Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction
Abstract
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.
- Authors:
-
[2];
[1];
[3]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Washington State Univ., Pullman, WA (United States)
- Montana State Univ., Bozeman, MT (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1572935
- Alternate Identifier(s):
- OSTI ID: 1525550
- Report Number(s):
- PNNL-SA-137210
Journal ID: ISSN 1433-7851; ANIE; TRN: US2001089
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 34; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ammonia oxidation; dinitrogen; homogeneous catalysis; radical reactions; ruthenium
Citation Formats
Bhattacharya, Papri, Heiden, Zachariah M., Chambers, Geoffrey M., Johnson, Samantha I., Bullock, R. Morris, and Mock, Michael T. Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction. United States: N. p., 2019.
Web. doi:10.1002/anie.201903221.
Bhattacharya, Papri, Heiden, Zachariah M., Chambers, Geoffrey M., Johnson, Samantha I., Bullock, R. Morris, & Mock, Michael T. Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction. United States. https://doi.org/10.1002/anie.201903221
Bhattacharya, Papri, Heiden, Zachariah M., Chambers, Geoffrey M., Johnson, Samantha I., Bullock, R. Morris, and Mock, Michael T. Tue .
"Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction". United States. https://doi.org/10.1002/anie.201903221. https://www.osti.gov/servlets/purl/1572935.
@article{osti_1572935,
title = {Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction},
author = {Bhattacharya, Papri and Heiden, Zachariah M. and Chambers, Geoffrey M. and Johnson, Samantha I. and Bullock, R. Morris and Mock, Michael T.},
abstractNote = {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.},
doi = {10.1002/anie.201903221},
journal = {Angewandte Chemie (International Edition)},
number = 34,
volume = 58,
place = {United States},
year = {Tue May 21 00:00:00 EDT 2019},
month = {Tue May 21 00:00:00 EDT 2019}
}
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