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- W2785207088 abstract "Proton transfer often accompanies electron transfer in organic redox couples due to the large changes in acidity or basicity that result from oxidation or reduction. Classically, the overall reaction is thought to occur in two separate steps, either proton transfer followed by electron transfer, PT-ET, or electron transfer followed by proton transfer, ET-PT. More recently it has become abundantly apparent that a third option is also possible in which the proton and electron move together in a single kinetic step. This is concerted proton-electron transfer, CPET, and is generally believed to occur within a H-bonded intermediate. It is straightforward to show that E° of this step will have a value in between the E° values corresponding to the oxidation of the fully protonated and fully deprotonated forms. Experimental evidence for CPET is typically the observance of a significant deuterium isotope effect for the apparent one electron transfer. However, it is important to note that the electron-proton transfer does not have to be concerted within the H-bond complex. It could also occur step-wise. If slow electron transfer occurred followed by rapid proton transfer within the H-bond complex, no significant deuterium isotope effect would be expected, yet, at the same time, the overall reversibility of the electron-proton transfer would still be aided by providing a mechanistic pathway through the H-bond complex with its intermediate E°." @default.
- W2785207088 created "2018-02-02" @default.
- W2785207088 date "2018-01-01" @default.
- W2785207088 modified "2023-09-25" @default.
- W2785207088 title "The Role of Hydrogen Bonding in Proton-Coupled Electron Transfer. It Does Not Have to be Concerted Pcet: The Case of Phenylenediamines and Pyridines in Acetonitrile" @default.
- W2785207088 doi "https://doi.org/10.1149/ma2018-01/34/2033" @default.
- W2785207088 hasPublicationYear "2018" @default.
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