Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor
Abstract
We report that (TMP)Ru(NH3)2 (TMP = tetramesitylporphryin) is a molecular catalyst for oxidation of ammonia to dinitrogen. An aryloxy radical, tri-tert-butylphenoxyl (ArO•) abstracts H atoms from a bound ammonia ligand of (TMP)Ru(NH3)2, leading to the discovery of a new catalytic C-N coupling to the para position of ArO•, forming 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to contain a trityl group at the para position, 2,6-di-tert-butyl-4-tritylphenoxyl radical, prevents C-N coupling and diverts the reaction to catalytic oxidation of ammonia to give N2. We achieve 125(±5) turnovers at 22 °C for oxidation of NH3, the highest reported to date for a molecular catalyst.
- Authors:
-
[1];
[1];
[2];
[1]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1605349
- Report Number(s):
- PNNL-SA-150204
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 7; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ammonia; catalysis; hydrogen atom transfer
Citation Formats
Dunn, Peter L., Johnson, Samantha I., Kaminsky, Werner, and Bullock, R. Morris. Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor. United States: N. p., 2020.
Web. doi:10.1021/jacs.9b13706.
Dunn, Peter L., Johnson, Samantha I., Kaminsky, Werner, & Bullock, R. Morris. Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor. United States. https://doi.org/10.1021/jacs.9b13706
Dunn, Peter L., Johnson, Samantha I., Kaminsky, Werner, and Bullock, R. Morris. Sat .
"Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor". United States. https://doi.org/10.1021/jacs.9b13706. https://www.osti.gov/servlets/purl/1605349.
@article{osti_1605349,
title = {Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor},
author = {Dunn, Peter L. and Johnson, Samantha I. and Kaminsky, Werner and Bullock, R. Morris},
abstractNote = {We report that (TMP)Ru(NH3)2 (TMP = tetramesitylporphryin) is a molecular catalyst for oxidation of ammonia to dinitrogen. An aryloxy radical, tri-tert-butylphenoxyl (ArO•) abstracts H atoms from a bound ammonia ligand of (TMP)Ru(NH3)2, leading to the discovery of a new catalytic C-N coupling to the para position of ArO•, forming 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to contain a trityl group at the para position, 2,6-di-tert-butyl-4-tritylphenoxyl radical, prevents C-N coupling and diverts the reaction to catalytic oxidation of ammonia to give N2. We achieve 125(±5) turnovers at 22 °C for oxidation of NH3, the highest reported to date for a molecular catalyst.},
doi = {10.1021/jacs.9b13706},
journal = {Journal of the American Chemical Society},
number = 7,
volume = 142,
place = {United States},
year = {Sat Feb 01 00:00:00 EST 2020},
month = {Sat Feb 01 00:00:00 EST 2020}
}
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