Navegar

Colección

Datos Estadísticas

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:

Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.

Registro:

Documento: Artículo
Título:Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
Autor:Vilcachagua, J.D.; Ducati, L.C.; Rittner, R.; Contreras, R.H.; Tormena, C.F.
Filiación:Chemistry Institute, State University of Campinas, Caixa Postal 6154, 13084-971 Campinas, SP, Brazil
Department of Physics, FCEyN, University of Buenos Aires and IFIBA-CONICET, Buenos Aires, Argentina
Palabras clave:Cholesterol levels; Coupling constants; Ezetimibe; Fermi contact; Fluorobenzene; Hybrid functionals; Hyperconjugative interactions; NMR coupling; Paramagnetic spins; Qualitative approach; Second orders; Similar degree; Spin-spin coupling constants; Substituent effect; Virtual excitations; Virtual orbitals; Paramagnetism
Año:2011
Volumen:115
Número:7
Página de inicio:1272
Página de fin:1279
DOI: http://dx.doi.org/10.1021/jp110290b
Título revista:Journal of Physical Chemistry A
Título revista abreviado:J Phys Chem A
ISSN:10895639
CODEN:JPCAF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v115_n7_p1272_Vilcachagua

Referencias:

  • Michalik, M., Hein, M., Frank, M., (2000) Carbohydr. Res., 327, p. 185. , 218
  • O'Hagan, D., (2008) Chem. Soc. Rev., 37, p. 308
  • Grushin, V., (2010) Acc. Chem. Res., 43, p. 160
  • Purser, S., Moore, P.R., Swallow, S., Gouverneur, V., (2008) Chem. Soc. Rev., 37, p. 320
  • Kirk, K.L., (2006) J. Fluorine Chem., 127, p. 1013
  • Dolbier Jr., W.R., (2009) Guide to Fluorine NMR for Organic Chemists, , Wiley-VCH: Darmstadt, Germany
  • Hagmann, W.K., (2008) J. Med. Chem., 51, p. 4359
  • Helgaker, T., Pecul, M., Kaupp, M., Buhl, M., Malkin, V.G., (2004) Calculation of NMR and EPR Parameters, Theory and Application, p. 101. , In;, Eds.; Wiley-VCH Verlag: Weinheim, Germany,; Chapter 7, p
  • Malkina, O.L., Kaupp, M., Buhl, M., Malkin, V.G., (2004) Calculation of NMR and EPR Parameters, Theory and Application, p. 307. , In;, Eds.; Wiley-VCH Verlag: Weinheim, Germany,; Chapter 19, p
  • Enevoldsen, T., Oddershede, J., Sauer, S.P.A., (1998) Theor. Chem. Acc., 100, p. 275
  • Sauer, S.P.A., (1997) J. Phys. B: At., Mol. Opt. Phys., 30, p. 3773
  • Koch, H., Jørgensen, P., (1990) J. Chem. Phys., 93, p. 3333
  • Stanton, J.F., Bartlett, R.J., (1993) J. Chem. Phys., 98, p. 7029
  • Koch, H., Kobayashi, R., Sánchez De Merás, A., Jørgensen, P., (1994) J. Chem. Phys., 100, p. 4393
  • Kállay, M., Gauss, J., (2004) J. Chem. Phys., 121, p. 9257
  • Del Bene, J.E., Provasi, P.F., Alkorta, I., Elguero, J., (2008) Magn. Reson. Chem., 46, p. 1003
  • Del Bene, J.E., Alkorta, I., Elguero, J., (2009) J. Chem. Theor. Comp., 5, p. 208
  • Ramsey, N.F., Purcell, E.M., (1952) Phys. Rev., 85, p. 143
  • Ramsey, N.F., (1953) Phys. Rev., 91, p. 303
  • Perez, J.E., Ortiz, F.S., Contreras, R.H., Giribet, C.G., Ruiz De Azúa, M.C., (1990) J. Mol. Struct. (Theochem), 210, p. 193
  • Oddershede, J., Löwdin, P.-O., Polarization Propagator Calculations (1978) Advances in Quantum Chemistry, 11, p. 272. , In;, Ed.; Elsevier: New York,; Vol., p
  • Diz, A.C., Giribet, C.G., Ruiz De Azúa, M.C., Contreras, R.H., (1990) Int. J. Quantum Chem., 37, p. 663
  • Contreras, R.H., Ruiz De Azúa, M.C., Giribet, C.G., Aucar, G.A., Lobayan De Bonczok, R., (1993) J. Mol. Struct. (Theochem), 284, p. 249
  • Giribet, C.G., Ruiz De Azúa, M.C., Contreras, R.H., Lobayan De Bonczok, R., Aucar, G.A., Gomez, S., (1993) J. Mol. Struct. (Theochem), 300, p. 467
  • Patchkovskii, S., Autscgbach, J., Ziegler, T., (2009) J. Chem. Phys., 115, p. 26
  • Keal, T.W., Helgaker, T., Salek, P., Tozer, D.J., (2006) Chem. Phys. Lett., 425, p. 163
  • Becke, A.D., (1988) Phys. Rev., 38, p. 3098
  • Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev., 37, p. 785
  • Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648
  • Becke, A.D., (1993) J. Chem. Phys., 98, p. 1372
  • Peréz-Jordá, J.M., Becke, A.D., (1995) Chem. Phys. Lett., 233, p. 134
  • Barone, B., Contreras, R.H., Díez, E., Esteban, A.L., (2003) Mol. Phys., 101, p. 1297
  • Barone, V., Provasi, P.F., Peralta, J.E., Snyder, J.P., Stephan, P.A., Sauer, S.P.A., Contreras, R.H., (2003) J. Phys. Chem. A, 107, p. 4748
  • Contreras, R.H., Esteban, A.L., Díez, E., Della, E.W., Lochert, I.J., Dos Santos, F.P., Tormena, C.F., (2006) J. Phys. Chem. A, 110, p. 4266
  • Esteban, A.L., Díez, E., Della, E.W., Ian Lochert J, I.J., Dos Santos, F.P., Tormena, C.F., (2006) J. Phys. Chem. A, 110, p. 4266
  • Cunha Neto, A., Ducati, L.C., Rittner, R., Tormena, C.F., Contreras, R.H., Frenking, G., (2009) J. Chem. Theory Comp., 5, p. 2222
  • Contreras, R.H., Llorente, T., Pagola, G.I., Bustamante, M.G., Pasqualini, E.E., Melo, J.I., Tormena, C.F., (2009) J. Phys. Chem. A, 113, p. 9874
  • Contreras, R.H., Gotelli, G., Ducati, L.C., Barbosa, T.M., Tormena, C.F., (2010) J. Phys. Chem. A, 114, p. 1044
  • Reed, A.E., Curtiss, L.A., Weinhold, F., (1988) Chem. Rev., 88, p. 899
  • Weinhold, F., Schleyer V. P, R., (1998) Encyclopedia of Computational Chemistry, 3, p. 1792. , In;, Ed.; Wiley: New York,; Vol., p
  • Contreras, R.H., Giribet, C.G., Ruiz De Azúa, M.C., Ferraro, M.B., Fraga, S., Electronic origin of high resolution NMR parameters (1992) Computational Chemistry: Structure, Interactions and Reactivity, 77, p. 212. , In;, Ed.; Studies in Physical and Theoretical Chemistry; Elsevier Science Publishers B.V: New York,; Vol., p
  • Fifolt, M.J., Soyka, S.A., Roger, R.A., Hojnicki, D.S., (1989) J. Org. Chem., 54, p. 3019
  • Dunning Jr., T.H., (1989) J. Chem. Phys., 90, p. 1007
  • Kendall, R.A., Dunning Jr., T.H., Harrison, R.J., (1992) J. Chem. Phys., 96, p. 6769
  • Barone, V., (1994) J. Chem. Phys., 101, p. 6834
  • (2005), http://www.kjemi.uio.no/software/dalton/dalton.html, DALTON, a molecular electronic structure program, Release 2.0. Available from; 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., (2004) Gaussian 03, Revision E.01, , Gaussian, Inc.: Wallingford, CT
  • Alkorta, I., Blanco, F., Elguero, J., (2010) J. Mol. Struct., 964, p. 119
  • Keal, T.W., Tozer, D.J., (2003) J. Chem. Phys., 119, p. 3015
  • Keal, T.W., Helgaker, T., Tozer, D.J., (2004) Chem. Phys. Lett., 391, p. 374
  • Keal, W.T., Helgaker, T., Salek, P., Tozer, D.J., (2006) Chem. Phys. Lett., 425, p. 163
  • Helgaker, T., Jaszunski, M., Pecul, M., (2008) Prog. Nucl. Magn. Reson. Spectrosc., 53, p. 249
  • Lanto, P., Vaara, J., Helgaker, T., (2002) J. Chem. Phys., 117, p. 5998
  • Li, S., Chesnut, D.B., (1985) Magn. Reson. Chem., 23, p. 625
  • Li, S., Chesnut, D.B., (1986) Magn. Reson. Chem., 24, p. 93

Citas:

---------- APA ----------
Vilcachagua, J.D., Ducati, L.C., Rittner, R., Contreras, R.H. & Tormena, C.F. (2011) . Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives. Journal of Physical Chemistry A, 115(7), 1272-1279.
http://dx.doi.org/10.1021/jp110290b
---------- CHICAGO ----------
Vilcachagua, J.D., Ducati, L.C., Rittner, R., Contreras, R.H., Tormena, C.F. "Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives" . Journal of Physical Chemistry A 115, no. 7 (2011) : 1272-1279.
http://dx.doi.org/10.1021/jp110290b
---------- MLA ----------
Vilcachagua, J.D., Ducati, L.C., Rittner, R., Contreras, R.H., Tormena, C.F. "Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives" . Journal of Physical Chemistry A, vol. 115, no. 7, 2011, pp. 1272-1279.
http://dx.doi.org/10.1021/jp110290b
---------- VANCOUVER ----------
Vilcachagua, J.D., Ducati, L.C., Rittner, R., Contreras, R.H., Tormena, C.F. Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives. J Phys Chem A. 2011;115(7):1272-1279.
http://dx.doi.org/10.1021/jp110290b