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Structures of Transition States in Metal‐Mediated O 2 ‐Activation Reactions
Author(s) -
Lanci Michael P.,
Brinkley David W.,
Stone Kristie L.,
Smirnov Valeriy V.,
Roth Justine P.
Publication year - 2005
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.200502096
Subject(s) - chemistry , kinetic isotope effect , intermolecular force , isotope , mechanism (biology) , transition metal , reaction rate constant , kinetic energy , metal , transition state , computational chemistry , molecule , catalysis , physics , organic chemistry , kinetics , atomic physics , nuclear physics , quantum mechanics , deuterium
Kinetic isotope effects (KIEs) have been used to probe the mechanism of the binding of O 2 to classic inorganic compounds. The intermolecular 18 O KIEs decrease with increasing rate constants, and the correlation of the KIEs with the log k O 2values establishes that the same oxidative addition mechanism is operative in all cases, but with marked differences in the transition‐state structure (see figure).