AI Article Synopsis
- The study focuses on the oxidation of alcohols using a luminescent osmium(VI) nitrido complex, an area that hasn't been thoroughly explored before.
- It suggests that the oxidation process involves a hydrogen-atom transfer from the alcohol to the osmium complex as a key step.
- Additionally, attempts to use PhIO as a terminal oxidant led to the formation of new osmium(IV) iminato complexes, while indicating that PhIO can generate highly reactive oxidants capable of activating alcohols.
Article 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 (). The proposed mechanism involves initial rate-limiting hydrogen-atom transfer (HAT) from the α-carbon of the alcohol to . Attempts to develop catalytic oxidation of alcohols by 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 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.
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| http://dx.doi.org/10.1021/jacs.3c00760 | DOI Listing |
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