| Abstract
| - Atomic oxygen O(3P) is a potent oxidant that has been well-studied in the gas phase. However,exploration of its reactivity in the condensed organic phase has been hampered by the lack of an appropriatesource. Dibenzothiophene-S-oxide (DBTO) and related derivatives have been promoted as photochemicalO(3P) sources but suffer from low quantum yields. Photolysis of dibenzoselenophene-Se-oxide (DBSeO)results in the formation of dibenzoselenophene and oxidized solvent in significantly higher quantum yields,ca. 0.1. The oxidation product ratios from toluene obtained from the photolysis of dibenzothiophene-S-oxide and the corresponding selenoxide are the same, strongly suggesting a common oxidizing intermediate,which is taken to be O(3P). An additional product, proposed to be the corresponding selenenic ester, isalso observed under deoxygenated conditions. The photochemistry of diphenyl selenoxide includes a minorportion of oxidant-forming deoxygenation, in contrast to previous conclusions (Yamazaki, Y.; Tsuchiya, T.;Hasegawa, T. Bull. Chem. Soc. Jpn. 2003, 201−202).
|
