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

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


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 languageEnglish
Pages (from-to)3361-3365
Number of pages5
JournalJournal of the American Chemical Society
Issue number7
Publication statusPublished - Feb 19 2020

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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