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Abstract:

Cyclohexane is an extremely flexible molecule that oscillates, at room temperature, between two clearly distinct and extreme conformations that cannot be distinguished at room temperature; so much so that the NMR spectrum is a single line that includes all 12 protons be they axial or equatorial. This raises the interesting question as to what happens when there are equal substituents at the 1 and 4 carbon atoms of the ring. Therefore substitution in the 1,4-positions in the cyclohexane ring has been the subject of considerable interest because some form of interconversion between extreme conformations could lead to the existence of a rather unusual behavior. To study this problem, the interconversion in (di- or tetra-1,4)-substituted six-membered cyclohexane-type rings, trans-1,4-dibromo-1,4-dicyanocyclohexane, was found to be a particularly suitable candidate. Although X-ray diffraction studies on the crystalline solid found the molecule to be centrosymmetric, it still shows a significant dipole moment μ in solution, as determined with a procedure that leads to the vapor phase values of μ. Furthermore, the low magnetic field proton NMR spectrum at ambient temperature appears as a single line, a situation that changes with increasing field intensity and different solvents. Both these effects are attributed to dynamics, because small distortions can easily disrupt the exact cancellation of the individual dipoles (which are quite strong) associated with each end of the molecule. The molecule can exist in two forms, with both the bromines in an axial geometry or both in an equatorial position. Interconversion between these forms is observed, as in the parent cyclohexane. The single NMR line observed at low magnetic fields is due to fast exchange and requires that the two forms have roughly equal populations. Spectra obtained at low temperature confirm this, and variable-temperature studies allow measurement of the rates, leading to an enthalpy of activation of 62 kJ mol-1. More details of the interconversion are provided by some new calculation methods. Even for a relatively small molecule like this, calculation of a full potential energy surface is prohibitive. However, methods are now available to follow the molecule along the reaction coordinate in quite an efficient way. The results of these calculations lead to an extremely detailed picture of chair-chair interconversion in a di- and tetrasubstituted six-membered ring of the cyclohexane family. © 2011 American Chemical Society.

Registro:

Documento: Artículo
Título:Interconversion study in 1,4-substituted six-membered cyclohexane-type rings. structure and dynamics of trans -1,4-dibromo-1,4-dicyanocyclohexane
Autor:Bain, A.D.; Baron, M.; Burger, S.K.; Kowalewski, V.J.; Rodríguez, M.B.
Filiación:Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON L8S 4M1, Canada
Facultad de Ciencias Exactas y Naturales, Universidad de Belgrano, Villanueva 1324, 1426 Buenos Aires, Argentina
Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires Pabellón 1, Ciudad Universitaria, 1426 Buenos Aires, Argentina
Palabras clave:Calculation methods; Carbon atoms; Centrosymmetric; Crystalline solids; Cyclohexane ring; Different solvents; Enthalpy of activation; Equatorial positions; Field intensity; Flexible molecules; Interconversions; Low magnetic fields; Low temperatures; NMR spectrum; Proton NMR; Reaction coordinates; Room temperature; Six-membered rings; Small molecules; Structure and dynamics; Vapor Phase; Variable temperature; X-ray diffraction studies; Behavioral research; Bromine; Conformations; Magnetic fields; Molecules; Nuclear magnetic resonance; Nuclear magnetic resonance spectroscopy; Protons; Quantum chemistry; X ray diffraction; Cyclohexane
Año:2011
Volumen:115
Número:33
Página de inicio:9207
Página de fin:9216
DOI: http://dx.doi.org/10.1021/jp205375f
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_v115_n33_p9207_Bain

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Citas:

---------- APA ----------
Bain, A.D., Baron, M., Burger, S.K., Kowalewski, V.J. & Rodríguez, M.B. (2011) . Interconversion study in 1,4-substituted six-membered cyclohexane-type rings. structure and dynamics of trans -1,4-dibromo-1,4-dicyanocyclohexane. Journal of Physical Chemistry A, 115(33), 9207-9216.
http://dx.doi.org/10.1021/jp205375f
---------- CHICAGO ----------
Bain, A.D., Baron, M., Burger, S.K., Kowalewski, V.J., Rodríguez, M.B. "Interconversion study in 1,4-substituted six-membered cyclohexane-type rings. structure and dynamics of trans -1,4-dibromo-1,4-dicyanocyclohexane" . Journal of Physical Chemistry A 115, no. 33 (2011) : 9207-9216.
http://dx.doi.org/10.1021/jp205375f
---------- MLA ----------
Bain, A.D., Baron, M., Burger, S.K., Kowalewski, V.J., Rodríguez, M.B. "Interconversion study in 1,4-substituted six-membered cyclohexane-type rings. structure and dynamics of trans -1,4-dibromo-1,4-dicyanocyclohexane" . Journal of Physical Chemistry A, vol. 115, no. 33, 2011, pp. 9207-9216.
http://dx.doi.org/10.1021/jp205375f
---------- VANCOUVER ----------
Bain, A.D., Baron, M., Burger, S.K., Kowalewski, V.J., Rodríguez, M.B. Interconversion study in 1,4-substituted six-membered cyclohexane-type rings. structure and dynamics of trans -1,4-dibromo-1,4-dicyanocyclohexane. J Phys Chem A. 2011;115(33):9207-9216.
http://dx.doi.org/10.1021/jp205375f