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, Larry Que

Research output: Contribution to journalArticle

1 Citation (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)8484-8488
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number25
DOIs
StatePublished - Jun 17 2019

Fingerprint

methane monooxygenase
Methane
Iron
Chemical activation
Lewis Acids
Oxygenases
Hydroxylation
Cyclohexane
Benzene
Oxidants
Enzymes
Acids

Keywords

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

Cite this

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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.",
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