Document Type
Article
Publication Date
1-2020
Publication Title
Results in Chemistry
Abstract
The unusual cobalt(II) diphenylazodioxide complex salts [Co(az)4](PF6)2 and [Co(bpy)(az)2](PF6)2 have been shown to catalyze the allylic amination/C–C double bond transposition reaction of 2-methyl-2-pentene with PhNHOH, with a turnover number of about 4. The mechanism is proposed to involve a nitroso-ene-like transfer of a PhNO moiety from the azodioxide ligand to the alkene, followed by reduction of the organic product to yield a cobalt(III) intermediate, which is itself reduced back to cobalt(II) by PhNHOH, regenerating PhNO. Hetero-Diels-Alder trapping experiments suggest that an “off-metal” mechanism, in which PhNO is released from the cobalt complexes and reacts with the alkenes, is operative, in contrast to an “on-metal” mechanism observed by Nicholas and coworkers for [Fe(az)3](FeCl4)2.
Recommended Citation
Emhoff, Kylin A.; Salem, Ahmed M.H.; Balaraman, Lakshmi; Kingery, Drew M.; and Boyd, W. Christropher, "Allylic Amination and Carbon–carbon Double Bond Transposition Catalyzed by Cobalt(II) azodioxide Complexes" (2020). Chemistry Faculty Publications. 531.
https://engagedscholarship.csuohio.edu/scichem_facpub/531
Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.
DOI
10.1016/j.rechem.2019.100016
Version
Publisher's PDF
Volume
2
Comments
Open access
K.A.E. was supported by a Graduate Student Research Award from Cleveland State University.