TY - JOUR
T1 - Activation of a Non-Heme FeIII-OOH by a Second FeIII to Hydroxylate Strong C−H Bonds
T2 - Possible Implications for Soluble Methane Monooxygenase
AU - Kal, Subhasree
AU - Que, Lawrence
N1 - Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/6/17
Y1 - 2019/6/17
N2 - 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.
AB - 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.
KW - C−H activation
KW - benzene hydroxylation
KW - bioinspired iron oxidation
KW - iron(III) hydroperoxo
KW - non-heme iron
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U2 - 10.1002/anie.201903465
DO - 10.1002/anie.201903465
M3 - Article
C2 - 30997707
AN - SCOPUS:85065667923
SN - 1433-7851
VL - 58
SP - 8484
EP - 8488
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 25
ER -