Abstract:
19F chemical shifts are reported for a series of alkyl‐substituted fluoronaphthalenes and related compounds that exhibit steric crowding around the fluorine atom due to the proximity of methyl groups. Comparisons of these chemical shifts with others measured in similar compounds but without the corresponding methyl groups show that this crowding effect produces a large low‐field shift of the 19F signal. Similar effects, but with an even larger sensitivity to the steric crowding, were recently reported for 17O chemical shifts. The electronic origin for this proximity effect on 19F chemical shifts is analyzed within the molecular orbital theory, at the INDO level, using the inner projections of the polarization propagator technique. It is found that the presence of the methyl group produces an increase in the absolute value of the paramagnetic term of the magnetic shielding constant. Copyright © 1991 John Wiley & Sons Ltd.
Registro:
Documento: |
Artículo
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Título: | Fluorine deshielding in the proximity of a methyl group. An experimental and theoretical study |
Autor: | Gribble, G.W.; Keavy, D.J.; Olson, E.R.; Rae, I.D.; Staffa, A.; Herr, T.E.; Ferraro, M.B.; Contreras, R.H. |
Filiación: | Department of Chemistry, Dartmouth College, Hanover, New Hampshire, 03755, United States Department of Chemistry, Monash University, Clayton, Victoria, 3186, Australia Departamento de Fisica, Facultad de Ciencias Exactas Y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 1, Buenos Aires, 1428, Argentina
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Palabras clave: | 19F chemical shift theory; 19F NMR; 1‐Alkyl‐8‐fluoronaphthalenes; Fluorine deshielding; Magnetic shielding tensor calculations |
Año: | 1991
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Volumen: | 29
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Número: | 5
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Página de inicio: | 422
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Página de fin: | 432
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DOI: |
http://dx.doi.org/10.1002/mrc.1260290504 |
Título revista: | Magnetic Resonance in Chemistry
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Título revista abreviado: | Magn. Reson. Chem.
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ISSN: | 07491581
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v29_n5_p422_Gribble |
Referencias:
- Foster, M.J., (1989) Nuclear Mag Magnetic Resonance, 18. , edited by, G. A. Webb, Specialist Periodical Report, Vol, Chapt. 2., Royal Society of Chemistry, London
- Li, S., Chesnut, D.B., Intramolecular van der waals interactions and chemical shifts: A model for β- and γ-effects (1985) Magnetic Resonance in Chemistry, 23, p. 625
- Allinger, N.L., (1977) J. Am. Chem. Soc., 99, p. 8127
- Li, S., Chesnut, D.B., Intramolecular van der Waals interactions and13C chemical shifts: Substituent effects in some cyclic and bicyclic systems (1986) Magnetic Resonance in Chemistry, 24, p. 93
- Boykin, D.W., Hertzler, R.L., Delphon, J.K., Eisenbraun, E.J., (1989) J. Org. Chem., 54, p. 1418
- Boykin, D.W., Dewprashad, B., Eisenbraun, E.J., (1990) J. Org. Chem., 55, p. 425
- Baumstark, A.L., Dotrong, M., Stark, R.R., Boykin, D.W., (1988), p. 2143. , Tetrahedron Lett; Ferraro, M.B., Natiello, M.A., Contreras, R.H., The use of inner projections of the polarization propagator to study different contributions to the magnetic shielding tensor. I. Proton deshielding by steric compression (1986) International Journal of Quantum Chemistry, 30, p. 77
- Ferraro, M.B., De Kowalewski, D.G., Contreras, R.H., Ortiz, F.S., (1987) Chem. Phys., 118, p. 325
- Contreras, R.H., de Azüa, Giribet, C.G., Ferraro, M.B., Diz, A.C., (1989) Quimica Teorica, 2. , edited by, S. Fraga, Chapt, 16., CSIC, Madrid
- Kutzelnigg, W., Theory of Magnetic Susceptibilities and NMR Chemical Shifts in Terms of Localized Quantities (1980) Israel Journal of Chemistry, 19, p. 193
- Schindler, M., Kutzelnigg, W., (1983) J. Am. Chem. Soc., 105, p. 1360
- Bouman, T.D., Hansen, A.E., (1988) Chem. Phys. Lett., 149, p. 510
- Fleischer, U., Schindler, M., (1988) Chem. Phys., 120, p. 103
- Contreras, R.H., Natiello, M.A., Scuseria, G.E., (1985) Magn. Reson. Rev., 9, p. 239
- Beer, M.D., CNINDO 3.3.3 Program, , NMR Program Library, Daresbury, Warrington, UK
- Pople, J.A., Beveridge, D.L., (1970) Approximate Molecular Orbital Theory, , McGraw‐Hill, New York
