ArticleJournal of the American Chemical Society2015
Strong Inhibition of O-Atom Transfer Reactivity for Mn(IV)(O)(π-Radical-Cation)(Lewis Acid) versus Mn(V)(O) Porphyrinoid Complexes.
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 11 papers.
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Who cites it
11 citing papers in PubMed, 50 citations in OpenAlex.
- Redox Processes Involving Oxygen: The Surprising Influence of Redox-Inactive Lewis Acids.JACS Au · 2024Review
- Mechanistic insights into dioxygen activation by a manganese corrole complex: a broken-symmetry DFT study.RSC advances · 2021Article
- Concerted proton-electron transfer reactions of manganese-hydroxo and manganese-oxo complexes.Chemical communications (Cambridge, England) · 2020Article
- Effects of Noncovalent Interactions on High-Spin Fe(IV)-Oxido Complexes.Journal of the American Chemical Society · 2020Article
- A Manganese(V)-Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies.Chemistry (Weinheim an der Bergstrasse, Germany) · 2018Article
- Lewis-Acid-assisted Hydrogen Atom Transfer to Manganese(V)-Oxo Corrole through Valence Tautomerization.ChemistryOpen · 2016Article
- High-Valent Manganese-Oxo Valence Tautomers and the Influence of Lewis/Brönsted Acids on C-H Bond Cleavage.Inorganic chemistry · 2016Article
- The Influence of Peripheral Substituent Modification on P(V), Mn(III), and Mn(V)(O) Corrolazines: X-ray Crystallography, Electrochemical and Spectroscopic Properties, and HAT and OAT Reactivities.Inorganic chemistry · 2016Article
- Photocatalytic Oxygenation of Substrates by Dioxygen with Protonated Manganese(III) Corrolazine.Inorganic chemistry · 2016Article
- Rhenium(V)-oxo corrolazines: isolating redox-active ligand reactivity.Chemical communications (Cambridge, England) · 2016Article
- A Balancing Act: Stability versus Reactivity of Mn(O) Complexes.Accounts of chemical research · 2015Article
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4 authors at 1 institution in 1 country.
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Abstract
The oxygen atom transfer (OAT) reactivity of two valence tautomers of a Mn(V)(O) porphyrinoid complex was compared. The OAT kinetics of Mn(V)(O)(TBP8Cz) (TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)) reacting with a series of triarylphosphine (PAr3) substrates were monitored by stopped-flow UV-vis spectroscopy, and revealed second-order rate constants ranging from 16(1) to 1.43(6) × 10(4) M(-1) s(-1). Characterization of the OAT transition state analogues Mn(III)(OPPh3)(TBP8Cz) and Mn(III)(OP(o-tolyl)3)(TBP8Cz) was carried out by single-crystal X-ray diffraction (XRD). A valence tautomer of the closed-shell Mn(V)(O)(TBP8Cz) can be stabilized by the addition of Lewis and Brønsted acids, resulting in the open-shell Mn(IV)(O)(TBP8Cz(•+)):LA (LA = Zn(II), B(C6F5)3, H(+)) complexes. These Mn(IV)(O)(π-radical-cation) derivatives exhibit dramatically inhibited rates of OAT with the PAr3 substrates (k = 8.5(2) × 10(-3) - 8.7 M(-1) s(-1)), contrasting the previously observed rate increase of H-atom transfer (HAT) for Mn(IV)(O)(TBP8Cz(•+)):LA with phenols. A Hammett analysis showed that the OAT reactivity for Mn(IV)(O)(TBP8Cz(•+)):LA is influenced by the Lewis acid strength. Spectral redox titration of Mn(IV)(O)(TBP8Cz(•+)):Zn(II) gives Ered = 0.69 V vs SCE, which is nearly +700 mV above its valence tautomer Mn(V)(O)(TBP8Cz) (Ered = -0.05 V). These data suggest that the two-electron electrophilicity of the Mn(O) valence tautomers dominate OAT reactivity and do not follow the trend in one-electron redox potentials, which appear to dominate HAT reactivity. This study provides new fundamental insights regarding the relative OAT and HAT reactivity of valence tautomers such as M(V)(O)(porph) versus M(IV)(O)(porph(•+)) (M = Mn or Fe) found in heme enzymes.
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