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Title: Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex

Abstract

We report ammonia oxidation by homolytic cleavage of all three H atoms from a Mo-15NH3 complex using the 2,4,6-tri-tert-butylphenoxyl radical to afford a Mo-alkylimido (Mo=15NR) complex (R = 2,4,6-tri-t-butylcyclohexa-2,5-dien-1-one). Reductive cleavage of Mo=15NR generates a terminal Mo≡N nitride, and a [Mo-15NH]+ complex is formed by protonation. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from the Mo-15NH3 complex and the formation of Mo=15NR. 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.

Authors:
; ORCiD logo; ORCiD logo; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1358470
Report Number(s):
PNNL-SA-121628
Journal ID: ISSN 0002-7863; 49375; KC0307010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 8; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
Molybdenum; ammonia; phosphines; pendant amines; hydrogen atom abstraction; Environmental Molecular Sciences Laboratory

Citation Formats

Bhattacharya, Papri, Heiden, Zachariah M., Wiedner, Eric S., Raugei, Simone, Piro, Nicholas A., Kassel, W. Scott, Bullock, R. Morris, and Mock, Michael T. Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex. United States: N. p., 2017. Web. doi:10.1021/jacs.7b00002.
Bhattacharya, Papri, Heiden, Zachariah M., Wiedner, Eric S., Raugei, Simone, Piro, Nicholas A., Kassel, W. Scott, Bullock, R. Morris, & Mock, Michael T. Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex. United States. https://doi.org/10.1021/jacs.7b00002
Bhattacharya, Papri, Heiden, Zachariah M., Wiedner, Eric S., Raugei, Simone, Piro, Nicholas A., Kassel, W. Scott, Bullock, R. Morris, and Mock, Michael T. Wed . "Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex". United States. https://doi.org/10.1021/jacs.7b00002.
@article{osti_1358470,
title = {Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex},
author = {Bhattacharya, Papri and Heiden, Zachariah M. and Wiedner, Eric S. and Raugei, Simone and Piro, Nicholas A. and Kassel, W. Scott and Bullock, R. Morris and Mock, Michael T.},
abstractNote = {We report ammonia oxidation by homolytic cleavage of all three H atoms from a Mo-15NH3 complex using the 2,4,6-tri-tert-butylphenoxyl radical to afford a Mo-alkylimido (Mo=15NR) complex (R = 2,4,6-tri-t-butylcyclohexa-2,5-dien-1-one). Reductive cleavage of Mo=15NR generates a terminal Mo≡N nitride, and a [Mo-15NH]+ complex is formed by protonation. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from the Mo-15NH3 complex and the formation of Mo=15NR. 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.},
doi = {10.1021/jacs.7b00002},
url = {https://www.osti.gov/biblio/1358470}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 8,
volume = 139,
place = {United States},
year = {2017},
month = {2}
}