Artículo
Peralta, J.E.; Contreras, R.H.; Taurian, O.E.; Ortiz, F.S.; De Kowalewski, D.G.; Kowalewski, V.J. "Methyl β-substituent effect on NMR 17O chemical shifts in two-coordinated oxygen atoms: DFT GIAO and NBO and experimental studies" (1999) Magnetic Resonance in Chemistry. 37(1):31-35
Consulte la política de Acceso Abierto del editor
Abstract:
Methyl β-substituent effects on 17O chemical shifts in dicoordinated oxygen atoms in compounds of the type CH3 - O - X are found to be insensitive to the nature of the X substrate, even for strongly conjugating groups. Such behavior is rationalized in terms of intramolecular electron delocalizing using the natural bond orbitals approach to calculate NBO E(2) charge-transfer energies. The level of theory employed in this analysis was chosen in such a way that DFT GIAO at the same level could describe the experimental trends adequately. In this way, it was found that charge transfers to (O - C)* antibonds render important deshielding effects on the 17O chemical shifts. In the particular case of the methyl β-substituent effect quoted above, such charge transfer originates in the preferential orientation that the CαH2 - CβH3 group adopts in these compounds CH3 - O - X. Analogies with 19F chemical shifts are discussed. © 1999 John Wiley & Sons, Ltd.
Registro:
| Documento: | Artículo |
| Título: | Methyl β-substituent effect on NMR 17O chemical shifts in two-coordinated oxygen atoms: DFT GIAO and NBO and experimental studies |
| Autor: | Peralta, J.E.; Contreras, R.H.; Taurian, O.E.; Ortiz, F.S.; De Kowalewski, D.G.; Kowalewski, V.J. |
| Filiación: | Departamento de Fisica, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 1, 1428 Buenos Aires, Argentina Depto. Química y Fisica, Fac. Cs. Exs. Fco.-Quim. y Nat., UNRC, Ruta 8, Km 603, 5800 Río Cuarto, Argentina |
| Palabras clave: | 17O chemical shifts; 17O NMR; DFT-NBO; DFT-GIAO; NMR; Substituent effects |
| Año: | 1999 |
| Volumen: | 37 |
| Número: | 1 |
| Página de inicio: | 31 |
| Página de fin: | 35 |
| 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_n1_p31_Peralta |
Referencias:
- Jameson, C.J., (1987) Multinuclear NMR, , edited by J. Mason, Chapt. 4. Plenum Press, New York
- Boykin, D.W., (1990) 17O NMR Spectroscopy in Organic Chemistry, , CRC Press, Boca Raton, FL
- Jameson, C.J., (1994) Nuclear Magnetic Resonance, 23-26. , edited by G. A. Webb, Specialist Periodical Report, Chapt. 2. Royal Society of Chemistry, Cambridge
- Yamaguchi, M., (1994) Nuclear Magnetic Resonance, 23-26. , edited by G. A. Webb, Specialist Periodical Report, Chapt. 3. Royal Society of Chemistry, Cambridge
- Adcock, W., Angus, D.I., Lowe, D.A., (1996) Magn. Reson. Chem., 34, p. 675
- Delseth, C., Kintzinger, J.-P., (1978) Helv. Chim. Acta, 61, p. 1327
- Kalabin, G.A., Kushnarev, D.F., Valeyev, R.B., Trofimov, B.A., Fedotov, M.A., (1982) Org. Magn. Reson., 18, p. 1
- Chandrasekaran, S., (1990) 17O NMR Spectroscopy in Organic Chemistry, p. 141. , edited by D. W. Boykin, Chapt. 7, CRC Press, Boca Raton, FL
- Taskinen, E., Hellman, J., (1994) Magn. Reson. Chem., 32, p. 353
- De Kowalewski, D.G., Kowalewski, V.J., Contreras, R.H., Díez, E., Esteban, A.L., (1998) Magn. Reson. Chem., 36, p. 336
- Contreras, R.H., Biekofsky, R.R., Esteban, A.L., Diez, E., San Fabian, J., (1996) Magn. Reson. Chem., 34, p. 447
- Facelli, J.C., Orendt, A.M., Contreras, R.H., Tufró, M.F., De Kowalewski, D.G., (1992) J. Phys. Chem., 96, p. 7895
- Reed, A.E., Curtiss, L.A., Weinhold, F., (1988) Chem. Rev., 88, p. 899
- Ditchfleld, R., (1974) Mol. Phys., 27, p. 789
- Wolinski, K., Hinton, J.F., Pulay, P., (1990) J. Am. Chem. Soc., 112, p. 8251
- Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648
- Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650
- Glendening, E.D., Reed, A.E., Carpenter, J.E., Weinhold, F., NBO Version 3.1, , included in Ref. 17
- Frisch, M.J., Trucks, G.W., Schlegel, H.B., Gili, P.M.W., Johnson, B.G., Robb, M.A., Cheeseman, J.R., Pople, J.A., (1995) Gaussian 94, Revision D.4, , Gaussian, Pittsburgh, PA
- Bond, D., Schleyer, P.V.R., (1990) J. Org. Chem., 55, p. 1003
- Riveros, J.M., Wilson E.B., Jr., (1969) J. Chem. Phys., 46, p. 4605
- De Kowalewski, D.G., Kowalewski, V.J., Botek, E., Contreras, R.H., Facelli, J.C., (1997) Magn. Reson. Chem., 35, p. 351
Citas:
---------- APA ----------
Peralta, J.E., Contreras, R.H., Taurian, O.E., Ortiz, F.S., De Kowalewski, D.G. & Kowalewski, V.J. (1999) . Methyl β-substituent effect on NMR 17O chemical shifts in two-coordinated oxygen atoms: DFT GIAO and NBO and experimental studies. Magnetic Resonance in Chemistry, 37(1), 31-35.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n1_p31_Peralta [ ]
---------- CHICAGO ----------
Peralta, J.E., Contreras, R.H., Taurian, O.E., Ortiz, F.S., De Kowalewski, D.G., Kowalewski, V.J. "Methyl β-substituent effect on NMR 17O chemical shifts in two-coordinated oxygen atoms: DFT GIAO and NBO and experimental studies" . Magnetic Resonance in Chemistry 37, no. 1 (1999) : 31-35.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n1_p31_Peralta [ ]
---------- MLA ----------
Peralta, J.E., Contreras, R.H., Taurian, O.E., Ortiz, F.S., De Kowalewski, D.G., Kowalewski, V.J. "Methyl β-substituent effect on NMR 17O chemical shifts in two-coordinated oxygen atoms: DFT GIAO and NBO and experimental studies" . Magnetic Resonance in Chemistry, vol. 37, no. 1, 1999, pp. 31-35.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n1_p31_Peralta [ ]
---------- VANCOUVER ----------
Peralta, J.E., Contreras, R.H., Taurian, O.E., Ortiz, F.S., De Kowalewski, D.G., Kowalewski, V.J. Methyl β-substituent effect on NMR 17O chemical shifts in two-coordinated oxygen atoms: DFT GIAO and NBO and experimental studies. Magn. Reson. Chem. 1999;37(1):31-35.Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v37_n1_p31_Peralta [ ]
