Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction

Catalysts for the oxidation of NH3 are critical for the utilization of NH3 as a large-scale energy carrier. Molecular catalysts capable of oxidizing NH3 to N2 are rare. This report describes the use of [Cp*Ru(PtBu2 NPh2 )(15 NH3 )][BArF4 ], (PtBu2 NPh2 =1,5-di(phenylaza)-3,7-di(tert-butylphospha)cyclooctane; ArF =3,5-(CF3 )2 C6 H3 ), to catalytically oxidize NH3 to dinitrogen under ambient conditions. The cleavage of six N-H bonds and the formation of an N≡N bond was achieved by coupling H+ and e- transfers as net hydrogen atom abstraction (HAA) steps using the 2,4,6-tri-tert-butylphenoxyl radical (t Bu3 ArO. ) as the H atom acceptor. Employing an excess of t Bu3 ArO. under 1 atm of NH3 gas at 23 °C resulted in up to ten turnovers. Nitrogen isotopic (15 N) labeling studies provide initial mechanistic information suggesting a monometallic pathway during the N⋅⋅⋅N bond-forming step in the catalytic cycle.