A Laser Flash-Photolysis Study of the Bimolecular Reactions of Singlet Fluorinated Arylnitrenes

The kinetics and mechanisms of the reactions of singlet perfluoro-4-biphenylnitrene and N-propyl-4-nitreno-2,3,5,6-tetrafluorobenzylamide with various amines, pyridine, and dimethylsulfoxide were studied by laser flash photolysis. The reactions of singlet arylnitrenes with amines are two-step processes. The primary step of the process is adduct formation; the rate constant of this reaction is high and lies within the range 4 × 10⁷–2 × 10⁸l mol^–1s^–1for the tested secondary amines. The second step (1,2-hydrogen shift) was accelerated in the presence of water.