Artículo

La versión final de este artículo es de uso interno. El editor solo permite incluir en el repositorio el artículo en su versión post-print. Por favor, si usted la posee enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

J(13C,13C) spin-spin couplings were measured at natural abundance in five pyridine aldehyde derivatives. Such couplings were also calculated at the DFT-B3LYP-6-311G**/EPR-III level of theory where special attention was paid to their possible stereospecific behaviors. Dielectric solvent effects were calculated on all four isotropic contributions to J(13C,13C) couplings using the polarization continuum model, PCM. It is observed that the inclusion of dielectric solvent effects in general leads to a better agreement between calculated and experimental couplings. 2J(13CC,13CA) couplings were observed to be sensitive to the aldehyde side-chain conformation (coupling pathway: CC-Ci-CA, where C C stands for the carbonyl-, Ci is the aromatic ipso- and CA is an adjacent aromatic-C atom). This is a positive coupling and becomes unusually large for a trans configuration between the carbonyl CO and the CC-Ci bonds. In this conformation, there is an enhancement of conjugative interactions involving the π(CO) and π(C CCi) bonding and antibonding orbitals. © 2005 Elsevier B.V. All rights reserved.

Registro:

Documento: Artículo
Título:NMR J(13C,13C) spin-spin coupling constants in pyridine-carboxaldehydes. Experimental and DFT-B3LYP studies
Autor:Taurian, O.E.; De Kowalewski, D.G.; Pérez, J.E.; Contreras, R.H.
Filiación:Departamento de Física, FCEFQyN, Universidad Nacional de Río Cuarto, Ruta Nacional No. 36, Km 601, 5800 Río Cuarto, Argentina
Area Química-Física, Facultad de Química, Bioquímica Y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700 San Luis, Argentina
Departamento de Física, FCEyN, Ciudad Universitaria, P.1, C1428EHA Buenos Aires, Argentina
Palabras clave:Conjugative interactions; Geminal couplings; Negative hyperconjugative interactions; Scalar couplings; Stereospecificity; Aldehydes; Carbon monoxide; Conformations; Continuum mechanics; Antibonding orbitals; Conjugative interactions; Pyridine aldehydes; Molecular structure
Año:2005
Volumen:754
Número:1-3
Página de inicio:1
Página de fin:9
DOI: http://dx.doi.org/10.1016/j.molstruc.2005.06.002
Título revista:Journal of Molecular Structure
Título revista abreviado:J. Mol. Struct.
ISSN:00222860
CODEN:JMOSB
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00222860_v754_n1-3_p1_Taurian

Referencias:

