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Which Oxidant Is Really Responsible for P450 Model Oxygenation Reactions? A Kinetic Approach
Author(s) -
Franke Alicja,
Fertinger Christoph,
van Eldik Rudi
Publication year - 2008
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200800907
Subject(s) - heterolysis , chemistry , catalysis , kinetic energy , substrate (aquarium) , cleavage (geology) , bond cleavage , oxygen , kinetics , oxygenation , medicinal chemistry , photochemistry , organic chemistry , materials science , physics , ecology , quantum mechanics , fracture (geology) , composite material , biology
A rate‐fate fête : Direct kinetic studies on epoxidation and sulfoxidation reactions revealed that the oxygenating capability of [(TMP +. )Fe IV O] is orders of magnitude higher than that of [Fe III (TMP)( m ‐CPBA)]. Under catalytic turnover conditions, the relative ratio between the rate of OO bond heterolytic cleavage and the rate of oxygen transfer from the [Fe III (TMP)( m ‐CPBA)] intermediate to the substrate, should be taken into consideration. m ‐CPBA =m ‐chloroperbenzoic acid, TMP= meso ‐tetramesitylporphyrin.