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Ghiviriga, I.; Zhang, L.; Martinez, H.; Contreras, R.H.; Tormena, C.F.; Nodin, L.; Dolbier Jr., W.R. "19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes" (2011) Magnetic Resonance in Chemistry. 49(3):93-105
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Abstract:

In the process of studying the chemistry of perfluoro[2.2]paracyclophanes (PFPCs), a novel class of compounds, it became necessary to identify some disubstituted products. To achieve this goal, we characterize in this work some monosubstituted PFPCs, identifying their 19F-19F coupling patterns, and establishing a methodology for the assignment of their 19F chemical shifts. The pattern of coupling constants indicates a skewed geometry in which the upper deck moves towards or away from the substituent, depending on the substituent electron-donor character and size. Quantum chemical calculations, performed at the HF/6-311 + G(d,p)//B3LYP/EPR-III level of theory, confirmed the conformations inferred from coupling constants and reproduced well the values of the couplings. Transmission mechanisms for the FC term of four-and five-bond 19F-19F couplings are discussed in detail. Understanding the conformational preferences of PFPCs and how they are reflected by the coupling constants facilitates the assignment of 19F chemical shifts in monosubstituted PFPCs and the identification of the disubstituted products. Copyright © 2011 John Wiley & Sons, Ltd.

Registro:

Documento: Artículo
Título:19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes
Autor:Ghiviriga, I.; Zhang, L.; Martinez, H.; Contreras, R.H.; Tormena, C.F.; Nodin, L.; Dolbier Jr., W.R.
Filiación:Chemistry Department, University of Florida, Gainesville, FL 32611-7200, United States
Departamento de Física, FCEyN, Cdad. Universitaria, Pab. I, 1428 Buenos Aires, Argentina
Organic Chemistry Department, Chemistry Institute, University of Campinas, 13084-971 Campinas, São Paulo, Brazil
Palabras clave:19F chemical shifts; 19F-19F couplings; conformation; FCCP-CMO; Fermi hole; NMR; paracyclophane; perfluoro[2.2]paracyclophane; through-space
Año:2011
Volumen:49
Número:3
Página de inicio:93
Página de fin:105
DOI: http://dx.doi.org/10.1002/mrc.2713
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_v49_n3_p93_Ghiviriga

Referencias:

