Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]

Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

doi:10.1002/anie.201508777

Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O₂ activation by non-adiabatic oxidative addition to a single metal center]

Journal Article · Fri Oct 16 00:00:00 EDT 2015 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201508777· OSTI ID:1342854

Akturk, Eser S. ^[1]; Yap, Glenn P. A. ^[2]; Theopold, Klaus H. ^[2]

Univ. of Delaware, Newark, DE (United States); Office of Scientific and Technical Information (OSTI)
Univ. of Delaware, Newark, DE (United States)

A chromium(I) dinitrogen complex reacts rapidly with O₂ 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(S₂)]. The transformation of the putative peroxo intermediate [Tp^tBu,MeCr^III(O₂)] (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 O₂ activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-92ER14273

OSTI ID:: 1342854

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 54; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (3)

Rhodium Complexes Promoting C−O Bond Formation in Reactions with Oxygen: The Role of Superoxo Species Vilella-Arribas, Laia; García-Melchor, Max; Balcells, David Chemistry - A European Journal, Vol. 23, Issue 22 https://doi.org/10.1002/chem.201605959	journal	March 2017
The Influence of Alkali Metal Ions on the Stability and Reactivity of Chromium(III) Superoxide Moieties Spanned by Siloxide Ligands Wind, Marie‐Louise; Hoof, Santina; Herwig, Christian Chemistry – A European Journal, Vol. 25, Issue 22 https://doi.org/10.1002/chem.201900236	journal	March 2019
Scorpionates of the “Tetrahedral Enforcer” Variety as Ancillary Ligands for Dinitrogen Complexes of First Row Transition Metals (Cr-Co): Scorpionates of the “Tetrahedral Enforcer” Variety as Ancillary Ligands for Dinitrogen Complexes of First Row Transition Metals (Cr-Co) Cummins, Daniel C.; Yap, Glenn P. A.; Theopold, Klaus H. European Journal of Inorganic Chemistry, Vol. 2016, Issue 15-16 https://doi.org/10.1002/ejic.201501326	journal	February 2016

Figures / Tables (3)

Figure 1(p. 6)

Figure 2(p. 7)

Figure 3(p. 8)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ab initio calculations
chromium
dioxygen activation
spin-forbidden reactions
sulfur

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