ArticleJournal of the American Chemical Society2015
Ferryl protonation in oxoiron(IV) porphyrins and its role in oxygen transfer.
Article in Journal of the American Chemical Society, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 24 papers.
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Who cites it
24 citing papers in PubMed, 74 citations in OpenAlex.
- Conjugates of Heme and Intrinsically Disordered Peptides toward the Development of Synthetic Artificial Oxygen Carriers.Bioconjugate chemistry · 2026Article
- Enhanced Reactivities of Iron(IV)-Oxo Porphyrin Species in Oxidation Reactions Promoted by Intramolecular Hydrogen-Bonding.Advanced science (Weinheim, Baden-Wurttemberg, Germany) · 2024Article
- A Porphyrin Iron(III) π-Dication Species and its Relevance in Catalyst Design for the Umpolung of Nucleophiles.Angewandte Chemie (International ed. in English) · 2023Article
- Dopamine as a polymerizable reagent for enzyme-linked immunosorbent assay using horseradish peroxidase.Heliyon · 2023Article
- Common Reactivity and Properties of Heme Peroxidases: A DFT Study of Their Origin.Antioxidants (Basel, Switzerland) · 2023Article
- M[TPP]Cl (M = Fe or Mn)-Catalyzed Oxidative Amination of Phenols by Primary and Secondary Anilines.Organic letters · 2020Article
- Enhanced Rates of C-H Bond Cleavage by a Hydrogen-Bonded Synthetic Heme High-Valent Iron(IV) Oxo Complex.Journal of the American Chemical Society · 2019Article
- Tuning the Geometric and Electronic Structure of Synthetic High-Valent Heme Iron(IV)-Oxo Models in the Presence of a Lewis Acid and Various Axial Ligands.Journal of the American Chemical Society · 2019Article
- Synthetic Fe/Cu Complexes: Toward Understanding Heme-Copper Oxidase Structure and Function.Chemical reviews · 2018Review
- Effects of Charged Ligand Substituents on the Properties of the Formally Copper(III)-Hydroxide ([CuOH]Inorganic chemistry · 2018Article
- Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins.Chemical reviews · 2018Review
- Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes.Chemical reviews · 2017Article
- Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex.Journal of the American Chemical Society · 2017Article
- Function Coupling Mechanism of PhuS and HemO in Heme Degradation.Scientific reports · 2017Article
- Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in FeAngewandte Chemie (International ed. in English) · 2017Article
- Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C-H activation.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2017Review
- A new look at the role of thiolate ligation in cytochrome P450.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2017Review
- Fast Hydrogen Atom Abstraction by a Hydroxo Iron(III) Porphyrazine.Journal of the American Chemical Society · 2017Article
- Direct visualization of a Fe(IV)-OH intermediate in a heme enzyme.Nature communications · 2016Article
- High-Valent Manganese-Oxo Valence Tautomers and the Influence of Lewis/Brönsted Acids on C-H Bond Cleavage.Inorganic chemistry · 2016Article
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3 authors at 1 institution in 1 country.
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Abstract
Ferryl porphyrins, P-Fe(IV)═O, are central reactive intermediates in the catalytic cycles of numerous heme proteins and a variety of model systems. There has been considerable interest in elucidating factors, such as terminal oxo basicity, that may control ferryl reactivity. Here, the sulfonated, water-soluble ferryl porphyrin complexes tetramesitylporphyrin, oxoFe(IV)TMPS (FeTMPS-II), its 2,6-dichlorophenyl analogue, oxoFe(IV)TDClPS (FeTDClPS-II), and two other analogues are shown to be protonated under turnover conditions to produce the corresponding bis-aqua-iron(III) porphyrin cation radicals. The results reveal a novel internal electromeric equilibrium, P-Fe(IV)═O ⇆ P(+)-Fe(III)(OH2)2. Reversible pKa values in the range of 4-6.3 have been measured for this process by pH-jump, UV-vis spectroscopy. Ferryl protonation has important ramifications for C-H bond cleavage reactions mediated by oxoiron(IV) porphyrin cation radicals in protic media. Both solvent O-H and substrate C-H deuterium kinetic isotope effects are observed for these reactions, indicating that hydrocarbon oxidation by these oxoiron(IV) porphyrin cation radicals occurs via a solvent proton-coupled hydrogen atom transfer from the substrate that has not been previously described. The effective FeO-H bond dissociation energies for FeTMPS-II and FeTDClPS-II were estimated from similar kinetic reactivities of the corresponding oxoFe(IV)TMPS(+) and oxoFe(IV)TDClPS(+) species to be ∼92-94 kcal/mol. Similar values were calculated from the two-proton P(+)-Fe(III)(OH2)2 pKa(obs) and the porphyrin oxidation potentials, despite a 230 mV range for the iron porphyrins examined. Thus, the iron porphyrin with the lower ring oxidation potential has a compensating higher basicity of the ferryl oxygen. The solvent-derived proton adds significantly to the driving force for C-H bond scission.
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