Highly Selective and Catalytic Oxygenations of C−H and C=C Bonds by a Mononuclear Nonheme High‐Spin Iron(III)‐Alkylperoxo Species

The reactivity of a mononuclear high‐spin iron(III)‐alkylperoxo intermediate [FeIII(t‐BuLUrea)(OOCm)(OH2)]2+(2), generated from [FeII(t‐BuLUrea)(H2O)(OTf)](OTf) (1) [t‐BuLUrea=1,1′‐(((pyridin‐2‐ylmethyl)azanediyl)bis(ethane‐2,1‐diyl))bis(3‐(tert‐butyl)urea), OTf=trifluoromethanesulfonate] with cumyl...

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Published in:Angewandte Chemie International Edition Vol. 58; no. 36; pp. 12534 - 12539
Main Authors: Ghosh, Ivy, Banerjee, Sridhar, Paul, Satadal, Corona, Teresa, Paine, Tapan Kanti
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 02.09.2019
Edition:International ed. in English
Subjects:
Aliphatic compounds
Bonding strength
Catalysis
Ethane
Hydrocarbons
Iron
ligand design
oxidation
Oxidizing agents
Oxygenation
peroxides
reaction mechanisms
Stereoselectivity
Substrates
Urea
ligand design
oxidation
reaction mechanisms
iron
peroxides
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:The reactivity of a mononuclear high‐spin iron(III)‐alkylperoxo intermediate [FeIII(t‐BuLUrea)(OOCm)(OH2)]2+(2), generated from [FeII(t‐BuLUrea)(H2O)(OTf)](OTf) (1) [t‐BuLUrea=1,1′‐(((pyridin‐2‐ylmethyl)azanediyl)bis(ethane‐2,1‐diyl))bis(3‐(tert‐butyl)urea), OTf=trifluoromethanesulfonate] with cumyl hydroperoxide (CmOOH), toward the C−H and C=C bonds of hydrocarbons is reported. 2 oxygenates the strong C−H bonds of aliphatic substrates with high chemo‐ and stereoselectivity in the presence of 2,6‐lutidine. While 2 itself is a sluggish oxidant, 2,6‐lutidine assists the heterolytic O−O bond cleavage of the metal‐bound alkylperoxo, giving rise to a reactive metal‐based oxidant. The roles of the urea groups on the supporting ligand, and of the base, in directing the selective and catalytic oxygenation of hydrocarbon substrates by 2 are discussed. Role playing: A transient (t1/2=3 min at 283 K) high‐spin iron(III)‐alkylperoxo intermediate, supported by a ligand bearing urea groups, exhibits selective and catalytic oxygen‐atom transfer and hydrogen atom transfer reactions in the presence of a general‐base promoter. The urea groups on the ligand backbone play a pivotal role in driving the selectivity and catalytic activity.
Bibliography:Dedicated to Professor Phalguni Chaudhuri on the occasion of his 75th birthday
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201906978