Ab initio study of the mechanisms of reactions of NF3 with aliphatic and benzylic substrates

At temperatures around 400 °C, nitrogen trifluoride (NF3) readily reacts with alkanes and benzene as well as ethers to produce stable N,N-difluoroamines. Difluoroamination of benzylic substrates results in initial N,N-difluoroamines that undergo eliminations or rearrangements. Toluene and ethylbenzene produce benzonitrile. Cumene produces α-methylstyrene. Diphenylmethane produces benzanilide. Little or no direct fluorination or radical dimerization is observed. This study uses ab initio calculations to help understand the reasons for such diverse reaction pathways.