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Abstract:

Nuclear magnetic resonance spectrometers presently available are unable to recognize the two mirror-image forms of a chiral molecule, because in the absence of a chiral solvent, the NMR spectral parameters (chemical shifts and spin-spin coupling constants) are identical for the two enantiomers. This paper discusses how chirality may nevertheless, at least in theory, be recognized in liquid-state NMR spectroscopy by applying strong d. c. electric fields and measuring a pseudoscalar contribution to nuclear spin-spin coupling polarizability. Calculations are reported for medium-size chiral molecules, (2R)-N-methyloxaziridine, (Ra)-1,3-dimethylallene, and (2R)-2-methyloxirane. The very small contributions provided by the pseudoscalar of nuclear spin-spin coupling polarizability seem rather difficult to detect via NMR experiments in disordered phase. © 2010 Springer-Verlag.

Registro:

Documento: Artículo
Título:Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy
Autor:Pagola, G.I.; Ferraro, M.B.; Pelloni, S.; Lazzeretti, P.; Sauer, S.P.A.
Filiación:Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and IFIBA, CONICET Ciudad Universitaria, Pabellon 1, 1428 Buenos Aires, Argentina
Dipartimento di Chimica dell'Università degli Studi di Modena e Reggio Emilia, Via Campi 183, 41124 Modena, Italy
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark
Palabras clave:Chiral discrimination; Electric dipole polarizability of nuclear spin-spin coupling; Enantiomeric molecules in disordered phase; Nuclear magnetic resonance spectroscopy
Año:2011
Volumen:129
Número:3-5
Página de inicio:359
Página de fin:366
DOI: http://dx.doi.org/10.1007/s00214-010-0851-2
Título revista:Theoretical Chemistry Accounts
Título revista abreviado:Theor. Chem. Acc.
ISSN:1432881X
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1432881X_v129_n3-5_p359_Pagola

Referencias:

