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Reactivity of gaseous XeF ions with acetonitrile. A joint mass spectrometric and theoretical study of isomeric CHNF and CHNXe cations

Journal of Physical Chemistry A, ISSN: 1089-5639, Vol: 104, Issue: 32, Page: 7574-7579
2000
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The gas-phase reactivity of XeF toward a model nucleophile, acetonitrile, was investigated by the joint application of experimental and theoretical methods. The results of mass spectrometric experiments and theoretical calculations up to the B3LYP/CCSD(T) level of theory show that XeF promotes both F and Xe+ transfer to CH3CN. Both processes involve the preliminary association of the reactants to yield two ion-molecule complexes, [CH3CNFXe] and [CH3CNXeF], of comparable stability. The former can undergo Xe loss, yielding CHsCNF, which can consequently rearrange into the CH2FCNH isomer, more stable by 263.6 kJ mol at the CCSD(T) level of theory. The isomerization can proceed by two independent pathways and requires the overcoming of significant barriers computed to be 147.3 and 187.0 kJ mol at the same level of theory. The CHCNF cation reacts with typical nucleophiles (CHCOCH, CH, 1, 1-CHF, CHOH, CH) according to three processes, i.e., charge exchange, F transfer, and ion-molecule complex formation, whose 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 with the fluorination of unsaturated molecules by XeF2 in solution. © 2000 American Chemical Society.

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