Premium
Electron Transfer and Structural Change: Distinguishing Concerted and Two‐Step Processes
Author(s) -
MacíasRuvalcaba Norma A.,
Evans Dennis H.
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700338
Subject(s) - electron transfer , concerted reaction , chemical physics , chemistry , transfer (computing) , mechanism (biology) , reaction mechanism , computer science , physics , photochemistry , catalysis , organic chemistry , parallel computing , quantum mechanics
In electron‐transfer reactions accompanied by structural changes, the structural change can be concerted with electron transfer or can occur in a separate reaction either preceding or following the electron‐transfer step. In this paper we discuss ways of distinguishing concerted reactions from the latter two‐step type. Included are recent examples in which no intermediates have been detected in the reactions, thus precluding the direct assignment to the two‐step category. In these cases, other means are used to build support for the two‐step mechanism with respect to the concerted process. These include an example of structural change preceding electron transfer, a demonstration that the current models of concerted reactions cannot fit the voltammetric data, and a case in which an independent measure of the inner reorganization energy was used to show that the reaction could not be a concerted electron transfer and structural change.