Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction

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

doi:10.1002/ange.201903221

Title: Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction

Journal Article · Tue Jun 11 00:00:00 UTC 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201903221 · OSTI ID:1525552

Bhattacharya, Papri ^[1];

^[2]; Chambers, Geoffrey M. ^[1]; Johnson, Samantha I. ^[1];

^[1];

^[3]

Center for Molecular Electrocatalysis Pacific Northwest National Laboratory P.O. Box 999 Richland WA 99352 USA
Washington State University Pullman WA 99164 USA
Department of Chemistry and Biochemistry Montana State University Bozeman MT 59717 USA

Abstract Catalysts for the oxidation of NH ₃ are critical for the utilization of NH ₃ as a large‐scale energy carrier. Molecular catalysts capable of oxidizing NH ₃ to N ₂ are rare. This report describes the use of [Cp*Ru(P ^{t Bu} ₂ N ^Ph ₂ )( ¹⁵ NH ₃ )][BAr ^F ₄ ], (P ^{t Bu} ₂ N ^Ph ₂ =1,5‐di(phenylaza)‐3,7‐di(tert‐butylphospha)cyclooctane; Ar ^F =3,5‐(CF ₃ ) ₂ C ₆ H ₃ ), to catalytically oxidize NH ₃ 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 Bu ₃ ArO ^. ) as the H atom acceptor. Employing an excess of ^t Bu ₃ ArO ^. under 1 atm of NH ₃ 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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1525552

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 34 Vol. 131; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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