ArticleThe Journal of organic chemistry2015
Conformational Change with Steric Interactions Affects the Inner Sphere Component of Concerted Proton-Electron Transfer in a Pyridyl-Appended Radical Cation System.
Article in The Journal of organic chemistry, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 3 papers.
What it found
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The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.
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Trials whose registry record cites this paper, or whose number appears in the abstract. A trial that started after this paper was published is citing it as background, not reporting it.
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Who cites it
3 citing papers in PubMed.
- Electrostatic Fields Induce Accelerated Proton Coupled Electron Transfer Rates in Chlorophyll Model Compounds.Journal of the American Chemical Society · 2025Article
- Establishing Thermodynamic Graphs of Nitrogenous Radical Cations Abstracting Hydrogen Atoms and Their Applications in Photoredox Reactions.Molecules (Basel, Switzerland) · 2025Article
- Article
Corrections and comments
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Authors and funding
11 authors.
Funding
Abstract
Proton-coupled electron transfer (PCET) model systems combine one-electron oxidants and bases to generate net hydrogen atom acceptors. We have generated two persistent pyridyl-appended radical cations: 10-(pyrid-2-yl)-10H-phenothiazinium (PPT•+) and 3-(pyrid-2-yl)-10-methyl-10H-phenothiazinium (MPTP•+). EPR spectra and corresponding calculations indicate phenothiazinium radical cations with minimal spin on the pyridine nitrogen. Addition of hindered phenols causes the radical cations to decay, and protonated products and the corresponding phenoxyl radicals to form. The ΔG° values for the formation of intermediates (determined through cyclic voltammetry and pKa measurements) rule out a stepwise mechanism, and kinetic isotope effects support concerted proton–electron transfer (CPET) as the mechanism. Calculations indicate that the reaction of PPT•+ + tBu3PhOH undergoes a significant conformational change with steric interactions on the diabatic surface while maintaining the hydrogen bond; in contrast, MPTP•+ + tBu3PhOH maintains its conformation throughout the reaction. This difference is reflected in both experiment and calculations with ΔG(⧧)MPTP•+ < ΔG(⧧)PPT•+ despite ΔG°MPTP•+ > ΔG°PPT•+. Experimental results with 2,6-di-tert-butyl-4-methoxyphenol are similar. Hence, despite the structural similarity between the compounds, differences in the inner sphere component for CPET affect the kinetics.
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Registered trials
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