Reactions of strong bases with vinyl fluoride formation and characterization of 1-fluorovinyl anion and the fluoride-acetylene hydrogen-bonded complex

Vinyl fluoride reacts with strong bases to afford I-fluorovinyl anion (1a) and a fluoride-acetylene cluster (1b). The former ion can be prepared independently, and cleanly, by the fluorodesilylation of 1-(trimethylsilyl) fluoroethylene. Reactions of 1a are reported, and its proton affinity is assigned (387 ± 3 kcal mol^?1). Vinyl fluoride is 22 kcal mol^?1 more acidic than ethylene. This unusually large substituent effect is reproduced by ab initio calculations, and can be accounted for by geometric changes which minimize the electron-electron repulsion in 1a. Computations on 2-fluorovinyl anions (1c and 1d) have also been carried out, and both ions are only slightly less stable than 1a. The cis isomer (1c) has a larger barrier for fluoride elimination and is a reasonable target for preparation.