Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia

Kim, Sangmin; Zhong, Hongyu; Park, Yoonsu; Loose, Florian; Chirik, Paul J.

doi:10.1021/jacs.0c03346

Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia

Journal Article · Mon Apr 27 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c03346· OSTI ID:1616530

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Princeton Univ., NJ (United States). Frick Lab.; Princeton University
Princeton Univ., NJ (United States). Frick Lab.

The catalytic hydrogenation of a metal nitride to make free ammonia using a rhodium hydride catalyst that promotes H₂ activation and hydrogen atom transfer is described. The phenylimine-substituted rhodium complex, (η⁵-C₅Me₅)Rh(^MePhI)H (^MePhI = N-methyl-1-phenylethan-1-imine) exhibited higher thermal stability compared to the previously reported (η⁵-C₅Me₅)Rh(ppy)H (ppy = 2-phenylpyridine). DFT calculations established that the two rhodium complexes have comparable Rh–H bond dissociation free energies of 51.8 kcal mol-1 for (η⁵-C₅Me₅)Rh(MePhI)H and 51.1 kcal mol^-1 for (η⁵-C₅Me₅)Rh(ppy)H. In the presence of 10 mol% of the phe-nylimine rhodium precatalyst and 4 atm of H₂ in THF, the manganese nitride, (^tBuSalen)Mn≡N underwent hydrogenation to liberate free ammonia with up to 6 total turnovers of NH₃ or 18 turnovers of H·. The phenylpyridine analogue proved inactive for ammonia synthesis under identical conditions owing to competing deleterious hydride transfer chemistry. Subsequent research showed that the use of a non-polar solvent such as benzene suppressed formation of the cationic rhodium product resulting from the hydride transfer and enabled catalytic ammonia synthesis by proton coupled electron transfer.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0006498

OSTI ID:: 1616530

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 20 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1992323: Experimental Crystal Structure Determination Sangmin, Kim,; Hongyu, Zhong,; Yoonsu, Park, https://doi.org/10.5517/ccdc.csd.cc24w5hq The current record is supplemented by this dataset	dataset	January 2020
CCDC 1992324: Experimental Crystal Structure Determination Sangmin, Kim,; Hongyu, Zhong,; Yoonsu, Park, https://doi.org/10.5517/ccdc.csd.cc24w5jr The current record is supplemented by this dataset	dataset	January 2020
CCDC 1992325: Experimental Crystal Structure Determination Sangmin, Kim,; Hongyu, Zhong,; Yoonsu, Park, https://doi.org/10.5517/ccdc.csd.cc24w5ks The current record is supplemented by this dataset	dataset	January 2020
CCDC 1992326: Experimental Crystal Structure Determination Sangmin, Kim,; Hongyu, Zhong,; Yoonsu, Park, https://doi.org/10.5517/ccdc.csd.cc24w5lt The current record is supplemented by this dataset	dataset	January 2020
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Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia

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