Details
| Original language | English |
|---|---|
| Pages (from-to) | 12486-12493 |
| Number of pages | 8 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 12 |
| Issue number | 39 |
| Publication status | Published - 21 Oct 2010 |
Abstract
The conformational equilibria of vanillin and ethylvanillin have been investigated in a supersonic jet expansion using rotational spectroscopy. Two conformers have been detected for each molecule, with a dominant O-H⋯O intramolecular hydrogen bond locking the local conformation of the hydroxyl and methoxy/ethoxy groups. As a consequence, the observed conformers of vanillin differ only in the orientation of the aldehyde group, either cis or trans with respect to the methoxy group. For ethylvanillin the ethoxy group would plausibly generate additional trans (in-plane) or gauche (out-of-plane) orientations. However, the two detected conformations exhibit only planar ethoxy trans arrangements, with the gauche forms most probably depopulated by collisional relaxation in the jet. Torsional tunneling effects due to internal rotation of the terminal methyl groups were not detectable, indicating internal rotation barriers above 12.3 kJ mol-1. The conformational population ratios in the jet have been estimated from relative intensity measurements. Ab initio (MP2) and DFT calculations using B3LYP and the recent M05-2X empirical functional supplemented the experimental work, describing the rotational parameters, conformational landscape and the aldehyde and methyl internal rotation barriers in these molecules.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- General Physics and Astronomy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Physical Chemistry Chemical Physics, Vol. 12, No. 39, 21.10.2010, p. 12486-12493.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Conformational equilibria in vanillin and ethylvanillin
AU - Cocinero, Emilio J.
AU - Lesarri, Alberto
AU - Écija, Patricia
AU - Grabow, Jens Uwe
AU - Fernández, José A.
AU - Castaño, Fernando
PY - 2010/10/21
Y1 - 2010/10/21
N2 - The conformational equilibria of vanillin and ethylvanillin have been investigated in a supersonic jet expansion using rotational spectroscopy. Two conformers have been detected for each molecule, with a dominant O-H⋯O intramolecular hydrogen bond locking the local conformation of the hydroxyl and methoxy/ethoxy groups. As a consequence, the observed conformers of vanillin differ only in the orientation of the aldehyde group, either cis or trans with respect to the methoxy group. For ethylvanillin the ethoxy group would plausibly generate additional trans (in-plane) or gauche (out-of-plane) orientations. However, the two detected conformations exhibit only planar ethoxy trans arrangements, with the gauche forms most probably depopulated by collisional relaxation in the jet. Torsional tunneling effects due to internal rotation of the terminal methyl groups were not detectable, indicating internal rotation barriers above 12.3 kJ mol-1. The conformational population ratios in the jet have been estimated from relative intensity measurements. Ab initio (MP2) and DFT calculations using B3LYP and the recent M05-2X empirical functional supplemented the experimental work, describing the rotational parameters, conformational landscape and the aldehyde and methyl internal rotation barriers in these molecules.
AB - The conformational equilibria of vanillin and ethylvanillin have been investigated in a supersonic jet expansion using rotational spectroscopy. Two conformers have been detected for each molecule, with a dominant O-H⋯O intramolecular hydrogen bond locking the local conformation of the hydroxyl and methoxy/ethoxy groups. As a consequence, the observed conformers of vanillin differ only in the orientation of the aldehyde group, either cis or trans with respect to the methoxy group. For ethylvanillin the ethoxy group would plausibly generate additional trans (in-plane) or gauche (out-of-plane) orientations. However, the two detected conformations exhibit only planar ethoxy trans arrangements, with the gauche forms most probably depopulated by collisional relaxation in the jet. Torsional tunneling effects due to internal rotation of the terminal methyl groups were not detectable, indicating internal rotation barriers above 12.3 kJ mol-1. The conformational population ratios in the jet have been estimated from relative intensity measurements. Ab initio (MP2) and DFT calculations using B3LYP and the recent M05-2X empirical functional supplemented the experimental work, describing the rotational parameters, conformational landscape and the aldehyde and methyl internal rotation barriers in these molecules.
UR - http://www.scopus.com/inward/record.url?scp=77957915875&partnerID=8YFLogxK
U2 - 10.1039/c0cp00585a
DO - 10.1039/c0cp00585a
M3 - Article
C2 - 20721403
AN - SCOPUS:77957915875
VL - 12
SP - 12486
EP - 12493
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 39
ER -