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 kequation/tex2gif-inf-3.gif values establishes that the same oxidative addition mechanism is operative in all cases, but with marked differences in the transition-state structure (see figure). Supporting information (experimental details and isotope-effect calculations) for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z502096_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.