Photochemistry of triarylsulfonium salts

• Published in: Journal of the American Chemical Society Vol. 112; no. 16; pp. 6004 - 6015
• Main Authors: Dektar, John L, Hacker, Nigel P
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.08.1990
• Subjects: CHEMICAL REACTIONS; CHEMISTRY; DATA; DATA ANALYSIS; DECOMPOSITION; Exact sciences and technology; EXPERIMENTAL DATA; General and physical chemistry; INFORMATION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MEASURING INSTRUMENTS; MEASURING METHODS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PHOTOCHEMICAL REACTIONS 400500 > Photochemistry; PHOTOCHEMISTRY; PHOTOLYSIS; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Solvent effect; Substituent effect; Organic cation; Singlet state; Quantum yield; Organic sulfide; Triplet state; Ultraviolet radiation; Salt effect; Photolysis; Radical mechanism; Benzenic compound; Ion radical pair; Excited state
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja00172a015

The photolysis of triphenylsulfonium, tris(4-methylphenyl)sulfonium, tris(4-chlorophenyl)sulfonium, several monosubstituted (4-F, 4-Cl, 4-Me, 4-MeO, 4-PhS, and 4-PhCO), and disubstituted (4,4{prime}-Me{sub 2} and 4,4{prime}-(MeO){sub 2}) triphenylsulfonium salts was examined in solution. It was found that direct irradiation of triphenylsulfonium salts produced new rearrangement products, phenylthiobiphenyls, along with diphenyl sulfide, which had been previously reported. Similarly, the triarylsulfonium salts, with the exception of the (4-(phenylthio)phenyl)diphenylsulfonium salts produced new rearrangement products, phenylthiobiphenyls, along with diphenyl sulfide, which had been previously reported. Similarly, the triarylsulfonium salts, with the exception of the (4-(phenylthio)phenyl)diphenylsulfonium salts, gave the new rearrangement products. The mechanism for direct photolysis is proposed to occur from the singlet excited states to give a predominant heterolytic cleavage along with some homolytic cleavage.