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.
Akturk, Eser S., et al. "Dioxygen Activation by Non‐Adiabatic Oxidative Addition to a Single Metal Center." Angewandte Chemie, vol. 127, no. 49, Oct. 2015. https://doi.org/10.1002/ange.201508777
Akturk, Eser S., Yap, Glenn P. A., & Theopold, Klaus H. (2015). Dioxygen Activation by Non‐Adiabatic Oxidative Addition to a Single Metal Center. Angewandte Chemie, 127(49). https://doi.org/10.1002/ange.201508777
Akturk, Eser S., Yap, Glenn P. A., and Theopold, Klaus H., "Dioxygen Activation by Non‐Adiabatic Oxidative Addition to a Single Metal Center," Angewandte Chemie 127, no. 49 (2015), https://doi.org/10.1002/ange.201508777
@article{osti_2279221,
author = {Akturk, Eser S. and Yap, Glenn P. A. and Theopold, Klaus H.},
title = {Dioxygen Activation by Non‐Adiabatic Oxidative Addition to a Single Metal Center},
annote = {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. },
doi = {10.1002/ange.201508777},
url = {https://www.osti.gov/biblio/2279221},
journal = {Angewandte Chemie},
issn = {ISSN 0044-8249},
number = {49},
volume = {127},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2015},
month = {10}}