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Dioxygen Activation by Non‐Adiabatic Oxidative Addition to a Single Metal Center
Author(s) -
Akturk Eser S.,
Yap Glenn P. A.,
Theopold Klaus H.
Publication year - 2015
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.201508777
Subject(s) - chemistry , chromium , oxidative addition , metal , oxidative phosphorylation , center (category theory) , sulfur , boron , stereochemistry , activation energy , medicinal chemistry , potential energy surface , transition metal , crystallography , molecule , organic chemistry , catalysis , biochemistry
Abstract A chromium(I) dinitrogen complex reacts rapidly with O 2 to form the mononuclear dioxo complex [Tp t Bu,Me Cr V (O) 2 ] (Tp t Bu,Me =hydrotris(3‐ tert ‐butyl‐5‐methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp t Bu,Me Cr III (S 2 )]. The transformation of the putative peroxo intermediate [Tp t Bu,Me Cr III (O 2 )] (S= 3 / 2 ) into [Tp t Bu,Me Cr V (O) 2 ] (S= 1 / 2 ) is spin‐forbidden. The minimum‐energy crossing point for the two potential energy surfaces has been identified. Although the dinuclear complex [(Tp t Bu,Me Cr) 2 (μ‐O) 2 ] exists, mechanistic experiments suggest that O 2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.