Reaction landscape of a mononuclear MnIII-hydroxo complex with hydrogen peroxide.

Peroxomanganese species have been proposed as key intermediates in the catalytic cycles of both manganese enzymes and synthetic catalysts. However, many of these intermediates have yet to be observed. Here, we report the formation of a series of intermediates, each generated from the reaction of the mononuclear MnIII-hydroxo complex [MnIII(OH)(dpaq2Me)]+ with hydrogen peroxide under slightly different conditions. By changing the acidity of the reaction mixture and/or the quantity of hydrogen peroxide added, we are able to control which intermediate forms. Using a combination of electronic absorption, 1H NMR, EPR, and X-ray absorption spectroscopies, as well as density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations, we formulate these intermediates as the bis(µ-oxo)dimanganese(III,IV) complex [MnIIIMnIV(µ-O)2(dpaq2Me)2]+, the MnIII-hydroperoxo complex [MnIII(OOH)(dpaq2Me)]+, and the MnIII-peroxo complex [MnIII(O2)(dpaq2Me)]. The formation of the MnIII-hydroperoxo species from the reaction of a MnIII-hydroxo complex with hydrogen peroxide mimics an elementary reaction proposed for many synthetic manganese catalysts that activate hydrogen peroxide.

Characterization and chemical reactivity of room-temperature-stable MnIII-alkylperoxo complexes.

While alkylperoxomanganese(iii) (MnIII-OOR) intermediates are proposed in the catalytic cycles of several manganese-dependent enzymes, their characterization has proven to be a challenge due to their inherent thermal instability. Fundamental understanding of the structural and electronic properties of these important intermediates is limited to a series of complexes with thiolate-containing N4S- ligands. These well-characterized complexes are metastable yet unreactive in the direct oxidation of organic substrates. Because the stability and reactivity of MnIII-OOR complexes are likely to be highly dependent on their local coordination environment, we have generated two new MnIII-OOR complexes using a new amide-containing N5 - ligand. Using the 2-(bis((6-methylpyridin-2-yl)methyl)amino)-N-(quinolin-8-yl)acetamide (H6Medpaq) ligand, we generated the [MnIII(OO t Bu)(6Medpaq)]OTf and [MnIII(OOCm)(6Medpaq)]OTf complexes through reaction of their MnII or MnIII precursors with t BuOOH and CmOOH, respectively. Both of the new MnIII-OOR complexes are stable at room-temperature (t 1/2 = 5 and 8 days, respectively, at 298 K in CH3CN) and capable of reacting directly with phosphine substrates. The stability of these MnIII-OOR adducts render them amenable for detailed characterization, including by X-ray crystallography for [MnIII(OOCm)(6Medpaq)]OTf. Thermal decomposition studies support a decay pathway of the MnIII-OOR complexes by O-O bond homolysis. In contrast, direct reaction of [MnIII(OOCm)(6Medpaq)]+ with PPh3 provided evidence of heterolytic cleavage of the O-O bond. These studies reveal that both the stability and chemical reactivity of MnIII-OOR complexes can be tuned by the local coordination sphere.

Steric control of dioxygen activation pathways for MnII complexes supported by pentadentate, amide-containing ligands.

Dioxygen activation at manganese centers is well known in nature, but synthetic manganese systems capable of utilizing O2 as an oxidant are relatively uncommon. These present investigations probe the dioxygen activation pathways of two mononuclear MnII complexes supported by pentacoordinate amide-containing ligands, [MnII(dpaq)](OTf) and the sterically modified [MnII(dpaq2Me)](OTf). Dioxygen titration experiments demonstrate that [MnII(dpaq)](OTf) reacts with O2 to form [MnIII(OH)(dpaq)](OTf) according to a 4 : 1 Mn : O2 stoichiometry. This stoichiometry is consistent with a pathway involving comproportionation between a MnIV-oxo species and residual MnII complex to form a (µ-oxo)dimanganese(iii,iii) species that is hydrolyzed by water to give the MnIII-hydroxo product. In contrast, the sterically modified [MnII(dpaq2Me)](OTf) complex was found to react with O2 according to a 2 : 1 Mn : O2 stoichiometry. This stoichiometry is indicative of a pathway in which a MnIV-oxo intermediate abstracts a hydrogen atom from solvent instead of undergoing comproportionation with the MnII starting complex. Isotopic labeling experiments, in which the oxygenation of the MnII complexes was carried out in deuterated solvent, supported this change in pathway. The oxygenation of [MnII(dpaq)](OTf) did not result in any deuterium incorporation in the MnIII-hydroxo product, while the oxygenation of [MnII(dpaq2Me)](OTf) in d3-MeCN showed [MnIII(OD)(dpaq2Me)]+ formation. Taken together, these observations highlight the use of steric effects as a means to select which intermediates form along dioxygen activation pathways.

Relationship between Hydrogen-Atom Transfer Driving Force and Reaction Rates for an Oxomanganese(IV) Adduct.

