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Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b13706· OSTI ID:1605349
 [1];  [1];  [2];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
+ Show Author Affiliations
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.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1605349
Report Number(s):
PNNL-SA--150204
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 7 Vol. 142; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia
catalysis
hydrogen atom transfer