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.
None:
Herein, we report the reactions of the Fe(II) alkyl and aryl complexes (Ph2B(tBuIm)2Fe(tBuImH)R, R = CH2tBu and Mes) with N2O and N-oxides (Me3NO and C5H5NO), affording oxygen-inserted Fe(II) alkoxide and aryloxide complexes (Ph2B(tBuIm)2Fe(tBuImH)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.
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