Distinct Reactivity Differences of Metal Oxo and Its Corresponding Hydroxo Moieties in Oxidations: Implications from a Manganese(IV) Complex Having Dihydroxide Ligand

The Mn+OH moiety in a manganese(IV) complex has more powerful electron‐transfer capability than its corresponding Mn+O moiety. An Mn+O moiety can hydrogen from a substrate, then rebind the OH group from its reduced M(n−1)+OH form to the substrate radical. In contrast, the active center with an Mn+OH cannot perform similar rebound from its reduced M(n−1)+OH2 group (see scheme; HAT=hydrogen ion).