Activation of a Non-Heme FeIII-OOH by a Second FeIII to Hydroxylate Strong C−H Bonds: Possible Implications for Soluble Methane Monooxygenase

Subhasree Kal; Lawrence Que

doi:10.1002/anie.201903465

Activation of a Non-Heme Fe^III-OOH by a Second Fe^III to Hydroxylate Strong C−H Bonds: Possible Implications for Soluble Methane Monooxygenase

Subhasree Kal, Lawrence Que

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

Non-heme iron oxygenases contain either monoiron or diiron active sites, and the role of the second iron in the latter enzymes is a topic of particular interest, especially for soluble methane monooxygenase (sMMO). Herein we report the activation of a non-heme Fe^III-OOH intermediate in a synthetic monoiron system using Fe^III(OTf)₃ to form a high-valent oxidant capable of effecting cyclohexane and benzene hydroxylation within seconds at −40 °C. Our results show that the second iron acts as a Lewis acid to activate the iron–hydroperoxo intermediate, leading to the formation of a powerful Fe^V=O oxidant—a possible role for the second iron in sMMO.

Original language	English (US)
Pages (from-to)	8484-8488
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	25
DOIs	https://doi.org/10.1002/anie.201903465
State	Published - Jun 17 2019

Bibliographical note

Funding Information:
We thank the US National Institutes of Health for support of this work (GM38767 to L.Q.)

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

C−H activation
benzene hydroxylation
bioinspired iron oxidation
iron(III) hydroperoxo
non-heme iron

Publisher link

10.1002/anie.201903465

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title = "Activation of a Non-Heme FeIII-OOH by a Second FeIII to Hydroxylate Strong C−H Bonds: Possible Implications for Soluble Methane Monooxygenase",

abstract = "Non-heme iron oxygenases contain either monoiron or diiron active sites, and the role of the second iron in the latter enzymes is a topic of particular interest, especially for soluble methane monooxygenase (sMMO). Herein we report the activation of a non-heme FeIII-OOH intermediate in a synthetic monoiron system using FeIII(OTf)3 to form a high-valent oxidant capable of effecting cyclohexane and benzene hydroxylation within seconds at −40 °C. Our results show that the second iron acts as a Lewis acid to activate the iron–hydroperoxo intermediate, leading to the formation of a powerful FeV=O oxidant—a possible role for the second iron in sMMO.",

keywords = "C−H activation, benzene hydroxylation, bioinspired iron oxidation, iron(III) hydroperoxo, non-heme iron",

author = "Subhasree Kal and Lawrence Que",

note = "Funding Information: We thank the US National Institutes of Health for support of this work (GM38767 to L.Q.) Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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