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Abstract:

In order to get insight into transmission mechanisms of the title spin-spin coupling constants, nJ(C, F1) couplings (n=4, 5) were calculated at the DFT-B3LYP-6-311-G/EPR-III level, and 5J(Cα, F1) couplings were measured in 9 members of the series 1-F,4-X-cubanes, where the α atom of the X group is a carbon atom. Hyperconjugative interactions were evaluated within the NBO approach, using the same level of theory as that employed for calculating spin-spin coupling constants. The unusual 4J(C4, F1) spin-spin coupling constants known in 1-F,4-Xcubanes are rationalized in this work as originating mainly due to two factors, namely, (i) the strong σ-hyperconjugative interactions involving as donors the cage C-C bonds; (ii) the particular arrangement of cage bonds not involving either the C1 or the C4 carbon atoms, Ci and Cj. For linear X substituents, the direction F1-C1 ...C4-X is a three-fold symmetry axis and there are six Ci-Cj equivalent cage bonds, which are involved in (Ci-Cj)→(C1-F1)and (Ci-Cj)→(C4-X)hyperconjugative interactions. This means that coupling pathways involving such interactions are amplified six times, rendering the substrate very efficient for transmitting 'trans-cage' coupling constants. The large halogen substituent effects observed for 4J(C4, F1) spin-spin coupling constants in 1-F,4-X-cubanes (X = halogen atom) are rationalized in terms of interactions between σ-hyperconjugative (involving C-C bonds) and negative hyperconjugative interactions involving the halogen lone-pairs. © 2006 Taylor & Francis.

Registro:

Documento: Artículo
Título:Transmission mechanisms of NMR long-range J(13C,19F) scalar couplings in 1-F,4-X-cubanes: A DFT and experimental study
Autor:Contreras, R.H.; ESTEBANz, Á.L.; Díez, E.; Head, N.J.; Della, E.W.
Filiación:Departamento de Física, FCEyN, Universidad de Buenos Aires, Ciudad Universitaria, P. 1 and CONICET (C1428EHA), Buenos Aires, Argentina
Departamento de Química Física, Universidad de Alicante, Apartado 99, Alicante, E-03080, Spain
Departamento de Química Física Aplicada, Facultad de Ciencias, C2, Universidad Autónoma de Madrid, Madrid, E-28049, Spain
Department of Chemistry, School of Physical Sciences, Flinders University, Bedford Park, South Australia 5042, Australia
Palabras clave:Atoms; Couplings; Coupling constants; Halogen atoms; Hyperconjugative interactions; Scalar coupling; Spin-spin coupling constants; Substituent effect; Three-fold symmetry; Transmission mechanisms; Fluorine
Año:2006
Volumen:104
Número:4
Página de inicio:485
Página de fin:492
DOI: http://dx.doi.org/10.1080/00268970500276499
Título revista:Molecular Physics
Título revista abreviado:Mol. Phys.
ISSN:00268976
CODEN:MOPHA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00268976_v104_n4_p485_Contreras

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Citas:

---------- APA ----------
Contreras, R.H., ESTEBANz, Á.L., Díez, E., Head, N.J. & Della, E.W. (2006) . Transmission mechanisms of NMR long-range J(13C,19F) scalar couplings in 1-F,4-X-cubanes: A DFT and experimental study. Molecular Physics, 104(4), 485-492.
http://dx.doi.org/10.1080/00268970500276499
---------- CHICAGO ----------
Contreras, R.H., ESTEBANz, Á.L., Díez, E., Head, N.J., Della, E.W. "Transmission mechanisms of NMR long-range J(13C,19F) scalar couplings in 1-F,4-X-cubanes: A DFT and experimental study" . Molecular Physics 104, no. 4 (2006) : 485-492.
http://dx.doi.org/10.1080/00268970500276499
---------- MLA ----------
Contreras, R.H., ESTEBANz, Á.L., Díez, E., Head, N.J., Della, E.W. "Transmission mechanisms of NMR long-range J(13C,19F) scalar couplings in 1-F,4-X-cubanes: A DFT and experimental study" . Molecular Physics, vol. 104, no. 4, 2006, pp. 485-492.
http://dx.doi.org/10.1080/00268970500276499
---------- VANCOUVER ----------
Contreras, R.H., ESTEBANz, Á.L., Díez, E., Head, N.J., Della, E.W. Transmission mechanisms of NMR long-range J(13C,19F) scalar couplings in 1-F,4-X-cubanes: A DFT and experimental study. Mol. Phys. 2006;104(4):485-492.
http://dx.doi.org/10.1080/00268970500276499