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

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

doi:10.1021/jacs.9b13706

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

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

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· to form 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to 2,6-di-tert-butyl-4-tritylphenoxyl radical, which contains a trityl group at the para position, prevents C-N coupling and diverts the reaction to catalytic oxidation of NH₃ to give N₂. We achieved 125 ± 5 turnovers at 22 °C for oxidation of NH₃, the highest turnover number (TON) reported to date for a molecular catalyst.

Original language	English
Pages (from-to)	3361-3365
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	142
Issue number	7
DOIs	https://doi.org/10.1021/jacs.9b13706
Publication status	Published - Feb 19 2020

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ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Cite this

Dunn, P. L., Johnson, S. I., Kaminsky, W., & Bullock, R. M. (2020). Diversion of Catalytic C-N Bond Formation to Catalytic Oxidation of NH₃ through Modification of the Hydrogen Atom Abstractor. Journal of the American Chemical Society, 142(7), 3361-3365. https://doi.org/10.1021/jacs.9b13706

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title = "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· to form 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to 2,6-di-tert-butyl-4-tritylphenoxyl radical, which contains a trityl group at the para position, prevents C-N coupling and diverts the reaction to catalytic oxidation of NH3 to give N2. We achieved 125 ± 5 turnovers at 22 °C for oxidation of NH3, the highest turnover number (TON) reported to date for a molecular catalyst.",

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N2 - 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· to form 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to 2,6-di-tert-butyl-4-tritylphenoxyl radical, which contains a trityl group at the para position, prevents C-N coupling and diverts the reaction to catalytic oxidation of NH3 to give N2. We achieved 125 ± 5 turnovers at 22 °C for oxidation of NH3, the highest turnover number (TON) reported to date for a molecular catalyst.

AB - 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· to form 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to 2,6-di-tert-butyl-4-tritylphenoxyl radical, which contains a trityl group at the para position, prevents C-N coupling and diverts the reaction to catalytic oxidation of NH3 to give N2. We achieved 125 ± 5 turnovers at 22 °C for oxidation of NH3, the highest turnover number (TON) reported to date for a molecular catalyst.

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10.1021/jacs.9b13706