“…This interaction leads to a strong preference of the trans orientation of the C−D bond relative to the lone pair. The influence of the anomeric effect on the conformational properties has been studied extensively by theoretical methods for the model compound dihydroxymethane (methanediol), CH 2 (OH) 2 . − Depending on the orientation of the O−X bonds, the following four conformations have to be considered for CY 2 (OX) 2 compounds: …”
The geometric structure and conformational properties
determined by gas electron diffraction and theoretical methods (ab
initio and density functional calculations). The
electron diffraction intensities are reproduced best by a mixture of
70(10)% (+sc,+sc) and 30(10)% (sc,ap)
corresponding to ΔH° =
H°(sc,ap) − H°(+sc,+sc)
= 0.9(3) kcal mol-1. This
experimental result is reproduced
very well by HF/6-31G* and MP2/6-31G* calculations (ΔE =
0.7 kcal mol-1), but not by the HF/3-21G and
density functional (SVWN/6-311G*, BLYP/6-311G*, B3LYP/6-311+G*)
approximations. In addition, the conformational properties of CF2(OH)2 and
CH2(OF)2 were investigated theoretically.
The experimental and theoretical
results are discussed in terms of anomeric effects.
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