Abstract

A highly luminescent Os(VI) nitrido complex [OsVI(N)(L)(CN)3]– (OsN, HL = 2-(2-hydroxy-5-nitrophenyl)benzoxazole) is readily excited by visible light and the excited state (OsN*) is highly reactive due to its [Os=N•] nitridyl character.1,2 Here, the photoreaction mechanism of a OsN with catechol (H2Cat) and hydroquinone (H2Q) was explored. DFT calculations show that the reaction of OsN* with H2Cat/H2Q produces initially semiquinone radical (HCat•/HQ•) and OsVNH intermediates; this is followed by substitution of C-OH bond by OsVNH and intramolecular attack of the resulting OH− at a CN− ligand, leading to the formation of CO.

Reference:

1. Xiang, J.; Jin, X. X.; Su, Q. Q.; Cheng, S. C.; Ko, C. C.; Man, W. L.; Xue, M. Y.; Wu, L. L.; Che, C. M.; Lau, T. C. Commun. Chem. 2019, 2, 40. 
2. Luo, L. J.; Su, Q. Q.; Cheng, S. C.; Xiang, J.; Man, W. L.; Shu, W. M.; Zeng, M.-H.; Yiu, S. M.; Ko, C. C.; Lau, T. C. Inorg. Chem. 2020, 59, 4406-4413.