Treating iminoxyl species with oxygen acceptors such as PPh3 resulted in oxygen atom transfer and afforded the corresponding iminyl radicals. DFT and other calculations revealed that association between the oxygen atom acceptors and the iminoxyl species results in the formation of key intermediates during the reaction. Subsequent dissociation is accompanied with homolytic cleavage of the N-O bond and generates iminyl radicals with spin densities that are localized on exocyclic nitrogen atoms.