Photochemistry of Tris(2,4-dibromophenyl)amine and its application to co-oxidation on sulfides and phosphines.

BONESI SERGIO M; MELLA, MARIELLA; MERLI, DANIELE; PROTTI, STEFANO

PHOTOCHEMISTRY AND PHOTOBIOLOGY

WILEY-BLACKWELL PUBLISHING, INC

Lugar: Londres; Año: 2021 vol. 97 p. 1278 - 1288

0031-8655

The photochemistry of tris(2,4-dibromophenyl)amine was investigated via time-resolved nanosecond spectroscopy. The tris(2,4-dibromophenyl)amine radical cation (?Magic Green?) was immediately detected after the laser pulse; this intermediate then cyclizes to N-aryl-4a,4b-dihydrocarbazole radical cation. The latter transient reacted with molecular oxygen to provide the corresponding hydroperoxyl radical which smoothly co-oxidize sulfides into sulfoxides. On the other hand, the photogenerated ?Magic Green? was exploited to promote the co-oxidation of nucleophilic triarylphosphines to triarylphosphine oxides through an electron transfer process preventing the amine cyclization. In this case, the intermediate Ar3POO?+ was found to play a key role in phosphine oxide formation.