Visible light-induced oxidation of alcohols by a luminescent osmium(VI) nitrido complex: Evidence for the generation of PhIO⁺ as a highly active oxidant in the presence of PhIO

Jing XIANG, Yi PAN, Lu-Lu LIU, Li-Xin WANG, Huan YANG, Shun-Cheung CHENG, Shek-Man YIU, Chi Fai LEUNG, Chi-Chiu KO, Kai-Chung LAU, Tai-Chu LAU

Research output: Contribution to journalArticlespeer-review

2 Citations (Scopus)

Abstract

Although alcohols are readily oxidized by a variety of oxidants, their oxidation by metal nitrido complexes is yet to be studied. We report herein visible-light-induced oxidation of primary and secondary alcohols to carbonyl compounds by a strongly luminescent osmium(VI) nitrido complex (OsN). The proposed mechanism involves initial rate-limiting hydrogen-atom transfer (HAT) from the α-carbon of the alcohol to OsN*. Attempts to develop catalytic oxidation of alcohols by OsN* using PhIO as the terminal oxidant resulted in the formation of novel osmium(IV) iminato complexes in which the nitrido ligand is bonded to a δ-carbon of the alcohol. Experimental and theoretical studies suggest that OsN* is reductively quenched by PhIO to generate PhIO⁺, which is a highly active oxidant that readily undergoes α- and δ-C–H activation of alcohols. Copyright © 2023 American Chemical Society.
Original languageEnglish
Pages (from-to)9129-9135
JournalJournal of the American Chemical Society
Volume145
Issue number16
Early online dateApr 2023
DOIs
Publication statusPublished - 2023

Citation

Xiang, J., Pan, Y., Liu, L.-L., Wang, L.-X., Yang, H., Cheng, S.-C., . . . Lau, T.-C. (2023). Visible light-induced oxidation of alcohols by a luminescent osmium(VI) nitrido complex: Evidence for the generation of PhIO⁺ as a highly active oxidant in the presence of PhIO. Journal of the American Chemical Society, 145(16), 9129-9135. doi: 10.1021/jacs.3c00760

Fingerprint

Dive into the research topics of 'Visible light-induced oxidation of alcohols by a luminescent osmium(VI) nitrido complex: Evidence for the generation of PhIO⁺ as a highly active oxidant in the presence of PhIO'. Together they form a unique fingerprint.