MECHANISTIC ASPECTS OF F-REACTIONS - A MODEL STUDY IN THE GAS-PHASE( TRANSFER)

The mechanism of the spin-forbidden formal FT transfer from (NF2+)-N-1 to CO with formation of (FCO+)-F-1 and (NF)-N-3 was investigated by m ass spectrometry and high-level theoretical calculations. The (NF2CO)( +) intermediates involved in this process, which were observed by chem ical ionization experiments, were structurally characterized by collis ionally activated dissociation spectrometry: and their unimolecular de composition processes were probed by mass-analyzed ion kinetic energy spectrometry, The results of these experiments are discussed in terms of the potential energy profile obtained by investigating the potentia l energy surfaces of singlet and triplet (NF2CO)(+), as well as the hy perline corresponding to their intersection, Our findings provide prob ably the first detailed description of the mechanism of a formally sim ple F+ transfer reaction, They also have mechanistic implications for related oxidative fluorination reactions in solution, which have been extensively investigated in the last thirty years.