ArticleJournal of the American Chemical Society2013
Dichotomous hydrogen atom transfer vs proton-coupled electron transfer during activation of X-H bonds (X = C, N, O) by nonheme iron-oxo complexes of variable basicity.
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 70 papers.
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Who cites it
70 citing papers in PubMed.
- Net fluorine atom transfer from the perspective of a PCET chemist.Chemical communications (Cambridge, England) · 2026Review
- Mapping Proton-Coupled Electron Transfer With Real Space Coordinates.Angewandte Chemie (International ed. in English) · 2026Article
- Reversible hydrogen atom exchange between phenoxyl radical and phenol at cobalt(ii): role of coordination-induced bond activation.Chemical science · 2026Article
- Antioxidant Chemistry of Phenolics in Chinese Herbal Medicines: A Holism-Based Review.Chemistry & biodiversity · 2026Review
- A Systematic Topological Picture of ROS Scavenging Activity via Formal Hydrogen Atom Transfer in Phenols and Polyphenols.The Journal of organic chemistry · 2026Article
- High-Valent Late Transition Metal-Oxo Complexes: Breaking Boundaries at the Oxo Wall and Beyond.Chemical reviews · 2026Review
- Driving Forces and Spin-Gated Reactivity of N5-Hydropyrimidopteridinetetraone Radicals in Photocatalysis.The Journal of organic chemistry · 2026Article
- Theoretical Screening of the Water Oxidation Electrocatalytic Cycle Promoted by Single-Site Macrocyclic Copper(II) Complexes: Unraveling the Role of the HPOACS organic & inorganic Au · 2026Article
- Sulfur-ligated iron(iv)-imido and iron(iv)-oxo complexes, which one is more reactive?Chemical science · 2026Article
- Substrate Epoxidation Catalyzed by the Nonheme Iron Dioxygenase Dapdiamide Biosynthesis Enzyme C. Why Is the Substrate Tethered?Chemistry (Weinheim an der Bergstrasse, Germany) · 2025Article
- Generation and Reactivity of a High-Spin Iron(IV)-Oxo Complex That Is Stable at Ambient Temperatures.Journal of the American Chemical Society · 2025Article
- The Role of Chalcogen in the ROS Scavenging Mechanism of Model Phenyl Compounds.Molecules (Basel, Switzerland) · 2025Article
- Disentangling Driving Force Effects, Polar Effects,Journal of the American Chemical Society · 2025Article
- A 5,000-fold increase in the HAT reactivity of a nonheme FeProceedings of the National Academy of Sciences of the United States of America · 2025Article
- Proton Tunneling Allows a Proton-Coupled Electron Transfer Process in the Cancer Cell.JACS Au · 2024Article
- High pressure-derived nonsymmetrical [CuScience advances · 2024Article
- Copper-oxygen adducts: new trends in characterization and properties towards C-H activation.Chemical science · 2024Review
- Radical ligand transfer: mechanism and reactivity governed by three-component thermodynamics.Chemical science · 2024Article
- Axial Ligation Impedes Proton-Coupled Electron-Transfer Reactivity of a Synthetic Compound-I Analogue.Journal of the American Chemical Society · 2024Article
- Polar Effects in Hydrogen Atom Transfer Reactions from a Proton-Coupled Electron Transfer (PCET) Perspective: Abstractions from Toluenes.The Journal of organic chemistry · 2023Article
10 more citing papers are in PubMed but not listed here.
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4 authors.
Funding
Abstract
We describe herein the hydrogen-atom transfer (HAT)/proton-coupled electron-transfer (PCET) reactivity for Fe(IV)-oxo and Fe(III)-oxo complexes (1-4) that activate C-H, N-H, and O-H bonds in 9,10-dihydroanthracene (S1), dimethylformamide (S2), 1,2-diphenylhydrazine (S3), p-methoxyphenol (S4), and 1,4-cyclohexadiene (S5). In 1-3, the iron is pentacoordinated by tris[N'-tert-butylureaylato)-N-ethylene]aminato ([H3buea](3-)) or its derivatives. These complexes are basic, in the order 3 ≫ 1 > 2. Oxidant 4, [Fe(IV)N4Py(O)](2+) (N4Py: N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), is the least basic oxidant. The DFT results match experimental trends and exhibit a mechanistic spectrum ranging from concerted HAT and PCET reactions to concerted-asynchronous proton transfer (PT)/electron transfer (ET) mechanisms, all the way to PT. The singly occupied orbital along the O···H···X (X = C, N, O) moiety in the TS shows clearly that in the PCET cases, the electron is transferred separately from the proton. The Bell-Evans-Polanyi principle does not account for the observed reactivity pattern, as evidenced by the scatter in the plot of calculated barrier vs reactions driving forces. However, a plot of the deformation energy in the TS vs the respective barrier provides a clear signature of the HAT/PCET dichotomy. Thus, in all C-H bond activations, the barrier derives from the deformation energy required to create the TS, whereas in N-H/O-H bond activations, the deformation energy is much larger than the corresponding barrier, indicating the presence of a stabilizing interaction between the TS fragments. A valence bond model is used to link the observed results with the basicity/acidity of the reactants.
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