Reactions of nitrophenide and halonitrophenide ions with acrylonitrile and alkyl acrylates in the gas phase: The case of [M−2]− ion formation

► Nitrophenide ions react with α,β-unsaturated compounds via formation of β-adducts. ► Unstable β-adducts rearrange to derivatives of o-nitrosobenzylic anion ([M−2]−). ► The mechanism involves an O-atom transfer via a six-membered intermediate. ► The formation of [M−2]− ions is characteristic of nitrophenide ions.