Ab Initio Calculations of the Barriers to Rotation in 1,1-Difluoroallyl Radical and an Analysis of the Factors That Govern Rotational Barriers in Fluorinated Allylic Radicals
ΣυγγραφέαςNicolaïdes, Andrew N.
Borden, W. T.
SourceJournal of the American Chemical Society
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The energies required to rotate the CF2 and the CH2 group out of conjugation in 1,1-difluoroallyl radical have been calculated at the SD-CI/6–31G*//UHF/6–31G* level of theory. In agreement with experiment, the barrier to CF2 group rotation in this allylic radical is computed to be much larger than that in 1,1,3,3-tetrafluoroallyl radical. The factors that govern the size of rotational barrieirs in allylic radicals are analyzed, and the origin of the difference in barriers to CF2 group rotation in these two fluorinated allylic radicals is discussed. © 1992, American Chemical Society. All rights reserved.