Investigating Ligand Sphere Perturbations on MnIII-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 MnIII-hydroperoxo complexes, MnIII-alkylperoxo complexes are employed to understand factors that affect the mechanism of the O-O cleavage. Herein, we report a series of novel complexes, including two room-temperature-stable MnIII-alkylperoxo species, supported by a new amide-containing pentadentate ligand (6Medpaq5NO2). We use a combination of spectroscopic methods and density functional theory computations to probe the effects of the electronic changes in the ligand sphere trans to the hydroxo and alkylperoxo units to thermal stability and reactivity. The structural characterizations for both MnII(OTf)(6Medpaq5NO2) and [MnIII(OH)(6Medpaq5NO2)](OTf) were obtained via single-crystal X-ray crystallography. A perturbation to the ligand sphere allowed for a marked increase in reactivity towards an organic substrate, a modest change in the distribution of the O-O cleavage products from homolytic and heterolytic pathways, and little change in thermal stability.

Electronic structure contributions to O-O bond cleavage reactions for MnIII-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 via heterolytic O-O bond cleavage to generate a Mn(V)-oxo species that initiates substrate oxidation. Due to the paucity of well-defined MnIII-hydroperoxo complexes, MnIII-alkylperoxo complexes are often employed to understand the factors that affect the O-O cleavage reaction. Herein, we examine the decay pathways of the MnIII-alkylperoxo complexes [MnIII(OOtBu)(6Medpaq)]+ and [MnIII(OOtBu)(N4S)]+, which have distinct coordination environments (N5- and N4S-, respectively). Through the use of density functional theory (DFT) calculations and comparisons with published experimental data, we are able to rationalize the differences in the decay pathways of these complexes. For the [MnIII(OOtBu)(N4S)]+ system, O-O homolysis proceeds via a two-state mechanism that involves a crossing from the quintet reactant to a triplet state. A high energy singlet state discourages O-O heterolysis for this complex. In contrast, while quintet-triplet crossing is unfavorable for [MnIII(OOtBu)(6Medpaq)]+, a relatively low-energy single state accounts for the observation of both O-O homolysis and heterolysis products for this complex. The origins of these differences in decay pathways are linked to variations in the electronic structures of the MnIII-alkylperoxo complexes.