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Catalytic Transfer Hydrogenation of N to NH Via a Photoredox Catalysis Strategy

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Journal Sci Adv
Specialties Biology
Science
Date 2022 Oct 26
PMID 36288295
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Abstract

Inspired by momentum in applications of reductive photoredox catalysis to organic synthesis, photodriven transfer hydrogenations toward deep (>2 e) reductions of small molecules are attractive compared to using harsh chemical reagents. Noteworthy in this context is the nitrogen reduction reaction (NRR), where a synthetic photocatalyst system had yet to be developed. Noting that a reduced Hantzsch ester (HEH) and related organic structures can behave as 2 e/2 H photoreductants, we show here that, when partnered with a suitable catalyst (Mo) under blue light irradiation, HEH facilitates delivery of successive H equivalents for the 6 e/6 H catalytic reduction of N to NH; this catalysis is enhanced by addition of a photoredox catalyst (Ir). Reductions of additional substrates (nitrate and acetylene) are also described.

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References
1.
Zhu D, Wu Q, Li H, Li H, Lang J . Hantzsch Ester as a Visible-Light Photoredox Catalyst for Transition-Metal-Free Coupling of Arylhalides and Arylsulfinates. Chemistry. 2020; 26(16):3484-3488. DOI: 10.1002/chem.201905281. View

2.
Wang D, Loose F, Chirik P, Knowles R . N-H Bond Formation in a Manganese(V) Nitride Yields Ammonia by Light-Driven Proton-Coupled Electron Transfer. J Am Chem Soc. 2019; 141(12):4795-4799. DOI: 10.1021/jacs.8b12957. View

3.
Ilic S, Kadel U, Basdogan Y, Keith J, Glusac K . Thermodynamic Hydricities of Biomimetic Organic Hydride Donors. J Am Chem Soc. 2018; 140(13):4569-4579. DOI: 10.1021/jacs.7b13526. View

4.
Tanaka H, Arashiba K, Kuriyama S, Sasada A, Nakajima K, Yoshizawa K . Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia. Nat Commun. 2014; 5:3737. PMC: 4015321. DOI: 10.1038/ncomms4737. View

5.
Brown K, Harris D, Wilker M, Rasmussen A, Khadka N, Hamby H . Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid. Science. 2016; 352(6284):448-50. DOI: 10.1126/science.aaf2091. View