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Abstract:

para-Difluorobenzene (I) and 1,1,4,4-tetra-fluoro-1,3-butadiene (II) were studied as model compounds in order to obtain an insight into the factors determining the large values of long- {A figure is presented} range F-F couplings which are known for conjugated systems. The role played by the π-electronic system in transmitting the spin information associated with the Fermi contact (FC), the spindipolar (SD) and the paramagnetic spin-orbital (PSO) interactions was evaluated using the inner projections of the polarization propagator technique (IPPP). The important SD contributions to such couplings were analysed using the contributions from localized molecular orbitais within the polarization propagator approach (CLOPPA) method. Comparison of analogous coupling pathways in I and II indicates that a conjugated system is more efficient in transmitting the SD coupling the more "concentrated" is the π-electronic system. This behaviour parallels that known for the FC interaction in long-range H-H couplings. © 1990.

Registro:

Documento: Artículo
Título:Large spin-dipolar long-range F-F coupling constants in conjugative compounds: their study using propagators
Autor:Peruchena, N.M.; Aucar, G.A.; Contreras, R.H.
Filiación:Area de Química-Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, U.N.N.E., (3400) CorrientesArgentina
Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 1. (1428) Buenos AiresArgentina
Año:1990
Volumen:210
Número:C
Página de inicio:205
Página de fin:210
DOI: http://dx.doi.org/10.1016/0166-1280(90)80043-N
Título revista:Journal of Molecular Structure: THEOCHEM
Título revista abreviado:J. Mol. Struct. THEOCHEM
ISSN:01661280
CODEN:THEOD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v210_nC_p205_Peruchena

Referencias:

  • Kowalewski, (1977) Prog. NMR Spectrosc., 11, p. 1
  • Kowalewski, (1982) Ann. Rep. NMR Spectrosc., 12, p. 82
  • G.A. Webb (Ed.), Nuclear Magnetic Resonance, Specialist Periodical Reports, Royal Society of Chemistry, London; Contreras, Natiello, Scuseria, (1985) Magn. Reson. Rev., 9, p. 239
  • Engelmann, Contreras, Transmission mechanisms of spin-spin coupling constants within theCHF approximation: Their study using inner projections of the polarization propagator (1983) International Journal of Quantum Chemistry, 23, p. 1033
  • Diz, de Azúa, Giribet, Contreras, The use of localized molecular orbitals and the polarization propagator to identify transmission mechanisms in nuclear spin-spin couplings (1990) International Journal of Quantum Chemistry, 37, p. 663
  • Barfield, Chakrabarti, (1969) Chem. Rev., 69, p. 757
  • Günther, Jikeli, Proton nuclear magnetic resonance spectra of cyclic monoenes: hydrocarbons, ketones, heterocycles, and benzo derivatives (1977) Chemical Reviews, 77, p. 599
  • Hilton, Sutcliffe, (1975) Prog. NMR Spectrosc., 10, p. 27
  • Servis, Roberts, (1965) J. Am. Chem. Soc., 87, p. 1339
  • Weigert, Roberts, (1971) J. Am. Chem. Soc., 93, p. 236
  • Natiello, Scuseria, Contreras, (1984) Chem. Phys. Lett., 108, p. 589
  • Contreras, de Azúa, Giribet, Ferraro, Diz, (1989) Química Teórica (Theoretical Chemistry), 2. , S. Fraga, Consejo Superior de Investigaciones Científicas, Madrid, Chap. 16
  • Pople, Beveridge, (1970) Approximate Molecular Orbital Theory, , McGraw-Hill, New York
  • Oddershede, (1970) Advances in Quantum Chemistry, 11. , P.O. Löwdin, Academic Press, New York
  • Engelmann, Scuseria, Contreras, (1982) J. Magn. Reson., 50, p. 21
  • Linderberg, Öhrn, (1973) Propagators in Quantum Chemistry, , Academic Press, New York
  • M.J. Dewar and J.J.P. Stewart, AMPAC, Quantum Chemistry Program Exchange, Program No. 527, University of Indiana, Bloomington, IN; Natiello, Scuseria, Contreras, (1983) J. Mol. Struct. (Theochem), 105, p. 233
  • Engelmann, Contreras, Facelli, (1981) Theor. Chim. Acta, 59, p. 17
  • Facelli, Contreras, de Kowalewski, Kowalewski, Piegaia, (1983) J. Mol. Struct. (Theochem), 94, p. 163

Citas:

---------- APA ----------
Peruchena, N.M., Aucar, G.A. & Contreras, R.H. (1990) . Large spin-dipolar long-range F-F coupling constants in conjugative compounds: their study using propagators. Journal of Molecular Structure: THEOCHEM, 210(C), 205-210.
http://dx.doi.org/10.1016/0166-1280(90)80043-N
---------- CHICAGO ----------
Peruchena, N.M., Aucar, G.A., Contreras, R.H. "Large spin-dipolar long-range F-F coupling constants in conjugative compounds: their study using propagators" . Journal of Molecular Structure: THEOCHEM 210, no. C (1990) : 205-210.
http://dx.doi.org/10.1016/0166-1280(90)80043-N
---------- MLA ----------
Peruchena, N.M., Aucar, G.A., Contreras, R.H. "Large spin-dipolar long-range F-F coupling constants in conjugative compounds: their study using propagators" . Journal of Molecular Structure: THEOCHEM, vol. 210, no. C, 1990, pp. 205-210.
http://dx.doi.org/10.1016/0166-1280(90)80043-N
---------- VANCOUVER ----------
Peruchena, N.M., Aucar, G.A., Contreras, R.H. Large spin-dipolar long-range F-F coupling constants in conjugative compounds: their study using propagators. J. Mol. Struct. THEOCHEM. 1990;210(C):205-210.
http://dx.doi.org/10.1016/0166-1280(90)80043-N