Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10424
Title: Conformational Study of Monomeric 2,3-Butanediols by Matrix-Isolation Infrared Spectroscopy and DFT Calculations
Authors: Jesus, A. J. Lopes 
Rosado, Mário T. S. 
Reva, Igor 
Fausto, Rui 
Eusébio, M. Ermelinda 
Redinha, J. S. 
Issue Date: 30-Mar-2006
Publisher: American Chemical Society
Citation: The Journal of Physical Chemistry A. 110:12 (2006) 4169-4179
Abstract: The FT-IR spectra of two diastereomers of 2,3-butanediol, (R,S) and (S,S), isolated in low-temperature argon and xenon matrixes were studied, allowing the identification of two different conformers for each compound. These conformers were characterized by a ±gauche arrangement around the O−C−C−O dihedral angle, thus enabling the establishment of a very weak intramolecular hydrogen bond of the O···H−O type. No other forms of these compounds were identified in matrixes, despite the fact that these four conformers had calculated relative energies from 0 to 5.1 kJ mol-1 and were expected to be thermally populated from 50 to 6% in the gaseous phase of each compound. The nonobservation of additional conformers was explained in terms of low barriers to intramolecular rotation, resulting in the conformational relaxation of the compounds during deposition of the matrixes. The barriers to internal rotation of the OH groups were computed to be less than 4 kJ mol-1 and are easily overcome in matrixes within the family of conformers with the same heavy atom backbone. The barriers for intramolecular rearrangement of the O−C−C−O dihedral angle in both diastereomers were calculated to range from 20 to 30 kJ mol-1. Interconversions between the latter conformers were not observed in matrixes, even after annealing up to 65 K. Energy calculations, barriers, and calculated infrared spectra were carried out at the DFT(B3LYP)/6-311++G** theory. Additional MP2/6-311++G** calculations of energies and vibrational frequencies were performed on the most relevant conformers. Finally, independent estimations of the hydrogen-bond enthalpy in the studied molecules were also obtained based on theoretical structural data and from vibrational frequencies (using well-established empirical correlations). The obtained values for −ΔH for both diastereomers of 2,3-butanediol amount to ca. 6−8 kJ mol-1.
URI: http://hdl.handle.net/10316/10424
ISSN: 1089-5639
DOI: 10.1021/jp0572737
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

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