Laser Flash Photolysis of 2,2'-Dithiobls(pyridine N-oxide): Reactivity of N-Oxypyridyl-2-thio Radical

Abstract— Reaction kinetics of radicals produced by the nanosecond laser flash photolysis of 2,2'-dithiobis(pyridine N -oxide) and related compounds have been studied. The transient absorption band at 360 nm was attributed to the radical in which the unpaired electron mainly localizes on the S atom ( N -oxypyridyl-2-thio radical). The reactivities of the radical for conjugated dienes are lower than those of the pyridyl-2-thio radical, suggesting that a considerable unpaired electron density on the S atom delocalizes onto the N -oxypyridine moiety. The addition reaction rate of the radical to the conjugating diene was accelerated with hydrogen-bonding solvents and with addition of the cation, which may stabilize the N+-O^- canonical structure, increasing the unpaired electron density on the S atom. By the photolysis of N -hydroxypyridine-2-thione, the N-O bond was predominantly dissociated producing a pyr-idyl-2-thio radical. By the photolysis of its anion, photoejection took place followed by the N-O bond fission, yielding pyridine-2-thione.