Nonheme Diiron Oxygenase Mimic That Generates a Diferric–Peroxo Intermediate Capable of Catalytic Olefin Epoxidation and Alkane Hydroxylation Including Cyclohexane

Williamson N Oloo, Miklós Szávuly, József Kaizer, Lawrence Que

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

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 languageEnglish (US)
Pages (from-to)37-41
Number of pages5
JournalInorganic chemistry
Volume61
Issue number1
DOIs
StatePublished - Jan 10 2022

Bibliographical note

Funding 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.).

Publisher Copyright:
© 2021 American Chemical Society.

Fingerprint

Dive into the research topics of 'Nonheme Diiron Oxygenase Mimic That Generates a Diferric–Peroxo Intermediate Capable of Catalytic Olefin Epoxidation and Alkane Hydroxylation Including Cyclohexane'. Together they form a unique fingerprint.

Cite this