Two Faces of a Biomimetic Non‐Heme HOFeVO Oxidant: Olefin Epoxidation versus cis‐Dihydroxylation

Reactivity along two channels is shown by the HOFeVO species responsible for Fe(tpa)-catalyzed olefin oxidation (tpa=tris(2-pyridylmethyl)amine). Attack of the oxo ligand on an olefinic carbon atom yields epoxide and attack of the hydroxo ligand affords cis-diol (see scheme). Hybrid density functional theory now demonstrates that the two processes have comparable activation energies.