Benzene Oxidation by ‘Bare’ FeO⁺ in the Gas Phase

Bare FeO + reacts in the gas phase with benzene at collision rate ( k = 1.3 × 10 −9 cm 3 molecule −1 s −1 ), giving rise to the formation of Fe(C 6 H 4 ) + /H 2 O(5%), Fe(C 5 H 6 ) + /CO(37%), Fe(C 5 H 5 ) + /CO/H. (2%), and Fe + /C 6 H 5 OH (56%). Neither the reaction rate nor the product distribution are subject to a significant kinetic isotope effect, thus, ruling out several mechanistic variants described in the literature to the operative for ‘analogous’ arene oxidation processes in solution. A mechanism is suggested which is in keeping with the experimental findings, and which also accounts for some remarkable results obtained, when two [Fe, C 6 ,H 6 H 6 O] + isomers are generated and subjected to a neutralization‐re‐ionization experiment in the gas phase.