ArticleJournal of the American Chemical Society2019
Rate-Driving Force Relationships in the Multisite Proton-Coupled Electron Transfer Activation of Ketones.
Article in Journal of the American Chemical Society, 2019. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 29 papers.
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Who cites it
29 citing papers in PubMed, 79 citations in OpenAlex.
- Repositioning Proton and Electron Donors in a Family of Proton-Coupled Electron Transfer Mediators.Inorganic chemistry · 2026Article
- Overcoming the Barrier to Intermolecular Alkoxy Radical Reactivity: Proton-Coupled Electron Transfer-Mediated Alkene Hydroetherification.Journal of the American Chemical Society · 2026Article
- Tunable Multisite Proton-Coupled Electron Transfer Mediators: Distinct Pathways for Substrate Reduction Versus Competing Hydrogen Evolution.Journal of the American Chemical Society · 2026Article
- Multisite Proton-Coupled Electron Transfer Facilitates Oxidative Photocatalysis in a Molecular Zr-Based Coordination Compound.Angewandte Chemie (International ed. in English) · 2025Article
- Photoredox-Catalyzed Hydroalkylation of C(spChemistry (Weinheim an der Bergstrasse, Germany) · 2025Article
- Proton-coupled electron transfer controls peroxide activation initiated by a solid-water interface.Nature communications · 2025Article
- The Role of Electron Transfer in Copper-Mediated C(spAngewandte Chemie (International ed. in English) · 2025Article
- Exceptions, Paradoxes, and Their Resolutions in Chemical Reactivity.The Journal of organic chemistry · 2024Review
- Intermolecular Proton-Coupled Electron Transfer Reactivity from a Persistent Charge-Transfer State for Reductive Photoelectrocatalysis.Journal of the American Chemical Society · 2024Article
- Luminescence and Excited-State Reactivity in a Heteroleptic Tricyanido Fe(III) Complex.Journal of the American Chemical Society · 2024Article
- The Intrinsic Barrier Width and Its Role in Chemical Reactivity.ACS central science · 2023Article
- Pre-Equilibrium Reaction Mechanism as a Strategy to Enhance Rate and Lower Overpotential in Electrocatalysis.Journal of the American Chemical Society · 2023Article
- C(spChemical science · 2023Article
- Structural and Thermodynamic Effects on the Kinetics of C-H Oxidation by Multisite Proton-Coupled Electron Transfer in Fluorenyl Benzoates.The Journal of organic chemistry · 2022Article
- Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis.Chemical reviews · 2022Review
- Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications.Chemical reviews · 2022Review
- Defective Ultrathin ZnInAdvanced science (Weinheim, Baden-Wurttemberg, Germany) · 2022Article
- C-H oxidation in fluorenyl benzoates does not proceed through a stepwise pathway: revisiting asynchronous proton-coupled electron transfer.Chemical science · 2021Article
- Bimodal Evans-Polanyi Relationships in Hydrogen Atom Transfer from C(spJournal of the American Chemical Society · 2021Article
- Concerted proton-electron transfer reactions of manganese-hydroxo and manganese-oxo complexes.Chemical communications (Cambridge, England) · 2020Article
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Authors and funding
2 authors at 1 institution in 1 country.
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Abstract
Here we present a detailed kinetic study of the multisite proton-coupled electron transfer (MS-PCET) activations of aryl ketones using a variety of Brønsted acids and excited-state Ir(III)-based electron donors. A simple method is described for simultaneously extracting both the hydrogen-bonding equilibrium constants and the rate constants for the PCET event from deconvolution of the luminescence quenching data. These experiments confirm that these activations occur in a concerted fashion, wherein the proton and electron are transferred to the ketone substrate in a single elementary step. The rates constants for the PCET events were linearly correlated with their driving forces over a range of nearly 19 kcal/mol. However, the slope of the rate-driving force relationship deviated significantly from expectations based on Marcus theory. A rationalization for this observation is proposed based on the principle of non-perfect synchronization, wherein factors that serve to stabilize the product are only partially realized at the transition state. A discussion of the relevance of these findings to the applications of MS-PCET in organic synthesis is also presented.
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Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.