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

Title: 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.

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.

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

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

Grant/Contract Number:: SC0006498

OSTI ID:: 1616530

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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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
CCDC 1992327: Experimental Crystal Structure Determination Sangmin, Kim,; Hongyu, Zhong,; Yoonsu, Park, https://doi.org/10.5517/ccdc.csd.cc24w5mv The current record is supplemented by this dataset	dataset	January 2020

Title: Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia

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