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Title: Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O 2 activation by non-adiabatic oxidative addition to a single metal center]

A chromium(I) dinitrogen complex reacts rapidly with O 2 to form the mononuclear dioxo complex [Tp tBu,MeCr V(O) 2] (Tp tBu,Me=hydrotris(3- tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp tBu,MeCr III(S 2)]. The transformation of the putative peroxo intermediate [Tp tBu,MeCr III(O 2)] (S= 3/ 2) into [Tp tBu,MeCr V(O) 2] (S= 1/ 2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(Tp tBu,MeCr) 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.
Authors:
 [1] ;  [1] ;  [1]
  1. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Grant/Contract Number:
FG02-92ER14273
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 49; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculations; chromium; dioxygen activation; spin-forbidden reactions; sulfur
OSTI Identifier:
1342854

Akturk, Eser S., Yap, Glenn P. A., and Theopold, Klaus H.. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]. United States: N. p., Web. doi:10.1002/anie.201508777.
Akturk, Eser S., Yap, Glenn P. A., & Theopold, Klaus H.. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]. United States. doi:10.1002/anie.201508777.
Akturk, Eser S., Yap, Glenn P. A., and Theopold, Klaus H.. 2015. "Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]". United States. doi:10.1002/anie.201508777. https://www.osti.gov/servlets/purl/1342854.
@article{osti_1342854,
title = {Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]},
author = {Akturk, Eser S. and Yap, Glenn P. A. and Theopold, Klaus H.},
abstractNote = {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. Finally, 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.},
doi = {10.1002/anie.201508777},
journal = {Angewandte Chemie (International Edition)},
number = 49,
volume = 54,
place = {United States},
year = {2015},
month = {10}
}