M. Attina et al., Reactivity of gaseous XeF+ ions with acetonitrile. A joint mass spectrometric and theoretical study of isomeric C2H3NF+ and C2H3NXe+ cations, J PHYS CH A, 104(32), 2000, pp. 7574-7579
The gas-phase reactivity of XeF+ toward a model nucleophile, acetonitrile,
was investigated by the joint application of experimental and theoretical m
ethods. The results of mass spectrometric experiments and theoretical calcu
lations up to the B3LYP/CCSD(T) level of theory show that XeF+ promotes bot
h F+ and Xe+ transfer to CH3CN. Both processes involve the preliminary asso
ciation of the reactants to yield two ion-molecule complexes, [CH3CNFXe](+)
and [CH3CNXeF](+), of comparable stability. The former can undergo Xe loss
, yielding CH3CNF+, which can consequently rearrange into the CH2FCNH+ isom
er, more stable by 263.6 kJ mol(-1) at the CCSD(T) level of theory. The iso
merization can proceed by two independent pathways and requires the overcom
ing of significant barriers computed to be 147.3 and 187.0 kJ mol(-1) at th
e same level of theory. The CH3CNF+ cation reacts with typical nucleophiles
(CH3COCH3, C2H4, 1,1-C2H2F2, CH3-OH, C6H6) according to three processes, i
.e., charge exchange, F+ transfer, and ion-molecule complex formation, whos
e relative efficiency and thermochemistry were investigated. The formation
of CH3CNXe+ occurs via the loss of F from the primary ion-neutral complex [
CH3CNXeF](+). The gas-phase reactivity of XeF+ is discussed in comparison w
ith the fluorination of unsaturated molecules by XeF2 in solution.