Comparison of the Photochemistry of Diarylchloronium, Diarylbromonium, and Diaryliodonium Salts

Article abstract of DOI:10.1021/jo00005a033

The direct and triplet-sensitized photochemistry of diphenylchloronium, diphenylbromonium, bis(4-methylphenyl)chloronium, and bis(4-methylphenyl)bromonium salts was studied.Direct photolysis of the diarylhalonium salts gave haloarene, 2-, 3-, and 4-halobiaryls, and acetanilide, predominantly from a heterolytic cleavage mechanism via the aryl cation-haloarene pair, via in-cage recombination and cage-escape reactions.However, triplet-sensitized photolysis gave haloarene, 2-, 3-, and 4-halobiaryl, and reduced arene mainly from homolytic cleavage to the arene radical-haloarene radical cation pair, which also gave in-cage recombination and cage-escape products.There is evidence for singlet-triplet interconversion of the excited states by spin-orbit coupling and interconversion of the singlet-triplet radical pairs by spin-spin coupling.In addition, electron transfer between the singlet arene cation-haloarene and arene radical-haloarene radical cation pairs is also possible.The effect of halogen and arene substituent on these interconversions is discussed.