Gas-phase chemistry of vanadium oxide cluster cations.: 1.: Reactions with C2F6 and CH3CF3

The reactivities of mass-selected vanadium oxide cluster cations with fluorocarbons were studied by using a triple-quadrupole mass spectrometer coupled with a laser vaporization source. The vanadium oxide species V2O4-7+, V3O6-9+, V4O8-11+, V5O11-13+, V6O13-16+, and V7O16-18+ displayed unique reactivities with CH3CF3 and C2F6. Among the reaction pathways observed were association, HF elimination, cracking of the carbon-carbon bond, and fluorine abstraction with oxygen transfer from the cluster to the neutral reactant molecule. Interestingly, the reactions differed for clusters within the same series and also from series to series. For example, the reaction of V2O4+ with CH3CF3 produces the HF-elimination product V2O4. HF+. However, the cluster V2O5+ reacts with CH3CF3 to produce the cracking product V2O5. CF3+ but also reacts to abstract 2 fluorine atoms with transfer of an oxygen atom to the neutral reactant molecule. The reaction of these 2 clusters with C2F6 generates only association products.