Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH3 Complex

Bhattacharya, Papri; Heiden, Zachariah M.; Wiedner, Eric S.; Raugei, Simone; Piro, Nicholas A.; Kassel, W. Scott; Bullock, R. Morris; Mock, Michael T.

doi:10.1021/jacs.7b00002

Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH₃ Complex

Journal Article · Tue Feb 14 23:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b00002· OSTI ID:1491705

Bhattacharya, Papri ^[1]; ^[2]; ^[1]; Raugei, Simone ^[1]; Piro, Nicholas A. ^[3]; Kassel, W. Scott ^[3]; ^[1]; ^[1]

Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States
Department of Chemistry, Washington State University, Pullman, Washington 99164, United States
Department of Chemistry, Villanova University, Villanova, Pennsylvania 19085, United States

We report ammonia oxidation by homolytic cleavage of all three H atoms from a Mo৶¹⁵NH³ complex using the 2,4,6-tri-tert-butylphenoxyl radical to afford a Mo-alkylimido (Mo৶¹⁵NR) complex (R = 2,4,6-tri-t-butylcyclohexa-2,5-dien-1-one). Reductive cleavage of Mo৶15NR generates a terminal Mo৶N nitride, and a [Mo৶¹⁵NH]⁺ complex is formed by protonation. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from the Mo৶¹⁵NH₃ complex and the formation of Mo৶¹⁵NR. Acknowledgment. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Re-search Center funded by the U.S. Department of Energy (U.S. DOE), Office of Science, Office of Basic Energy Sciences. EPR and mass spectrometry experiments were performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. The authors thank Dr. Eric D. Walter and Dr. Rosalie Chu for assistance in performing EPR and mass spectroscopy analysis, respectively. Computational resources provided by the National Energy Re-search Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific North-west National Laboratory is operated by Battelle for the U.S. DOE.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

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

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1491705

Report Number(s):: PNNL-SA-121628

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 8 Vol. 139; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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