  • Zhang, L.H., Ogawa, K., Ghiviriga, I., Dolbier, W.R., (2009) J. Org. Chem., 74, p. 6831
  • Ghiviriga, I., Dulong, F., Dolbier, W.R., (2009) Magn. Reson. Chem., 47, p. 313
  • GMNR Website, , ∼budzelaa/ gNMR/gNMR.html [15 September 2010]
  • 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) Revision E.01, , Gaussian: Wallingford, CT
  • Glendening, E.D., Badenhoop, J.K., Reed, A.E., Carpenter, J.E., Bohmann, J.A., Morales, C.M., Weinhold, F., (2001) NBO 5.0, , Theoretical Chemistry Institute: University of Wisconsin, Madison
  • Hogben, M.G., Graham, W.A.G., (1969) J. Am. Chem. Soc., 91, p. 283
  • Ernst, L., Ibrom, K., (1997) Magn. Reson. Chem., 35, p. 868
  • Rae, I.D., Burgess, D.A., Bombaci, S., Baron, M.L., Woolcock, M.L., (1984) Aust. J. Chem., 37, p. 1437
  • Gung, B.W., Amicangelo, J.C., (2006) J. Org. Chem., 71, p. 9261
  • Gallivan, J.P., Dougherty, D.A., (1999) Org. Lett., 1, p. 103
  • Lu, Y.-X., Wang, J.-W., Yu, Q.-S., (2007) Int. J. Quantum Chem., 107, p. 1479
  • Barfield, M., Chakrabarti, B., (1969) Chem. Rev., 69, p. 757
  • Schaefer, T., Schwenk, R., MacDonald, C.J., Reynolds, W.F., (1968) Can. J. Chem., 46, p. 2187
  • Mallory, F.B., Mallory, C.W., Butler, K.E., Lewis, M.B., Xia, A.Q., Luzik, E.D., Fredenburgh, L.E., Chirlian, L.E., (2000) J. Am. Chem. Soc., 122, p. 4108
  • Peralta, J.E., Barone, V., Contreras, R.H., Zaccari, D.G., Snyder, J.P., (2001) J. Am. Chem. Soc., 123, p. 9162
  • Ramsey, N.F., (1953) Phys. Rev., 91, p. 303
  • Arnold, W.D., Mao, J.H., Sun, H.H., Oldfield, E., (2000) J. Am. Chem. Soc., 122, p. 12164
  • Soncini, A., Lazzeretti, P., (2003) J. Chem. Phys., 119, p. 1343
  • Castillo, N., Matta, C.F., Boyd, R.J., (2005) J. Chem. Inf. Model, 45, p. 354
  • Contreras, R.H., Esteban, A.L., Díez, E., Head, N.J., Della, E.W., (2006) Mol. Phys., 104, p. 485
  • Dos Santos, F.P., Tormena, C.F., Contreras, R.H., Rittner, R., Magalhaes, A., (2008) Magn. Reson. Chem., 46, p. 107
  • Gauze, G.F., Basso, E.A., Contreras, R.H., Tormena, C.F., (2009) J. Phys. Chem. A, 113, p. 2647
  • Natiello, M.A., Contreras, R.H., (1984) Chem. Phys. Lett., 104, p. 568
  • Contreras, R.H., Peralta, J.E., (2000) Prog. Nucl. Mag. Res. Sp., 37, p. 321
  • Mallory, F.B., Mallory, C.W., Baker, M.B., (1990) J. Am. Chem. Soc., 112, p. 2577
  • Perez, C., Suardiaz, R., Ortiz, P.J., Crespo-Otero, R., Bonetto, G.M., Gavin, J.A., García De La Vega, J.M., Contreras, R.H., (2008) Magn. Reson. Chem., 46, p. 846
  • Provasi, P.F., Sauer, S.P.A., (2006) J. Chem. Theory Comput., 2, p. 1019
  • Contreras, R.H., Gotelli, G., Ducati, L.C., Barbosa, T.M., Tormena, C.F., (2010) J. Phys. Chem. A, 114, p. 1044
  • Oddershede, J., Löwdin, P.-O., (1978) Advances in Quantum Chemistry, p. 275. , (a), in, vol. 11 (Ed.:), Academic Press: London, p
  • Diz, A.C., Giribet, C.G., Ruiz De Azúa, M.C., Contreras, R.H., (1990) Int. J. Quantum Chem., 37, p. 663. , (b)
  • 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. , (c)

Citas:

---------- APA ----------
Ghiviriga, I., Zhang, L., Martinez, H., Contreras, R.H., Tormena, C.F., Nodin, L. & Dolbier Jr., W.R. (2011) . 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes. Magnetic Resonance in Chemistry, 49(3), 93-105.
http://dx.doi.org/10.1002/mrc.2713
---------- CHICAGO ----------
Ghiviriga, I., Zhang, L., Martinez, H., Contreras, R.H., Tormena, C.F., Nodin, L., et al. "19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes" . Magnetic Resonance in Chemistry 49, no. 3 (2011) : 93-105.
http://dx.doi.org/10.1002/mrc.2713
---------- MLA ----------
Ghiviriga, I., Zhang, L., Martinez, H., Contreras, R.H., Tormena, C.F., Nodin, L., et al. "19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes" . Magnetic Resonance in Chemistry, vol. 49, no. 3, 2011, pp. 93-105.
http://dx.doi.org/10.1002/mrc.2713
---------- VANCOUVER ----------
Ghiviriga, I., Zhang, L., Martinez, H., Contreras, R.H., Tormena, C.F., Nodin, L., et al. 19F chemical shifts, coupling constants and conformational preferences in monosubstituted perfluoroparacyclophanes. Magn. Reson. Chem. 2011;49(3):93-105.
http://dx.doi.org/10.1002/mrc.2713