  • Barra, A.L., Robert, J.B., (1996) Mol Phys, 88, pp. 875-886
  • Laubender, G., Berger, R., (2003) Chem Phys Chem, 4, pp. 395-399
  • Soncini, A., Faglioni, F., Lazzeretti, P., (2003) Phys Rev A, 68, pp. 0334021-0334024
  • Buckingham, A.D., (2004) Chem Phys Lett, 398, pp. 1-5
  • Buckingham, A.D., Fischer, P., (2006) Chem Phys, 324, pp. 111-116
  • Zanasi, R., Pelloni, S., Lazzeretti, P., (2007) J Comput Chem, 28, pp. 2159-2163
  • Pelloni, S., Lazzeretti, P., Zanasi, R., (2007) J Chem Theor Comput, 3, pp. 1691-1698
  • Lazzeretti, P., Soncini, A., Zanasi, R., (2008) Theor Chem Acc, 119, pp. 99-106
  • Grayson, M., (2003) Int J Mol Sci, 4, pp. 218-230
  • Buckingham, A.D., Pople, J.A., (1955) Proc Phys Soc A, 68, pp. 905-909
  • Barron, L.D., (1982) Molecular Light Scattering and Optical Activity, , Cambridge: Cambridge University Press
  • Buckingham, A.D., (1967) Adv Chem Phys, 12, pp. 107-142
  • Ramsey, N.F., (1953) Phys Rev, 91, pp. 303-307
  • Pyykkö, P., (2000) Theor Chem Acc, 103, pp. 214-216
  • Lazzeretti, P., (1989) Chem Phys, 134, pp. 269-278
  • Lazzeretti, P., (1987) Adv Chem Phys, 75, pp. 507-549
  • Lazzeretti, P., Electric and magnetic properties of molecules (2003) Handbook of Molecular Physics and Quantum Chemistry, 3. , Part 1, Chapter 3, Wiley, Chichester
  • Mohr, P.J., Taylor, B.N., (2005) Rev Mod Phys, 77, pp. 1-107
  • Linderberg, J., Öhrn, Y., (1973) Propagators in Quantum Chemistry, , London: Academic Press
  • Oddershede, J., Jørgensen, P., Yaeger, D.L., (1984) Computer Phys Rep, 2, pp. 33-92
  • Olsen, J., Jorgensen, P., (1985) J Chem Phys, 82, pp. 3235-3264
  • Becke, A.D., (1993) J Chem Phys, 98, pp. 5648-5652
  • Lee, C., Yang, W., Parr, R.G., (1988) Phys Rev B, 37, pp. 785-789
  • Vosko, S.H., Wilk, L., Nusair, M., (1980) Can J Phys, 58, pp. 1200-1211
  • Stephens, P.J., Devlin, F.J., Chabalowski, C.F., Frisch, M.J., (1994) J Phys Chem, 98, pp. 11623-11627
  • Keal, W., Tozer, D.J., (2003) J Chem Phys, 119, pp. 3015-3024
  • Keal, W., Tozer, D.J., (2004) J Chem Phys, 121, pp. 5654-5660
  • Perdew, J.P., Burke, K., Ernzerhof, M., (1996) Phys Rev Lett, 77, pp. 3865-3868
  • http://www.kjemi.uio.no/software/dalton/, DALTON, An electronic structure program, Release 2. 0; 2005; 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 2003, , Revision C. 02. Gaussian, Inc., Wallingford, CT
  • Sadlej, A.J., (1988) Collect Czech Chem Commun, 53, pp. 1995-2016
  • Dunning Jr., T.H., (1989) J Chem Phys, 90, pp. 1007-1023
  • Woon, D.E., Dunning Jr., T.H., (1995) J Chem Phys, 103, pp. 4572-4585
  • van Duijneveldt, F.B., Gaussian basis sets for the atoms H-Ne for use in molecular calculations (1971) Res Report RJ, p. 945. , IBM
  • Enevoldsen, T., Oddershede, J., Sauer, S.P.A., (1998) Theor Chem Acc, 100, pp. 275-284
  • Provasi, P.F., Aucar, G.A., Sauer, S.P.A., (2001) J Chem Phys, 115, pp. 1324-1334
  • Barone, V., Provasi, P.F., Peralta, J.E., Snyder, J.P., Sauer, S.P.A., Contreras, R.H., (2003) J Phys Chem A, 107, pp. 4748-4754
  • Rusakov, Y.Y., Krivdin, L.B., Sauer, S.P.A., Levanova, E.P., Levkovskaya, G.G., (2010) Magn Res Chem, 48, pp. 633-637
  • Provasi, P.F., Sauer, S.P.A., (2010) J Chem Phys, 133, p. 54308
  • Jensen, F., (2006) J Chem Theory Comput, 2, pp. 1360-1369
  • Benedikt, U., Auer, A.A., Jensen, F., (2008) J Chem Phys, 129, p. 64111
  • Giorgio, E., Viglione, R.G., Zanasi, R., Rosini, C., (2004) J Am Chem Soc, 126, p. 2968

Citas:

---------- APA ----------
Pagola, G.I., Ferraro, M.B., Pelloni, S., Lazzeretti, P. & Sauer, S.P.A. (2011) . Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy. Theoretical Chemistry Accounts, 129(3-5), 359-366.
http://dx.doi.org/10.1007/s00214-010-0851-2
---------- CHICAGO ----------
Pagola, G.I., Ferraro, M.B., Pelloni, S., Lazzeretti, P., Sauer, S.P.A. "Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy" . Theoretical Chemistry Accounts 129, no. 3-5 (2011) : 359-366.
http://dx.doi.org/10.1007/s00214-010-0851-2
---------- MLA ----------
Pagola, G.I., Ferraro, M.B., Pelloni, S., Lazzeretti, P., Sauer, S.P.A. "Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy" . Theoretical Chemistry Accounts, vol. 129, no. 3-5, 2011, pp. 359-366.
http://dx.doi.org/10.1007/s00214-010-0851-2
---------- VANCOUVER ----------
Pagola, G.I., Ferraro, M.B., Pelloni, S., Lazzeretti, P., Sauer, S.P.A. Electric field effects on nuclear spin-spin coupling tensors and chiral discrimination via NMR spectroscopy. Theor. Chem. Acc. 2011;129(3-5):359-366.
http://dx.doi.org/10.1007/s00214-010-0851-2