ArticleJournal of the American Chemical Society2016
Singlet versus Triplet Reactivity in an Mn(V)-Oxo Species: Testing Theoretical Predictions Against Experimental Evidence.
Article in Journal of the American Chemical Society, 2016. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 31 papers.
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Who cites it
31 citing papers in PubMed.
- Biomimetic Mn(III) porphyrin-catalyzed aromaticity-breaking epoxidation of electron-deficient naphthalene.Nature communications · 2025Article
- Mechanism of the Oxidative Ring-Closure Reaction during Gliotoxin Biosynthesis by Cytochrome P450 GliF.International journal of molecular sciences · 2024Article
- Redox Processes Involving Oxygen: The Surprising Influence of Redox-Inactive Lewis Acids.JACS Au · 2024Review
- Untangling ancillary ligand donationChemical science · 2024Article
- How Is Substrate Halogenation Triggered by the Vanadium Haloperoxidase fromACS catalysis · 2023Article
- On the Role of Noncovalent Ligand-Substrate Interactions in Au(I) Catalysis: An Experimental and Computational Study of Protodeauration.ACS catalysis · 2022Article
- Second Coordination Sphere Effects on the Mechanistic Pathways for Dioxygen Activation by a Ferritin: Involvement of a Tyr Radical and the Identification of a Cation Binding Site.Chembiochem : a European journal of chemical biology · 2022Article
- What Drives Radical Halogenation versus Hydroxylation in Mononuclear Nonheme Iron Complexes? A Combined Experimental and Computational Study.Journal of the American Chemical Society · 2022Article
- Benchmark Study of Redox Potential Calculations for Iron-Sulfur Clusters in Proteins.Inorganic chemistry · 2022Article
- Mechanistic insights into dioxygen activation by a manganese corrole complex: a broken-symmetry DFT study.RSC advances · 2021Article
- Product Distributions of Cytochrome P450 OleTInternational journal of molecular sciences · 2021Article
- Closed Shell Iron(IV) Oxo Complex with an Fe-O Triple Bond: Computational Design, Synthesis, and Reactivity.Angewandte Chemie (International ed. in English) · 2020Article
- Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni-MnNature communications · 2020Article
- How Does Replacement of the Axial Histidine Ligand in CytochromeInternational journal of molecular sciences · 2020Article
- Catalytic Mechanism of Aromatic Nitration by Cytochrome P450 TxtE: Involvement of a Ferric-Peroxynitrite Intermediate.Journal of the American Chemical Society · 2020Article
- Theoretical Study on the Structural-Function Relationship of Manganese(III)-Iodosylarene Adducts.Frontiers in chemistry · 2020Article
- Hydrogen Atom Abstraction by High-Valent Fe(OH) versus Mn(OH) Porphyrinoid Complexes: Mechanistic Insights from Experimental and Computational Studies.Inorganic chemistry · 2019Article
- Properties and reactivity of μ-nitrido-bridged dimetal porphyrinoid complexes: how does ruthenium compare to iron?Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2019Article
- Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis.Frontiers in chemistry · 2019Article
- Advances in Sustainable Catalysis: A Computational Perspective.Frontiers in chemistry · 2019Review
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6 authors.
Funding
Abstract
Discerning the factors that control the reactivity of high-valent metal-oxo species is critical to both an understanding of metalloenzyme reactivity and related transition metal catalysts. Computational studies have suggested that an excited higher spin state in a number of metal-oxo species can provide a lower energy barrier for oxidation reactions, leading to the conclusion that this unobserved higher spin state complex should be considered as the active oxidant. However, testing these computational predictions by experiment is difficult and has rarely been accomplished. Herein, we describe a detailed computational study on the role of spin state in the reactivity of a high-valent manganese(V)-oxo complex with para-Z-substituted thioanisoles and utilize experimental evidence to distinguish between the theoretical results. The calculations show an unusual change in mechanism occurs for the dominant singlet spin state that correlates with the electron-donating property of the para-Z substituent, while this change is not observed on the triplet spin state. Minimum energy crossing point calculations predict small spin-orbit coupling constants making the spin state change from low spin to high spin unlikely. The trends in reactivity for the para-Z-substituted thioanisole derivatives provide an experimental measure for the spin state reactivity in manganese-oxo corrolazine complexes. Hence, the calculations show that the V-shaped Hammett plot is reproduced by the singlet surface but not by the triplet state trend. The substituent effect is explained with valence bond models, which confirm a change from an electrophilic to a nucleophilic mechanism through a change of substituent.
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