Herein are described substrate oxidations with H2O2 catalyzed by [FeII(IndH)(CH3CN)3](ClO4)2 [IndH = 1,3-bis(2′-pyridylimino)isoindoline], involving a spectroscopically characterized (μ-oxo)(μ-1,2-peroxo)diiron(III) intermediate (2) that is capable of olefin epoxidation and alkane hydroxylation including cyclohexane. Species 2 also converts ketones to lactones with a decay rate dependent on [ketone], suggesting direct nucleophilic attack of the substrate carbonyl group by the peroxo species. In contrast, peroxo decay is unaffected by the addition of olefins or alkanes, but the label from H218O is incorporated into the the epoxide and alcohol products, implicating a high-valent iron–oxo oxidant that derives from O–O bond cleavage of the peroxo intermediate. These results demonstrate an ambiphilic diferric–peroxo intermediate that mimics the range of oxidative reactivities associated with O2-activating nonheme diiron enzymes.
|Original language||English (US)|
|Number of pages||5|
|State||Published - Jan 10 2022|
Bibliographical noteFunding Information:
This work is dedicated to the memory of Professor Elena Rybak-Akimova, an enthusiastic investigator of iron–oxygen chemistry. This work was supported by the Hungarian Research Fund (Grants K108489, TKP2020-IKA-07, and GINOP-2.3.2-15-2016-00049 to J.K.) and the U.S. National Institutes of Health (Grants R01 GM-38767 and R35 GM-131721 to L.Q.).
© 2021 American Chemical Society.
PubMed: MeSH publication types
- Journal Article