Synthesis, basicity, and dynamics of a perfluorocyclohexenyl anion.
Electron transfer to perfluoro-1,3-dimethylcyclohexane in moist THF has yielded two quite different products. Tetrabutylammonium iodide irradiated with ultraviolet light gives a tetrabutylammonium enolate, but potassium fluorenone ketyl affords a cyclohexenyl anion. This allylic anion was isolated as its conjugate acid, a rather strong carbon acid. Ring inversion in the anion, measured by (19)F NMR line shape analysis, is characterized by these activation parameter values: DeltaH(++) = 8.84 +/-0.14 kcal/mol and DeltaS(++) = 0.81 +/- 0.6 cal mol(-1) K(-1).
Chen
Xudong
X
Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA. xudong.chen@dartmouth.edu
Lemal
David M
DM
D000838:Anions / Q000138:chemical synthesis* / Q000737:chemistry*; D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction
D000838:Anions; D003510:Cyclohexanes