Ion chemistry of sulfuryl fluoride: An experimental and theoretical study on gas-phase reactions involving neutral and ionized SO2F2

The gas phase ion chemistry of sulfuryl fluoride is studied by ion trap mass spectrometry and ab ini- tio calculations. Reactions of ions of atmospheric relevance with neutral SO2F2 mainly result in SO2F2 depletion by dissociative electron transfer. In few cases, a different reaction mechanism involving F-abstraction is invoked, since dissociative ion products are observed despite the electron transfer channel being endothermic. Ab initio calculations revealed a nearly perfect distonic structure for the molecular SO2F2+ ion, whose capability of activating strong HX bonds (X = C, N, O) is ascribable to the high spin density located on the oxygen atoms, in line with literature reports. Among the ions produced by electron ionization of SO2F2, the FSOx+(x= 0-2) ions are capable of activating the HNH2 bond of ammonia. Theoretical investigation revealed that NH3 activation by SF+ requires a triplet to singlet conversion along the reaction pathway. This conversion is expected to be fast, the conceivable reaction rate determining step being the subsequent intramolecular hydrogen migration.