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Abstract:

A conceptual analysis of the CLOPPA (Contributions from Localized Orbitals within the Polarization Propagator Approach) expressions that deconvolute NMR spin-spin coupling constants [Diz A. C.; Giribet C. G.; Ruiz de Azúa, M. C.; Contreras, R. H. Int. J. Quantum Chem. 1990, 37, 663.] into orbital contributions can provide an in-depth insight into the features of the electronic molecular structure that originate a given 1JCH experimental trend. In this work, several 1-X-cyclopropane derivatives are taken as model compounds to apply such ideas to rationalize substituent effects on the Fermi contact term of 1JC1,H spin-spin coupling. It is shown that in this type of coupling, its experimental trend, as measured in this work, cannot be accounted for with only the "bond" and the "other bond" contributions, requiring the inclusion of "other antibonding contributions". Such effect is discussed in terms of hyperconjugative interactions. © 2008 American Chemical Society.

Registro:

Documento: Artículo
Título:Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
Autor:Neto, Á.C.; Dos Santos, F.P.; Contreras, R.H.; Rittner, R.; Tormena, C.F.
Filiación:Organic Chemistry Department, Chemistry Institute, University of Campinas, P.O. Box 6154, Campinas, São Paulo 13084-971, Brazil
Department of Physics, FCEyN, University of Buenos Aires, Buenos Aires, Argentina
Palabras clave:Experiments; Nuclear magnetic resonance; Propane; Quantum chemistry; Sulfur compounds; AS models; Conceptual analysis; DFT studies; Electronic origins; Fermi contact terms; Hyperconjugative interactions; Localized orbitals; Orbital contributions; Propagator approaches; Spin couplings; Spin-spin coupling constants; Substituent effects; Spin dynamics
Año:2008
Volumen:112
Número:46
Página de inicio:11956
Página de fin:11959
DOI: http://dx.doi.org/10.1021/jp8069805
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_v112_n46_p11956_Neto

Referencias:

  • Oddershede, J., Polarization Propagator Calculations (1978) Advances in Quantum Chemistry, 11, p. 275. , Löwdin, P.-O, Ed, Academic Press: New York
  • Engelmann, A.R., Contreras, R.H., (1983) Int. J. Quantum Chem, 23, p. 1033
  • 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., Giribet, C.G., Ruiz de Azúa, M.C., Ferraro, M.B., (1992) Electronic Origin of High Resolution NMR Parameters in Structure, Interactions, and Reactivity; Fraga, S, 77 B, p. 212. , Ed, Elsevier: New York, Cap. 7, p
  • 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
  • González, J.A., Aucar, G.A., Ruiz de Azúa, M.C., Contreras, R.H., (1997) Int. J. Quantum Chem, 61, p. 823
  • Peralta, J.E., Contreras, R.H., Snyder, J.P., (2000) J. Chem. Soc. Chem. Commun, p. 2025
  • Barone, V., Peralta, J.E., Contreras, R.H., Sosnin, A.V., Krivdin, L.B., (2001) Magn. Reson. Chem, 39, p. 600
  • Wilkens, S.J., Westler, W.M., Markley, J.L., Weinhold, F., (2001) J. Am. Chem. Soc, 123, p. 12026
  • Wu, A., Gräfenstein, J., Cremer, D., (2003) J. Phys. Chem. A, 107, p. 7043
  • Cremer, D., Gräfenstein, J., (2007) Phys. Chem. Chem. Phys, 9, p. 2791
  • 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
  • Ramsey, N.F., (1953) Phys. Rev, 91, p. 303
  • 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
  • Reed, A. E; Curtiss, L. A; Weinhold, F. Chem. Rev. 1988, 88, 899; Weinhold, F., (1998) Encyclopedia of Computational Chemistry, 3, p. 1792. , Schleyer, P. v. R, Ed, Wiley: New York
  • Dewar, M.J.S., Dougherty, R.C., (1975) The PMO Theory of Organic Chemistry, , Plenum Press: New York
  • Palmer III, A.G., Cavanagh, J., Wright, P.E., Rance, M., (1991) J. Magn. Reson, 93, p. 151
  • Kay, L.E., Keifer, P., Saarinen, T., (1992) J. Am. Chem. Soc, 114, p. 10663
  • Schleucher, J., Schwendinger, M., Sattler, M., Schmidt, P., Schedletzky, O., Glaser, S.J., Sorensen, O.W., Griesinger, C., (1994) J. Biomol. NMR, 4, p. 301
  • Sychrovshý, V., Gräfenstein, J., Cremer, D., (2000) J. Chem. Phys, 113, p. 3530
  • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, Jr, J. A, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keit; Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F. (NBO 5.0G. Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001);http://www.chem. wisc.edu/~nbo5. Program was implemented in the Gaussian 03 package; Becke, A.D., (1988) Phys. Rev. A, 38, p. 3098
  • Becke, A.D., (1993) J. Chem. Phys, 98, p. 5648
  • Woon, D.E., Dunning, T.H., (1993) J. Chem. Phys, 98, p. 1358
  • Barone, V., (1994) J. Chem Phys, 101, p. 6834
  • Peterson, K.A., (2003) J. Chem. Phys, 119, p. 11099
  • Muller, N., Pritchard, D.E., (1959) J. Chem. Phys, 31, p. 768
  • Contreras, R.H., Peralta, J.E., Giribet, C.G., Ruiz de Azúa, M.C., Facelli, J.C., (2000) Annu. Rep. NMR Spectrosc, 41, p. 55
  • Lacey, M.J., Macdonald, C.G., Pross, A., Shannon, J.S., Sternhell, S., (1970) Aust. J. Chem, 23, p. 1421
  • Hu, Z.-M., Zhan, C.-G., (1993) Theo. Chim. Acta, 84, p. 521

Citas:

---------- APA ----------
Neto, Á.C., Dos Santos, F.P., Contreras, R.H., Rittner, R. & Tormena, C.F. (2008) . Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study. Journal of Physical Chemistry A, 112(46), 11956-11959.
http://dx.doi.org/10.1021/jp8069805
---------- CHICAGO ----------
Neto, Á.C., Dos Santos, F.P., Contreras, R.H., Rittner, R., Tormena, C.F. "Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study" . Journal of Physical Chemistry A 112, no. 46 (2008) : 11956-11959.
http://dx.doi.org/10.1021/jp8069805
---------- MLA ----------
Neto, Á.C., Dos Santos, F.P., Contreras, R.H., Rittner, R., Tormena, C.F. "Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study" . Journal of Physical Chemistry A, vol. 112, no. 46, 2008, pp. 11956-11959.
http://dx.doi.org/10.1021/jp8069805
---------- VANCOUVER ----------
Neto, Á.C., Dos Santos, F.P., Contreras, R.H., Rittner, R., Tormena, C.F. Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study. J Phys Chem A. 2008;112(46):11956-11959.
http://dx.doi.org/10.1021/jp8069805