Bonesi Sergio M, Mella Mariella, Merli Daniele, Protti Stefano
Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, Argentina.
Centro de Investigaciones en Hidratos de Carbono (CIHIDECAR), CONICET-Universidad de Buenos Aires, Buenos Aires, Argentina.
Photochem Photobiol. 2021 Nov;97(6):1278-1288. doi: 10.1111/php.13403. Epub 2021 Mar 8.
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 Ar POO was found to play a key role in phosphine oxide formation.
