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Low energy electron induced reactions in the four fluorinated acetic acid esters CF 3 COOCH 3 , CF 3 COOC 2 H 5 , CF 3 COOCH 2 CF 3  and CH 3 COOCH 2 CF 3  are studied by means of a crossed electron-molecular beam experiment and mass spectrometric detection of the anions. All target molecules exhibit a prominent resonance located near 1 eV which is subjected to a variety of unimolecular reactions. The observation of the carboxylate anion CF 3 COO – /CH 3 COO –  indicates rupture of the O−R ester bond, which in turn demonstrates that the prominent cleavage of the O−H bond recently observed in trifluoroacetic acid and acetic acid is not blocked when O−H is replaced by O−R (R=−CH 3 , −C 2 H 5 , −CH 2 CF 3 ). In CF 3 COOCH 3  and CF 3 COOC 2 H 5  an ion of the form CF 2 COO –  is generated which is identified to arise from a complex reaction involving multiple bond cleavages and substantial rearrangement  in the transitory negative ion ultimately generating CH 3 F and C 2 H 5 F, respectively, as neutral counterpart. A fragment ion of the type (M-H) –  (M: target molecule), i.e. loss of a neutral hydrogen atom, is only observed in CH 3 COOCH 2 CF 3  which directly demonstrates that dehydrogenation selectively occurs at the CH 3  site.

Reactions in Fluorinated Acetic Acid Esters Triggered by Slow Electrons: Bond Cleavages, Hydrogen Transfer Reactions and Loss of Halocarbons