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Abstract:

Electron delocalization into the local environment of the fluorine nucleus in the anti (1) and syn (2) epimers of 7-norbornenyl fluoride, 7-fluoronorbornane (3), 7-fluoronobornadiene (4) and the equatorial and axial epimers of cyclohexyl fluoride (5 and 6, respectively) were studied using the natural bond orbital (NBO) approach. The level of theory, B3LYP/6-311G**, was chosen in such a way that the GIAO-calculated 19F magnetic shielding constants in all these compounds were in very good agreement with experimental values. The large 19F deshielding effects known experimentally in 1 and 4 with respect to 2 and 3 are rationalized in terms of differences in such electron delocalizations. The main contribution is that corresponding to the π → (C-F)* interaction, which is only efficient for an anti orientation of the C-F bond and the vinyl moiety. 19F and 13C NMR spectra of 5 and 6 were also measured because some ambiguity was detected in the literature. Despite the large calculated charge donation to the fluorine environment in 6, its 19F resonance appears upfield from that in 5. This trend is rationalized as originating in γ effects of the C-Hax bonds of the kind which have been invoked to explain 17O chemical shift trends in different cyclohexanols and their respective ethers. Electron delocalization effects on 1J(C,F) and 2J(C,F) couplings are also discussed. Copyright © 1999 John Wiley & Sons, Ltd.

Registro:

Documento: Artículo
Título:DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides
Autor:Adcock, W.; Lünsmann, D.; Peralta, J.E.; Contreras, R.H.
Filiación:Department of Chemistry, Flinders Univ. of South Australia, Adelaide, SA 5001, Australia
Departamento de Física, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 1, (1428) Buenos Aires, Argentina
Palabras clave:7-norbornenyl fluorides; 19F chemical shifts; 19F NMR; 1J(C,F)F and 2J(C,F) couplings; Cyclohexyl fluorides; DFT-GIAO; DFT-NBO; NMR
Año:1999
Volumen:37
Número:3
Página de inicio:167
Página de fin:172
Título revista:Magnetic Resonance in Chemistry
Título revista abreviado:Magn. Reson. Chem.
ISSN:07491581
CODEN:MRCHE
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n3_p167_Adcock

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Citas:

---------- APA ----------
Adcock, W., Lünsmann, D., Peralta, J.E. & Contreras, R.H. (1999) . DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides. Magnetic Resonance in Chemistry, 37(3), 167-172.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n3_p167_Adcock [ ]
---------- CHICAGO ----------
Adcock, W., Lünsmann, D., Peralta, J.E., Contreras, R.H. "DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides" . Magnetic Resonance in Chemistry 37, no. 3 (1999) : 167-172.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n3_p167_Adcock [ ]
---------- MLA ----------
Adcock, W., Lünsmann, D., Peralta, J.E., Contreras, R.H. "DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides" . Magnetic Resonance in Chemistry, vol. 37, no. 3, 1999, pp. 167-172.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n3_p167_Adcock [ ]
---------- VANCOUVER ----------
Adcock, W., Lünsmann, D., Peralta, J.E., Contreras, R.H. DFT-GIAO and DFT-NBO studies of the origin of 19F NMR shielding effects in alkyl fluorides. Magn. Reson. Chem. 1999;37(3):167-172.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n3_p167_Adcock [ ]