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PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View

Mayer, James M.·2004·Annual Review of Physical Chemistry

Abstract

▪ Abstract Proton-coupled electron transfer (PCET) reactions involve the concerted transfer of an electron and a proton. Such reactions play an important role in many areas of chemistry and biology. Concerted PCET is thermochemically more favorable than the first step in competing consecutive processes involving stepwise electron transfer (ET) and proton transfer (PT), often by ≥1 eV. PCET reactions of the form [Formula: see text] can be termed hydrogen atom transfer (HAT). Another PCET class involves outersphere electron transfer concerted with deprotonation by another reagent, [Formula: see text]. Many PCET/HAT rate constants are predicted well by the Marcus cross relation. The cross-relation calculation uses rate constants for self-exchange reactions to provide information on intrinsic barriers. Intrinsic barriers for PCET can be comparable to or larger than those for ET. These properties are discussed in light of recent theoretical treatments of PCET.

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Metadata

Authors
Mayer, J. M.
Venue
Annual Review of Physical Chemistry
Published
2004-06-01
Volume
55
Issue
1
Pages
363-390
ISSN
  • 0066-426X (ISSN-L)
  • 1545-1593
OpenAlex
W1972040015
Cited by
814
References
2
FWCI
2.50
Type
journal article
Language
en
Open access
closed

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CoChat. (2026). Citation check: PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View. https://app.cochat.ai/papers/10.1146/annurev.physchem.55.091602.094446
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Mayer, J. M. (2004). PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View. Annual Review of Physical Chemistry. https://doi.org/10.1146/annurev.physchem.55.091602.094446

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