  • Sychrovský, V., Gräfenstein, J., Cremer, D., (2000) J. Chem. Phys., 113, p. 3530
  • Helgaker, T., Watson, M., Handy, N.C., (2000) J. Chem. Phys., 113, p. 9402
  • Barone, V., Peralta, J.E., Contreras, R.H., Snyder, J.P., (2002) J. Phys. Chem., a, 106, p. 5607
  • Peralta, J.E., Barone, V., Scuseria, G.E., Contreras, R.H., (2004) J. Am. Chem. Soc., 126, p. 7428
  • Marshall, J.L., (1983) Methods in Stereochemical Analysis, 2. , A.P. Marchand Verlag Chemie Deerfield Beach, FL
  • Krivdin, L.B., Kalabin, G.A., (1989) Prog. NMR Spectrosc., 21, p. 293
  • Krivdin, L.B., Della, E.W., (1991) Prog. NMR Spectrosc., 23, p. 301
  • Kamienska-Trela, K., (1995) Ann. Rep. NMR Spectrosc., 30, p. 131
  • Krivdin, L.B., Zinchenko, S.V., (1998) Curr. Org. Chem, 2, p. 173
  • Karabastos, G.J., Vane, F.M., (1963) J. Am. Chem. Soc., 85, p. 3886
  • Wasylishen, R., Schaefer, T., (1971) Can. J. Chem., 49, p. 3216
  • Dorie, I.J.P., Martín, M.L., Barnier, S., Blain, M., Odiot, S., (1971) Org. Magn. Reson., 3, p. 661
  • Bramwell, M.R., Randall, E.W., (1970) Spectrochim. Acta, a, 26, p. 1877
  • Danchura, W., Schaefer, T., Rowbotham, J.B., Wood, D.J., (1974) Can. J. Chem., 52, p. 3986
  • Lefevre, R.J.W., Stiles, P.J., (1966) J. Chem. Soc. B, p. 420
  • Hansen, P.E., (1989) The Chemistry of Double-bonded Functional Groups, , S. Patai Wiley New York
  • De Kowalewski, D.G., Díez, E., Esteban, A.L., Barone, V., Peralta, J.E., Contreras, R.H., (2004) Magn. Reson. Chem., 42, p. 938
  • De Kowalewski, D.G., Contreras, R.H., Díez, E., Esteban, A.L., (2004) Mol. Phys., 102, p. 2607
  • Bax, A., Freeman, R., Frenkiel, T.A., (1981) J. Am. Chem. Soc., 103, p. 2102
  • Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648
  • Lantto, P., Vaara, J., Helgaker, T., (2002) J. Chem. Phys., 117, p. 1
  • Maximoff, S.N., Peralta, J.E., Barone, V., Scuseria, G.E., J. Chem. Theory Comput., , in press
  • Barone, V., (1994) J. Chem. Phys., 101, p. 6834
  • Peralta, J.E., Scuseria, G.E., Cheeseman, J.R., Frisch, M.J., (2003) Chem. Phys. Lett., 375, p. 452
  • Cossi, M., Barone, V., Mennuci, B., Tomasi, J., (1998) Chem. Phys. Lett., 286, p. 253
  • Mennucci, B., Tomasi, J., (1997) J. Chem. Phys., 106, p. 5151
  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Pople, J.A., (2003) Gaussian 03, Revision B.05, , Gaussian, Inc., Pittsburgh PA
  • Reed, A.E., Curtis, L.A., Weinhold, F., (1988) Chem. Rev., 88, p. 899
  • Glendening, E.D., Reed, A.E., Carpenter, J.E., Weinhold, F., Gaussian 03 Package of Programs, NBO Version 3.1, , Included
  • Kirby, A.J., (1983) The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, , Springer Berlin
  • Reed, A.E., Schleyer, V.P.R., (1990) J. Am. Chem. Soc., 112, p. 1434
  • Eliel, E.L., Giza, G.A., (1968) J. Org. Chem., 33, p. 3754
  • Lemeiux, R.U., Pavia, A.A., Marti, J.C., Watanabe, K.A., (1969) Can. J. Chem., 47, p. 4427
  • Zaccari, D.G., Snyder, J.P., Peralta, J.E., Taurian, O.E., Contreras, R.H., Barone, V., (2002) Mol. Phys., 100, p. 705
  • Zaccari, D., Barone, V., Peralta, J.E., Contreras, R.H., Taurian, O.E., Díez, E., Esteban, A.E., (2003) Int.J. Mol. Sci., 4, p. 93
  • Contreras, R.H., Peralta, E., (2000) Prog. NMR Spectrosc., 37, p. 321
  • Contreras, R.H., Barone, V., Peralta, J.E., Facelli, J.C., (2003) Ann. Rep. NMR Spectrosc., 51, p. 167
  • Watson, M.A., Salek, P., MacAk, P., Jaszunski, M., Helgaker, T., (2004) Chem. Eur. J., 10, p. 4627
  • Contreras, R.H., Peralta, J.E., Barone, V., Scuseria, G.E., (2005) Adv. Quantum Chem., 48, p. 127
  • Lee, W.S., Schulman, J.M., (1979) J. Chem. Phys., 70, p. 1530
  • Pérez, J.E., Ortiz, F.S., Contreras, R.H., Giribet, C.G., Ruiz De Azúa, M.C., (1990) J. Mol. Struct. (Theochem), 210, p. 193
  • Seel, H., Günther, H., (1980) J. Am. Chem. Soc., 102, p. 7051
  • Gil, V.M.S., Philipsborn, W.V., (1989) Magn. Reson. Chem., 27, p. 409
  • Contreras, R.H., Peralta, J.E., Giribet, C.G., Ruiz De Azúa, M.C., Facelli, J.C., (2000) Ann. Rep. NMR Spectrosc., 41, p. 55
  • Tormena, C.F., Rittner, R., Contreras, R.H., Peralta, J.E., (2004) J. Phys. Chem. a, 108, p. 7762
  • Contreras, R.H., Natiello, M.A., Tufró, M.F., De Kowalewski, G., (1986) Z. Physik. Chem., 267, p. 289
  • Barfield, M., Chakrabarti, B., (1969) Chem. Rev., 69, p. 757
  • Engelman, A.R., Scuseria, G.E., Contreras, H., (1982) J. Magn. Reson., 50, p. 21
  • Keal, T.W., Tozer, D.J., Helgaker, T., (2004) Chem. Phys. Lett., 391, p. 374
  • Lutnæs, O.B., Ruden, T.A., Helgaker, T., (2004) Magn. Reson. Chem., 42, p. 117
  • Wigglesworth, R.D., Raynes, W.T., Kirpekar, S., Oddershede, J., Sauer, P.A., (2000) J. Chem. Phys., 112, p. 3735
  • Ruden, T.A., Lutnæs, O.B., Helgaker, T., Ruud, K., (2003) J. Chem. Phys., 118, p. 9572
  • De Kowalewski, D.G., Kowalewski, V.J., Peralta, J.E., Eskuche, G., Contreras, R.H., Esteban, A.L., Galache, M.P., (1999) E. Díez, Magn. Reson. Chem., 37, p. 227

Citas:

---------- APA ----------
Taurian, O.E., De Kowalewski, D.G., Pérez, J.E. & Contreras, R.H. (2005) . NMR J(13C,13C) spin-spin coupling constants in pyridine-carboxaldehydes. Experimental and DFT-B3LYP studies. Journal of Molecular Structure, 754(1-3), 1-9.
http://dx.doi.org/10.1016/j.molstruc.2005.06.002
---------- CHICAGO ----------
Taurian, O.E., De Kowalewski, D.G., Pérez, J.E., Contreras, R.H. "NMR J(13C,13C) spin-spin coupling constants in pyridine-carboxaldehydes. Experimental and DFT-B3LYP studies" . Journal of Molecular Structure 754, no. 1-3 (2005) : 1-9.
http://dx.doi.org/10.1016/j.molstruc.2005.06.002
---------- MLA ----------
Taurian, O.E., De Kowalewski, D.G., Pérez, J.E., Contreras, R.H. "NMR J(13C,13C) spin-spin coupling constants in pyridine-carboxaldehydes. Experimental and DFT-B3LYP studies" . Journal of Molecular Structure, vol. 754, no. 1-3, 2005, pp. 1-9.
http://dx.doi.org/10.1016/j.molstruc.2005.06.002
---------- VANCOUVER ----------
Taurian, O.E., De Kowalewski, D.G., Pérez, J.E., Contreras, R.H. NMR J(13C,13C) spin-spin coupling constants in pyridine-carboxaldehydes. Experimental and DFT-B3LYP studies. J. Mol. Struct. 2005;754(1-3):1-9.
http://dx.doi.org/10.1016/j.molstruc.2005.06.002