Details

Autor(en) / Beteiligte

• Bhattacharya, Papri
• Heiden, Zachariah M.
• Chambers, Geoffrey M.
• Johnson, Samantha I.
• Bullock, R. Morris
• Mock, Michael T.

Titel

Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction

Ist Teil von

• Angewandte Chemie (International ed.), 2019-08, Vol.58 (34), p.11618-11624

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2019

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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(PtBu2NPh2)(15NH3)][BArF4], (PtBu2NPh2=1,5‐di(phenylaza)‐3,7‐di(tert‐butylphospha)cyclooctane; ArF=3,5‐(CF3)2C6H3), 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 ion (HAA) steps using the 2,4,6‐tri‐tert‐butylphenoxyl radical (tBu3ArO.) as the H atom acceptor. Employing an excess of tBu3ArO. under 1 atm of NH3 gas at 23 °C resulted in up to ten turnovers. Nitrogen isotopic (15N) labeling studies provide initial mechanistic information suggesting a monometallic pathway during the N⋅⋅⋅N bond‐forming step in the catalytic cycle. Totally radical: A molecular Ru complex catalytically oxidizes 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 ion (HAA) steps using the 2,4,6‐tri‐tert‐butylphenoxyl radical (tBu3ArO.) as the H atom acceptor, resulting in up to 10 turnovers.