Electronic structure contributions to O–O bond cleavage reactions for Mn<sup>III</sup>-alkylperoxo complexes

Brunclik, Samuel A; Opalade, Adedamola A.; Jackson, Timothy A.

doi:10.1039/d3dt01672b

Dalton Trans.

2023

DOI: 10.1039/d3dt01672b

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Electronic structure contributions to O–O bond cleavage reactions for Mn^III-alkylperoxo complexes

Samuel A Brunclik

Adedamola A. Opalade

Timothy A. Jackson

Abstract: 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...

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2024

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Cited by 3 publications

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Spectroscopic Properties and Reactivity of a Mn^III‐Hydroperoxo Complex that is Stable at Room Temperature

Grotemeyer,

Aghaei,

Jackson

2024

Chemistry A European J

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Manganese catalysts that activate hydrogen peroxide have seen increased use in organic transformations, such as olefin epoxidation and alkane C−H bond oxidation. Proposed mechanisms for these catalysts involve the formation and activation of MnIII‐hydroperoxo intermediates. Examples of well‐defined MnIII‐hydroperoxo complexes are rare, and the properties of these species are often inferred from MnIII‐alkylperoxo analogues. In this study, we show that the reaction of the MnIII‐hydroxo complex [MnIII(OH)(6Medpaq)]+ (1) with hydrogen peroxide and acid results in the formation of a dark‐green MnIII‐hydroperoxo species [MnIII(OOH)(6Medpaq)]+ (2). The formulation of 2 is based on electronic absorption, 1H NMR, IR, and ESI‐MS data. The thermal decay of 2 follows a first order process, and variable‐temperature kinetic studies of the decay of 2 yielded activation parameters that could be compared with those of a MnIII‐alkylperoxo analogue. Complex 2 reacts with the hydrogen‐atom donor TEMPOH two‐fold faster than the MnIII‐hydroxo complex 1. Complex 2 also oxidizes PPh3, and this MnIII‐hydroperoxo species is 600‐fold more reactive with this substrate than its MnIII‐alkylperoxo analogue [MnIII(OOtBu)(6Medpaq)]+. DFT and time‐dependent (TD) DFT computations are used to compare the electronic structure of 2 with similar MnIII‐hydroperoxo and MnIII‐alkylperoxo complexes.

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Spectroscopic Properties and Reactivity of a Mn^III‐Hydroperoxo Complex that is Stable at Room Temperature

Grotemeyer,

Aghaei,

Jackson

2024

Chemistry A European J

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Facile Synthesis of a Novel, Low Fabric Damage and Cost-Effective Bleach Catalyst for Cotton Fabric: 1,4-Dimethylpiperazine Manganese Complex

Hua,

Xu,

Zhang

et al. 2024

Fibers Polym

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Investigating Ligand Sphere Perturbations on MnIII–Alkylperoxo Complexes

Brunclik,

Grotemeyer,

Aghaei

et al. 2024

Molecules

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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.

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Electronic structure contributions to O–O bond cleavage reactions for Mn^III-alkylperoxo complexes

Abstract: 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...

Cited by 3 publications

References 52 publications

Spectroscopic Properties and Reactivity of a Mn^III‐Hydroperoxo Complex that is Stable at Room Temperature

Spectroscopic Properties and Reactivity of a Mn^III‐Hydroperoxo Complex that is Stable at Room Temperature

Facile Synthesis of a Novel, Low Fabric Damage and Cost-Effective Bleach Catalyst for Cotton Fabric: 1,4-Dimethylpiperazine Manganese Complex

Investigating Ligand Sphere Perturbations on MnIII–Alkylperoxo Complexes

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Electronic structure contributions to O–O bond cleavage reactions for MnIII-alkylperoxo complexes

Abstract: 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...

Cited by 3 publications

References 52 publications

Spectroscopic Properties and Reactivity of a MnIII‐Hydroperoxo Complex that is Stable at Room Temperature

Spectroscopic Properties and Reactivity of a MnIII‐Hydroperoxo Complex that is Stable at Room Temperature

Facile Synthesis of a Novel, Low Fabric Damage and Cost-Effective Bleach Catalyst for Cotton Fabric: 1,4-Dimethylpiperazine Manganese Complex

Investigating Ligand Sphere Perturbations on MnIII–Alkylperoxo Complexes

Contact Info

Product

Resources

About

Electronic structure contributions to O–O bond cleavage reactions for Mn^III-alkylperoxo complexes

Spectroscopic Properties and Reactivity of a Mn^III‐Hydroperoxo Complex that is Stable at Room Temperature

Spectroscopic Properties and Reactivity of a Mn^III‐Hydroperoxo Complex that is Stable at Room Temperature