Hydrogen atom transfer (HAT) reactions by high-valent metal-oxo intermediates are important in both biological and synthetic systems. While the HAT reactivity of FeIV-oxo adducts has been extensively investigated, studies of analogous MnIV-oxo systems are less common. There are several recent reports of MnIV-oxo complexes, supported by neutral pentadentate ligands, capable of cleaving strong C-H bonds at rates approaching those of analogous FeIV-oxo species. In this study, we provide a thorough analysis of the HAT reactivity of one of these MnIV-oxo complexes, [MnIV(O)(2pyN2Q)]2+, which is supported by an N5 ligand with equatorial pyridine and quinoline donors. This complex is able to oxidize the strong C-H bonds of cyclohexane with rates exceeding those of FeIV-oxo complexes with similar ligands. In the presence of excess oxidant (iodosobenzene), cyclohexane oxidation by [MnIV(O)(2pyN2Q)]2+ is catalytic, albeit with modest turnover numbers. Because the rate of cyclohexane oxidation by [MnIV(O)(2pyN2Q)]2+ was faster than that predicted by a previously published Bells-Evans-Polanyi correlation, we expanded the scope of this relationship by determining HAT reaction rates for substrates with bond dissociation energies spanning 20 kcal/mol. This extensive analysis showed the expected correlation between reaction rate and the strength of the substrate C-H bond, albeit with a shallow slope. The implications of this result with regard to MnIV-oxo and FeIV-oxo reactivity are discussed.

Spectroscopic and Structural Characterization of Mn(III)-Alkylperoxo Complexes Supported by Pentadentate Amide-Containing Ligands.

Manganese-alkylperoxo species have been proposed as important intermediates in certain enzymatic pathways and are presumed to play a key role in catalytic substrate oxidation cycles involving manganese catalysts and peroxide oxidants. However, structural and spectroscopic understanding of these intermediates is very limited, with only one series of synthetic MnIII-alkylperoxo complexes having been reported. In the present study, we describe the formation and properties of two new MnIII-alkylperoxo complexes, namely, [MnIII(OO tBu)(dpaq)]+ and [MnIII(OO tBu)(dpaq2Me)]+, which utilize the anionic, amide-containing pentadentate dpaq ligand platform. These complexes were generated by reacting the corresponding MnII precursors with a large excess of tBuOOH at -15 °C in MeCN. In both cases, the corresponding mononuclear MnIII-hydroxo complexes [MnIII(OH)(dpaq)]+ and [MnIII(OH)(dpaq2Me)]+ are observed as intermediates en route to the MnIII-alkylperoxo adducts. These new MnIII-alkylperoxo complexes were characterized by electronic absorption, infrared, and Mn K-edge X-ray absorption spectroscopies. Complementary density functional theory calculations were also performed to gain insight into their bonding and structural properties. Compared to previously reported MnIII-alkylperoxo adducts, the MnIII centers in these complexes exhibit significantly altered primary coordination spheres, with a strongly donating anionic amide nitrogen located trans to the alkylperoxo moiety. This results in MnIII-alkylperoxo bonding that is dominated by σ-interactions between the alkylperoxo πip*(O-O) orbital and the Mn d z2 orbital.

Steric and Electronic Influence on Proton-Coupled Electron-Transfer Reactivity of a Mononuclear Mn(III)-Hydroxo Complex.

A mononuclear hydroxomanganese(III) complex was synthesized utilizing the N5 amide-containing ligand 2-[bis(pyridin-2-ylmethyl)]amino-N-2-methyl-quinolin-8-yl-acetamidate (dpaq(2Me) ). This complex is similar to previously reported [Mn(III)(OH)(dpaq(H))](+) [Inorg. Chem. 2014, 53, 7622-7634] but contains a methyl group adjacent to the hydroxo moiety. This α-methylquinoline group in [Mn(III)(OH)(dpaq(2Me))](+) gives rise to a 0.1 Å elongation in the Mn-N(quinoline) distance relative to [Mn(III)(OH)(dpaq(H))](+). Similar bond elongation is observed in the corresponding Mn(II) complex. In MeCN, [Mn(III)(OH)(dpaq(2Me))](+) reacts rapidly with 2,2',6,6'-tetramethylpiperidine-1-ol (TEMPOH) at -35 °C by a concerted proton-electron transfer (CPET) mechanism (second-order rate constant k2 of 3.9(3) M(-1) s(-1)). Using enthalpies and entropies of activation from variable-temperature studies of TEMPOH oxidation by [Mn(III)(OH)(dpaq(2Me))](+) (ΔH(‡) = 5.7(3) kcal(-1) M(-1); ΔS(‡) = -41(1) cal M(-1) K(-1)), it was determined that [Mn(III)(OH)(dpaq(2Me))](+) oxidizes TEMPOH ∼240 times faster than [Mn(III)(OH)(dpaq(H))](+). The [Mn(III)(OH)(dpaq(2Me))](+) complex is also capable of oxidizing the stronger O-H and C-H bonds of 2,4,6-tri-tert-butylphenol and xanthene, respectively. However, for these reactions [Mn(III)(OH)(dpaq(2Me))](+) displays, at best, modest rate enhancement relative to [Mn(III)(OH)(dpaq(H))](+). A combination of density function theory (DFT) and cyclic voltammetry studies establish an increase in the Mn(III)/Mn(II) reduction potential of [Mn(III)(OH)(dpaq(2Me))](+) relative to [Mn(III)(OH)(dpaq(H))](+), which gives rise to a larger driving force for CPET for the former complex. Thus, more favorable thermodynamics for [Mn(III)(OH)(dpaq(2Me))](+) can account for the dramatic increase in rate with TEMPOH. For the more sterically encumbered substrates, DFT computations suggest that this effect is mitigated by unfavorable steric interactions between the substrate and the α-methylquinoline group of the dpaq(2Me) ligand. The DFT calculations, which reproduce the experimental activation free energies quite well, provide the first examination of the transition-state structure of mononuclear Mn(III)(OH) species during a CPET reaction.