_Rae |
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Citas:
---------- APA ----------
Rae, I.D., Staffa, A., Diz, A.C., Giribet, C.G., de Azúa, M.C.R. & Contreras, R.H. (1987) . Through-space transmission of 19F-13C coupling via an intermediate bond. An experimental and theoretical study. Australian Journal of Chemistry, 40(12), 1923-1940.http://dx.doi.org/10.1071/CH9871923
---------- CHICAGO ----------
Rae, I.D., Staffa, A., Diz, A.C., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H. "Through-space transmission of 19F-13C coupling via an intermediate bond. An experimental and theoretical study" . Australian Journal of Chemistry 40, no. 12 (1987) : 1923-1940.http://dx.doi.org/10.1071/CH9871923
---------- MLA ----------
Rae, I.D., Staffa, A., Diz, A.C., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H. "Through-space transmission of 19F-13C coupling via an intermediate bond. An experimental and theoretical study" . Australian Journal of Chemistry, vol. 40, no. 12, 1987, pp. 1923-1940.http://dx.doi.org/10.1071/CH9871923
---------- VANCOUVER ----------
Rae, I.D., Staffa, A., Diz, A.C., Giribet, C.G., de Azúa, M.C.R., Contreras, R.H. Through-space transmission of 19F-13C coupling via an intermediate bond. An experimental and theoretical study. Aust. J. Chem. 1987;40(12):1923-1940.http://dx.doi.org/10.1071/CH9871923