- de Azúa, Diz, A.C., Giribet, C.G., Contreras, R.H., Rae, I.D., (1986) Int. J. Quantum. Chem., 20 S, p. 585
- Diz, A.C., de Azúa, Giribet, C.G., Contreras, R.H., The use of localized molecular orbitals and the polarization propagator to identify transmission mechanisms in nuclear spin-spin couplings (1990) International Journal of Quantum Chemistry, 37, p. 663
- Krivdin, L.B., Zinchenko, S.V., Shcherbakov, V.V., Kalabin, G.A., Contreras, R.H., Tufro, M.F., de Azúa, Giribet, C.G., (1989) J. Magn. Reson., 84, p. 1
- Rae, I.D., Staffa, A., Diz, A.C., Giribet, C.G., de Azüa, Contreras, R.H., Through-Space Transmission of19F-13C Coupling Via an Intermediate Bond. An Experimental and Theoretical Study (1987) Australian Journal of Chemistry, 40, p. 1923
- Gribble, G.W., Sibi, M.P., Kumar, S., Kelly, W.J., (1983), p. 502. , Synthesis; Gribble, G.W., Allen, R.W., Le Houllier, C.S., Eaton, J.T., Easton, N.R., Jr., Slayton, R.I., Sibi, M.P., (1981) J. Org. Chem., 46, p. 1025
- Gribble, G.W., Kelly, W.J., Sibi, M.P., (1982), p. 143. , Synthesis; Gribble, G.W., Keavy, D.J., Branz, S.E., Kelly, W.J., Pals, M.A., (1988), p. 6227. , Tetrahedron Lett; Fitzpatrick, J.E., Milner, D.J., White, P., (1982) Synth. Commun., 12, p. 489
- Gilman, H., Calloway, N.O., (1933) J. Am. Chem. Soc., 55, p. 4197
- Benkeser, R.A., Currie, R.B., (1948) J. Am. Chem. Soc., 70, p. 1780
- Gribble, G.W., Kelly, W.J., (1981), p. 2475. , Tetrahedron Lett; Adcock, W., Rizvi, S.Q.A., Long-range proton-fluorine spin-spin coupling. Further evidence for a 'direct' mechanism (1973) Australian Journal of Chemistry, 26, p. 2659
- Adcock, W., Matthews, D.G., Rizvi, S.Q.A., Long-range proton-fluorine spin-spin coupling and19F substituent chemical shifts (SCS) in the naphthalene ring system (1971) Australian Journal of Chemistry, 24, p. 1829
- Sutton, L.E., (1965) Tables of Interatomic Distances and Configuration in Molecules and Ions, , Chemical Society, London, 1958; Supplement
- Löwdin, P.O., (1962) J. Math. Phys., 3, p. 969
- Engelmann, A.R., Contreras, R.H., Transmission mechanisms of spin-spin coupling constants within theCHF approximation: Their study using inner projections of the polarization propagator (1983) International Journal of Quantum Chemistry, 23, p. 1033
- Verwoerd, W.S., (1979) Chem. Phys., 44, p. 151
- Oddershede, J., (1978) Adv. Quantum Chem., 11, p. 275
- London, F., Théorie quantique des courants interatomiques dans les combinaisons aromatiques (1937) Journal de Physique et le Radium, 8, p. 397
- Nakatsuji, H., (1974) J. Chem. Phys., 61, p. 3728
- Cruickshank, W.J., Sparks, R.A., (1960), p. 258. , Proc. R. Soc. London, Ser. A; Pople, J.A., Gordon, M., (1967) J. Am. Chem. Soc., 89, p. 4253
- Jameson, M.B., Penfold, B.R., (1965), p. 528. , J. Chem. Soc; Fifolt, M.J., Sojka, S.A., Wolfe, R.A., Hojnicki, D.S., Bieron, J.F., Dinan, F.J., (1989) J. Org. Chem., 54, p. 3019
- Schaefer, T., Peeling, J., Wildman, T.A., Conformational preferences of 2-methoxy-acetophenone (1984) Organic Magnetic Resonance, 22, p. 477
- Mirarchi, D., Ritchie, G.L.D., (1984) J. Mol. Struct., 118, p. 303
- Contreras, R.H., Giribet, C.G., Natiello, M.A., Perez, J., Rae, I.D., Weigold, J.A., Experimental and Theoretical-Study of Carbon-Fluorine Couplings in the NMR-Spectra of 2-Fluoroaryl Ketones (1985) Australian Journal of Chemistry, 38, p. 1779
Citas:
---------- APA ----------
Gribble, G.W., Keavy, D.J., Olson, E.R., Rae, I.D., Staffa, A., Herr, T.E., Ferraro, M.B.,..., Contreras, R.H.
(1991)
. Fluorine deshielding in the proximity of a methyl group. An experimental and theoretical study. Magnetic Resonance in Chemistry, 29(5), 422-432.
http://dx.doi.org/10.1002/mrc.1260290504---------- CHICAGO ----------
Gribble, G.W., Keavy, D.J., Olson, E.R., Rae, I.D., Staffa, A., Herr, T.E., et al.
"Fluorine deshielding in the proximity of a methyl group. An experimental and theoretical study"
. Magnetic Resonance in Chemistry 29, no. 5
(1991) : 422-432.
http://dx.doi.org/10.1002/mrc.1260290504---------- MLA ----------
Gribble, G.W., Keavy, D.J., Olson, E.R., Rae, I.D., Staffa, A., Herr, T.E., et al.
"Fluorine deshielding in the proximity of a methyl group. An experimental and theoretical study"
. Magnetic Resonance in Chemistry, vol. 29, no. 5, 1991, pp. 422-432.
http://dx.doi.org/10.1002/mrc.1260290504---------- VANCOUVER ----------
Gribble, G.W., Keavy, D.J., Olson, E.R., Rae, I.D., Staffa, A., Herr, T.E., et al. Fluorine deshielding in the proximity of a methyl group. An experimental and theoretical study. Magn. Reson. Chem. 1991;29(5):422-432.
http://dx.doi.org/10.1002/mrc.1260290504