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

doi:10.1021/jacs.3c00760

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^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

6 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. © 2023 American Chemical Society

Original language	English
Pages (from-to)	9129–9135
Journal	Journal of the American Chemical Society
Volume	145
Issue number	16
Online published	13 Apr 2023
DOIs	https://doi.org/10.1021/jacs.3c00760
Publication status	Published - 26 Apr 2023

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Xiang, J., Pan, Y., Liu, L.-L., Wang, L.-X., Yang, H., Cheng, S.-C., Yiu, S.-M., Leung, C.-F., Ko, C.-C., Lau, K.-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. https://doi.org/10.1021/jacs.3c00760

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title = "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",

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. {\textcopyright} 2023 American Chemical Society",

author = "Jing Xiang and Yi Pan and Lu-Lu Liu and Li-Xin Wang and Huan Yang and Shun-Cheung Cheng and Shek-Man Yiu and Chi-Fai Leung and Chi-Chiu Ko and Kai-Chung Lau and Tai-Chu Lau",

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doi = "10.1021/jacs.3c00760",

language = "English",

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Xiang, J, Pan, Y, Liu, L-L, Wang, L-X, Yang, H, Cheng, S-C, Yiu, S-M, Leung, C-F, Ko, C-C , Lau, K-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, vol. 145, no. 16, pp. 9129–9135. https://doi.org/10.1021/jacs.3c00760

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. / Xiang, Jing; Pan, Yi; Liu, Lu-Lu et al.
In: Journal of the American Chemical Society, Vol. 145, No. 16, 26.04.2023, p. 9129–9135.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Visible Light-Induced Oxidation of Alcohols by a Luminescent Osmium(VI) Nitrido Complex

T2 - Evidence for the Generation of PhIO+ as a Highly Active Oxidant in the Presence of PhIO

AU - Xiang, Jing

AU - Pan, Yi

AU - Liu, Lu-Lu

AU - Wang, Li-Xin

AU - Yang, Huan

AU - Cheng, Shun-Cheung

AU - Yiu, Shek-Man

AU - Leung, Chi-Fai

AU - Ko, Chi-Chiu

AU - Lau, Kai-Chung

AU - Lau, Tai-Chu

PY - 2023/4/26

Y1 - 2023/4/26

N2 - 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. © 2023 American Chemical Society

AB - 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. © 2023 American Chemical Society

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DO - 10.1021/jacs.3c00760

M3 - RGC 21 - Publication in refereed journal

C2 - 37053567

SN - 0002-7863

VL - 145

SP - 9129

EP - 9135

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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