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Thermodynamics and kinetics of proton-coupled electron transfer: stepwise vs. concerted pathways.
Reactions that involve transfer of an electron and a proton can proceed by stepwise pathways involving initial electron transfer (ET) or initial proton transfer (PT), or by a concerted pathwayExpand
Concerted proton-electron transfer in the oxidation of hydrogen-bonded phenols.
Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants, among the first detailed analyses of CPET reactions where the proton and electron move to different sites. Expand
One-electron oxidation of a hydrogen-bonded phenol occurs by concerted proton-coupled electron transfer.
The isotope effect, thermochemical arguments, and the dependence of the rate on driving force all indicate that electron transfer from HOAr-NH2 must occur concerted with intramolecular proton transfer from the phenol to the amine (proton-coupled electron transfer, PCET). Expand
Probing concerted proton–electron transfer in phenol–imidazoles
A series of seven substituted 4,6-di-tert-butyl-2-(4,5-diarylimidazolyl)-phenols have been prepared and characterized, along with two related benzimidazole compounds, a valuable system in which to examine the key features of CPET. Expand
Kinetic effects of increased proton transfer distance on proton-coupled oxidations of phenol-amines.
The results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Expand
Models for Proton-coupled Electron Transfer in Photosystem II
The coupling of proton and electron transfers is a key part of the chemistry of photosynthesis. The oxidative side of photosystem II (PS II) in particular seems to involve a number of proton-coupledExpand
Oxidation of TpOsIII(NH2Ph)Cl2 to TpOsIV(NHPh)Cl2 by O2
Abstract The osmium(III) aniline complex TpOs(NH2Ph)Cl2 (OsIIINH2Ph) is formed on heating the triflate complex [Cp*2Fe][TpOsIII(OTf)Cl2] in the presence of aniline [Tp =Expand
Models for Proton-Coupled Electron Transfer in Photosystem II
An overview of recent studies of PCET model systems in the authors' laboratory is presented, including organic HAT reactions and reactions of iron-tris(alpha-diimine) and manganese-(mu-oxo) complexes. Expand
Carbocation Rearrangement in an Electrophilic Aromatic Substitution Discovery Laboratory
In this discovery laboratory, students performed electrophilic aromatic substitution reactions between 1,4-dimethoxybenzene and either 2-methyl-2-butanol or 3-methyl-2-butanol with sulfuric acid as aExpand