Oxo Ligand Insertion into Fe-C Bonds as a Platform for Oxygen Atom Insertion Catalysis
Bin Feng1, Yicheng Ji2, Nobuyuki Yamamoto1
1Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
Journal of the American Chemical Society
|January 1, 2026
Summary
Iron complexes react with oxidants to form oxygen-inserted products. Density functional theory (DFT) calculations reveal a mechanism involving an iron(IV) oxo intermediate, enabling catalytic conversion of Grignard reagents to arylphenols.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Computational Chemistry
Background:
- Iron complexes are versatile catalysts in oxidation reactions.
- Understanding reaction mechanisms is crucial for developing new catalytic processes.
Purpose of the Study:
- To investigate the reactions of iron(II) alkyl and aryl complexes with N2O and N-oxides.
- To elucidate the mechanism of oxygen insertion into iron complexes.
- To establish a catalytic cycle for converting Grignard reagents to arylphenols.
Main Methods:
- Synthesis and characterization of iron(II) complexes.
- Reactions with N2O and N-oxides.
- Experimentally calibrated density functional theory (DFT) calculations.
Main Results:
- Formation of oxygen-inserted Fe(II) alkoxide and aryloxide complexes.
- DFT calculations suggest a mechanism involving an iron(IV) oxo intermediate.
- Demonstration of a catalytic cycle for arylphenol synthesis from Grignard reagents.
Conclusions:
- The study reveals a novel oxygen insertion mechanism in iron catalysis.
- This work expands the repertoire of iron-catalyzed oxidation reactions.
- The findings complement existing knowledge of oxygenase mechanisms.
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