ArticleJournal of the American Chemical Society2013
Correlation between structural, spectroscopic, and reactivity properties within a series of structurally analogous metastable manganese(III)-alkylperoxo complexes.
Article in Journal of the American Chemical Society, 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 20 papers.
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Who cites it
20 citing papers in PubMed.
- Enzyme-inspired single-molecule photocatalyst enables singlet-oxygen-driven asymmetric epoxidation and sulfoximination.Nature communications · 2026Article
- Activation of alkyl hydroperoxides by manganese complexes of tmtacn for initiation of radical polymerisation of alkenes.Catalysis science & technology · 2024Article
- Investigating Ligand Sphere Perturbations on MnMolecules (Basel, Switzerland) · 2024Article
- A Combined Spectroscopic and Computational Study on the Mechanism of Iron-Catalyzed Aminofunctionalization of Olefins Using Hydroxylamine Derived N-O Reagent as the "Amino" Source and "Oxidant".Journal of the American Chemical Society · 2022Article
- Mimicking Elementary Reactions of Manganese Lipoxygenase Using Mn-hydroxo and Mn-alkylperoxo Complexes.Molecules (Basel, Switzerland) · 2021Article
- Characterization and chemical reactivity of room-temperature-stable MnChemical science · 2021Article
- Mechanistic insights into dioxygen activation by a manganese corrole complex: a broken-symmetry DFT study.RSC advances · 2021Article
- Ligand-Constraint-Induced Peroxide Activation for Electrophilic Reactivity.Angewandte Chemie (International ed. in English) · 2021Article
- Influence of Thiolate versus Alkoxide Ligands on the Stability of Crystallographically Characterized Mn(III)-Alkylperoxo Complexes.Journal of the American Chemical Society · 2021Article
- Comparison of two MnActa crystallographica. Section E, Crystallographic communications · 2020Article
- How Metal Ion Lewis Acidity and Steric Properties Influence the Barrier to Dioxygen Binding, Peroxo O-O Bond Cleavage, and Reactivity.Journal of the American Chemical Society · 2019Article
- Geometric and electronic structure of a crystallographically characterized thiolate-ligated binuclear peroxo-bridged cobalt(III) complex.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2019Article
- MnDalton transactions (Cambridge, England : 2003) · 2018Article
- Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of spThe Journal of organic chemistry · 2017Article
- Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.Journal of the American Chemical Society · 2017Article
- Tuning the Relative Stability and Reactivity of Manganese Dioxygen and Peroxo Intermediates via Systematic Ligand Modification.Accounts of chemical research · 2015Article
- X-ray Absorption and Emission Study of Dioxygen Activation by a Small-Molecule Manganese Complex.Inorganic chemistry · 2015Article
- Spectroscopic characterization and reactivity studies of a mononuclear nonheme Mn(III)-hydroperoxo complex.Journal of the American Chemical Society · 2014Article
- Peroxomanganese complexes as an aid to understanding redox-active manganese enzymes.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2014Review
- Reaction landscape of a pentadentate N5-ligated Mn(II) complex with O2˙- and H2O2 includes conversion of a peroxomanganese(III) adduct to a bis(μ-oxo)dimanganese(III,IV) species.Dalton transactions (Cambridge, England : 2003) · 2013Article
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Abstract
Manganese-peroxos are proposed as key intermediates in a number of important biochemical and synthetic transformations. Our understanding of the structural, spectroscopic, and reactivity properties of these metastable species is limited, however, and correlations between these properties have yet to be established experimentally. Herein we report the crystallographic structures of a series of structurally related metastable Mn(III)-OOR compounds, and examine their spectroscopic and reactivity properties. The four reported Mn(III)-OOR compounds extend the number of known end-on Mn(III)-(η(1)-peroxos) to six. The ligand backbone is shown to alter the metal-ligand distances and modulate the electronic properties key to bonding and activation of the peroxo. The mechanism of thermal decay of these metastable species is examined via variable-temperature kinetics. Strong correlations between structural (O-O and Mn···N(py,quin) distances), spectroscopic (E(πv*(O-O) → Mn CT band), ν(O-O)), and kinetic (ΔH(‡) and ΔS(‡)) parameters for these complexes provide compelling evidence for rate-limiting O-O bond cleavage. Products identified in the final reaction mixtures of Mn(III)-OOR decay are consistent with homolytic O-O bond scission. The N-heterocyclic amines and ligand backbone (Et vs Pr) are found to modulate structural and reactivity properties, and O-O bond activation is shown, both experimentally and theoretically, to track with metal ion Lewis acidity. The peroxo O-O bond is shown to gradually become more activated as the N-heterocyclic amines move closer to the metal ion causing a decrease in π-donation from the peroxo πv*(O-O) orbital. The reported work represents one of very few examples of experimentally verified relationships between structure and function.
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