Rotational barriers: Part 3. 2-Haloethanols
作者： Kenneth B. Wiberg , Mark A. Murcko
DOI: 10.1016/0166-1280(88)80376-2
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摘要: Abstract The geometries of the lowest energy gauche and trans conformers 2-fluoroethanol (2FE) 2-chloroethanol (2CE) have been calculated at 6-31G* level, energies with several basis sets inclusion electron correlation. global minimum for both compounds is found to be conformer, in agreement experiment. At MP3/6-31G* 2CE 1.66 kcal mol−1 higher than gauche, while 2FE 2.34 gauche. Geometries were also optimized various fixed values HOCC dihedral angle, from which barrier OH rotation was derived. Further calculations MP3/6-311+ +G** level lowered relative by only 0.3 2.03, but had a much larger effect on rotational barrier. Calculations MP3/6-311++G** done ethanol, comparison ethanol profiles indicates strongly attractive HF interaction which, after elimination non-bonding bending contributions, may most simply modelled as coulombic term. Vibrational frequencies estimated do not support idea that small separation responsible frequency differences between
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