Catalytic reduction of dinitrogen to ammonia using molybdenum porphyrin complexes

Porphyrin complexes are well-known in O 2 and CO 2 reduction, but their application to N 2 reduction is less developed. Here, we show that oxo and nitrido complexes of molybdenum supported by tetramesitylporphyrin (TMP) are effective precatalysts for catalytic N 2 reduction to ammonia, verified by 1...

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Bibliographic Details
Published in:Faraday discussions 2023-07, Vol.243, p.429-449
Main Authors: Hegg, Alexander S, Mercado, Brandon Q, Miller, Alexander J. M, Holland, Patrick L
Format: Article
Language:English
Subjects:
Ammonia
Catalysis
Chemical reduction
Energy of dissociation
Free energy
Hydrogen bonds
Molybdenum
Porphyrins
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Summary:Porphyrin complexes are well-known in O 2 and CO 2 reduction, but their application to N 2 reduction is less developed. Here, we show that oxo and nitrido complexes of molybdenum supported by tetramesitylporphyrin (TMP) are effective precatalysts for catalytic N 2 reduction to ammonia, verified by 15 N 2 labeling studies and other control experiments. Spectroscopic and electrochemical studies illuminate some relevant thermodynamic parameters, including the N-H bond dissociation free energy of (TMP)MoNH (43 ± 2 kcal mol −1 ). We place these results in the context of other work on homogeneous N 2 reduction catalysis. N 2 reduction to ammonia is catalyzed by molybdenum complexes of a bulky porphyrin, and the thermodynamics of the first PCET step are evaluated.
ISSN:1359-6640
1364-5498
DOI:10.1039/d2fd00166g