Dioxygen Activation by Non‐Adiabatic Oxidative Addition to a Single Metal Center |
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| Authors: | Eser S Akturk Dr Glenn P A Yap Prof Dr Klaus H Theopold |
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| Institution: | Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (USA) |
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| Abstract: | A chromium(I) dinitrogen complex reacts rapidly with O2 to form the mononuclear dioxo complex TptBu,MeCrV(O)2] (TptBu,Me=hydrotris(3‐tert‐butyl‐5‐methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex TptBu,MeCrIII(S2)]. The transformation of the putative peroxo intermediate TptBu,MeCrIII(O2)] (S=3/2) into TptBu,MeCrV(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 (TptBu,MeCr)2(μ‐O)2] exists, mechanistic experiments suggest that O2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface. |
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| Keywords: | ab initio calculations chromium dioxygen activation spin‐forbidden reactions sulfur |
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