Structures of Transition States in Metal-Mediated O2-Activation Reactions

Kinetic isotope effects (KIEs) have been used to probe the mechanism of the binding of O2 to classic inorganic compounds. The intermolecular 18O KIEs decrease with increasing rate constants, and the correlation of the KIEs with the log k O 2 values establishes that the same oxidative addition mechan...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2005-11, Vol.44 (44), p.7273-7276
Main Authors: Lanci, Michael P., Brinkley, David W., Stone, Kristie L., Smirnov, Valeriy V., Roth, Justine P.
Format: Article
Language:English
Subjects:
electron transfer
enzymes
Enzymes - metabolism
Inorganic Chemicals - chemistry
Inorganic Chemicals - metabolism
isotope effects
Kinetics
Metals - chemistry
Metals - metabolism
Models, Chemical
Molecular Structure
O-O activation
Oxygen - chemistry
Oxygen - metabolism
Oxygen Isotopes - chemistry
transition states
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Summary:Kinetic isotope effects (KIEs) have been used to probe the mechanism of the binding of O2 to classic inorganic compounds. The intermolecular 18O KIEs decrease with increasing rate constants, and the correlation of the KIEs with the log k O 2 values establishes that the same oxidative addition mechanism is operative in all cases, but with marked differences in the transition‐state structure (see figure).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200502096