Investigating Ligand Sphere Perturbations on Mn-Alkylperoxo Complexes.

Manganese catalysts that activate hydrogen peroxide carry out several different hydrocarbon oxidation reactions with high stereoselectivity. The commonly proposed mechanism for these reactions involves a key manganese(III)-hydroperoxo intermediate, which decays via O-O bond heterolysis to generate a Mn(V)-oxo species that institutes substrate oxidation. Due to the scarcity of characterized Mn-hydroperoxo complexes, Mn-alkylperoxo complexes are employed to understand factors that affect the mechanism of the O-O cleavage.

Electronic structure contributions to O-O bond cleavage reactions for Mn-alkylperoxo complexes.

Synthetic manganese catalysts that activate hydrogen peroxide perform a variety of hydrocarbon oxidation reactions. The most commonly proposed mechanism for these catalysts involves the generation of a manganese(III)-hydroperoxo intermediate that decays heterolytic O-O bond cleavage to generate a Mn(V)-oxo species that initiates substrate oxidation. Due to the paucity of well-defined Mn-hydroperoxo complexes, Mn-alkylperoxo complexes are often employed to understand the factors that affect the O-O cleavage reaction.