1,2-FLUORINE SHIFT REARRANGEMENT OF 1,1,1-TRIFLUOROMETHYLCARBENE TO TRIFLUOROETHYLENE
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AbstractThe 1,2-fluorine shift rearrangement of CF3CH to CF2=CHF has been studied by ab initio molecular orbital calculations. The effects of basis functions, electron correlation and zero-point energy (ZPE) are considered. The reaction on the singlet potential energy surface has been computed to be exothermic with a vibrationally corrected MP4SDTQ/6-31++G** reaction energy of 60.1 kcal mol(-1) and a shift barrier of 23.5 kcal mol(-1) which compares well with the experimental estimate of 29 +/- 4 kcal mol(-1). On the triplet surface, the reaction is, however, endothermic, and the corresponding energies are 6.05 and 16.0 kcal mol(-1) at the PMP4SDTQ/6-31++G** + ZPE level of theory. This result for the barrier to the 1,2-fluorine shift in CF3CH differs from the reported prediction that the 1,2-hydrogen shift barriers in triplet CH3CH and CH2=C: are over 50 kcal mol(-1) and about 10 times larger than those for the singlet species.
All Author(s) ListSO SP
Journal nameJOURNAL OF PHYSICAL CHEMISTRY
Year1993
Month11
Day18
Volume Number97
Issue Number46
PublisherAMER CHEMICAL SOC
Pages11908 - 11911
ISSN0022-3654
LanguagesEnglish-United Kingdom
Web of Science Subject CategoriesChemistry; Chemistry, Physical

Last updated on 2020-05-04 at 00:34