Oxo Ligand Insertion into Fe–C Bonds as a Platform for Oxygen Atom Insertion Catalysis
Abstract
Herein, we report the reactions of the Fe(II) alkyl and aryl complexes (Ph 2 B( t BuIm) 2 Fe( t BuImH)R, R = CH 2 t Bu and Mes) with N 2 O and N -oxides (Me 3 NO and C 5 H 5 NO), affording oxygen-inserted Fe(II) alkoxide and aryloxide complexes (Ph 2 B( t BuIm) 2 Fe( t BuImH)OR). Experimentally calibrated density functional theory (DFT) calculations implicate a mechanism in which the C–O bond is formed by oxygen atom insertion from an iron(IV) oxo intermediate. This stoichiometric oxygen insertion reaction forms the basis of a catalytic cycle to convert Grignard reagents to the corresponding arylphenols. This type of oxygen insertion enriches the family of iron-catalyzed oxidation mechanisms and complements the well-known oxygen rebound mechanism in oxygenases.
Fields of Study & Subjects
Metal-Catalyzed Oxygenation Mechanisms
Oxidative Organic Chemistry Reactions
Catalytic C–H Functionalization Methods
Publication details
- Journal / source
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Volume
- 148
- Issue
- 1
- Pages
- 1607–1613
- Publication date
- 1 January 2026
- Language
- EN