2003
DOI: 10.1016/s0009-2614(02)01786-4
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On the structure and torsional potential of trifluoromethoxybenzene: an ab initio and density functional study

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Cited by 41 publications
(50 citation statements)
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“…Interestingly, similarly twisted conformations are also found for aryl‐bound difluoroalkyloxy groups. Spectroscopic studies and high‐level quantum‐mechanical calculations further show that preference for the planar arrangement in anisole (Δ E ∼3 kcal mol −1 ) is inverted to the orthogonal orientation in trifluoromethylanisole (Δ E ∼−0.5 kcal mol −1 ) 28…”
Section: The Effect Of a F Substituent On Molecular Conformationsupporting
confidence: 61%
“…Interestingly, similarly twisted conformations are also found for aryl‐bound difluoroalkyloxy groups. Spectroscopic studies and high‐level quantum‐mechanical calculations further show that preference for the planar arrangement in anisole (Δ E ∼3 kcal mol −1 ) is inverted to the orthogonal orientation in trifluoromethylanisole (Δ E ∼−0.5 kcal mol −1 ) 28…”
Section: The Effect Of a F Substituent On Molecular Conformationsupporting
confidence: 61%
“…This perpendicular preference is in good agreement with ab initio calculations that indicate a global minimum geometry at an aryl-O torsion angle of 90°. 78 The preference for an orthogonal arrangement for R ) CF 3 vs planar for R ) CH 3 can be rationalized by (i) the larger volume of the trifluoromethyl group leading to higher 1,4 strain in the planar conformation and (ii) electronic effects of the highly electronegative CF 3 group reducing the amount of π-conjugation of the oxygen ether atom with the aryl system (anomeric effect between oxygen lone pairs and C-F bonds).…”
Section: Substituted Aryl Systems -Stereoelectronic and Steric Effectsmentioning
confidence: 99%
“…This finding was also confirmed by MP4(SDTQ) computations. [40] It follows that there is almost free rotation in the initial compounds 5, which should increase the total energy by approximately 0.5 kcal/mol. Taking into account that the internal rotation should also effectively increase the energy of deprotonated 5 at position C (2) Ϫ by roughly 0.5 kcal/ mol, we can safely conclude that acidity of 5 should not be affected by rotational motion of the OCF 3 group.…”
Section: Koopmentioning
confidence: 96%
“…[37Ϫ40] The most sophisticated calculations were performed by Karpfen et al, [40] who found that the ortho [o]-conformation of OϪCF 3 group relative to the benzene plane is 0.5 kcal/mol more stable than the eclipsed [e]-conformation by MP2/cc-pVTZ and B3LYP/cc-pVTZ procedures. These conformations correspond to two minima on the potential surface, separated by a low barrier with a height of about 0.2 kcal/mol above the [e] conformation.…”
Section: Koopmentioning
confidence: 99%