Electronic Resource
Palo Alto, Calif.
:
Annual Reviews
Annual Review of Physical Chemistry
55 (2004), S. 363-390
ISSN:
0066-426X
Source:
Annual Reviews Electronic Back Volume Collection 1932-2001ff
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
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 X-H + Y X + H-Y can be termed hydrogen atom transfer (HAT). Another PCET class involves outersphere electron transfer concerted with deprotonation by another reagent, Y+ + XH-B Y + X-HB+ . 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1146/annurev.physchem.55.091602.094446
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