VIBRATIONAL SPECTRA OF THE PERFLUOROCYCLOPROPENYL CATION: A POTENTIAL FUNCTION FOR THIS SUBSTANCE AND RELATED CATIONS
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Date
1984
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Publisher
Ohio State University
Abstract
The perfluorocyclopropenyl cation, $[FIGURE]$, is the product of the reaction of perfluorocyclopropene with Lewis acids, such as $BF_{3}$. From infrared spectra of the solid compounds, $C_{3}F_{3}^{+}BF_{4}^{-}$ and $C_{3}F{_{3}}^{+}SbF{_{6}}^{-}$, and from Raman spectra of $C_{3}F_{3}^{+}BF_{4}^{-}$ in solution in sulfur dioxide we have observed all but one of the spectroscopically active fundamentals of the $C_{3}F_{3}^{+}$ cation which has $D_{3h}$ symmetry. An overlay normal coordinate calculation for the monofluorocation, the $difluoracation,^{2}$ and the perfluorocation has led to a complete assignment of the fundamentals of the $C_{3}F_{3}^{+}$ cation. With calculated values in parentheses this assignment is (in $cm^{-1}$): $(a_{1}') 2013, 751; (a_{2}') (800); (e') (1589, 998, 287; (a_{2}'')(250); (e'') 640$. A discussion will be included of the effect of fluorine substitution on the CC stretching force constants.
Description
$^{1}$ N.C. Craig, R.K.-Y. Lai, L.G. Matus, J.H. Miller, and S.L. Palfrey, J. Am. Chem. Soc. 102, 38 (1980). $^{2}$ N.C. Craig, R.K.-Y. Lai, K.W. Penfield, and I.W. Levin, J. Phys. Chem. 84, 899 (1980).
Author Institution: Department of Chemistry, Oberlin College
Author Institution: Department of Chemistry, Oberlin College