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J Am Soc Mass Spectrom ; 3(2): 91-8, 1992 Feb.
Article in English | MEDLINE | ID: mdl-24242876

ABSTRACT

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.

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