Details
| Original language | English |
|---|---|
| Pages (from-to) | 6610-6618 |
| Number of pages | 9 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 13 |
| Issue number | 14 |
| Publication status | Published - 14 Apr 2011 |
Abstract
The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several 37Cl and 13C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C 1-C2-O-C3) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 31. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.
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. 13, No. 14, 14.04.2011, p. 6610-6618.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Structural evidence of anomeric effects in the anesthetic isoflurane
AU - Lesarri, Alberto
AU - Vega-Toribio, Alicia
AU - Suenram, Richard D.
AU - Brugh, Dale J.
AU - Nori-Shargh, Davood
AU - Boggs, James E.
AU - Grabow, Jens Uwe
PY - 2011/4/14
Y1 - 2011/4/14
N2 - The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several 37Cl and 13C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C 1-C2-O-C3) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 31. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.
AB - The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several 37Cl and 13C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C 1-C2-O-C3) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 31. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.
UR - http://www.scopus.com/inward/record.url?scp=79952960263&partnerID=8YFLogxK
U2 - 10.1039/c0cp02465a
DO - 10.1039/c0cp02465a
M3 - Article
C2 - 21384026
AN - SCOPUS:79952960263
VL - 13
SP - 6610
EP - 6618
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 14
ER -