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

Dunn, Peter L.; Johnson, Samantha I.; Kaminsky, Werner; Bullock, R. Morris

doi:10.1021/jacs.9b13706

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

Journal Article · 31 January 2020 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b13706 · OSTI ID:1605349

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

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.

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

CCDC 1972396: Experimental Crystal Structure Determination L., Dunn, Peter; I., Johnson, Samantha; Werner, Kaminsky, https://doi.org/10.5517/ccdc.csd.cc246fph The current record is supplemented by this dataset	dataset	January 2020
CCDC 1972397: Experimental Crystal Structure Determination L., Dunn, Peter; I., Johnson, Samantha; Werner, Kaminsky, https://doi.org/10.5517/ccdc.csd.cc246fqj The current record is supplemented by this dataset	dataset	January 2020
CCDC 1972399: Experimental Crystal Structure Determination L., Dunn, Peter; I., Johnson, Samantha; Werner, Kaminsky, https://doi.org/10.5517/ccdc.csd.cc246fsl The current record is supplemented by this dataset	dataset	January 2020

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

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