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

doi:https://doi.org/10.1021/jacs.7b00002

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

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Abstract

We report ammonia oxidation by homolytic cleavage of all three H atoms from a Mo৶ ¹⁵NH ³ complex using the 2,4,6-tri-tert-butylphenoxyl radical to afford a Mo-alkylimido (Mo৶ ¹⁵NR) complex (R = 2,4,6-tri-t-butylcyclohexa-2,5-dien-1-one). Reductive cleavage of Mo৶15NR generates a terminal Mo৶N nitride, and a [Mo৶ ¹⁵NH] ⁺ complex is formed by protonation. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from the Mo৶ ¹⁵NH ₃ complex and the formation of Mo৶ 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:

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

Publication Date:: 2017-02-15

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

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

OSTI Identifier:: 1491705

Report Number(s):: PNNL-SA-121628
Journal ID: ISSN 0002-7863

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

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–NH3 Complex.  United States: N. p., 2017. 
        Web.  doi:10.1021/jacs.7b00002.

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                    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–NH3 Complex.  United States.  https://doi.org/10.1021/jacs.7b00002

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                    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–NH3 Complex".  United States.  https://doi.org/10.1021/jacs.7b00002.

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@article{osti_1491705,

  title        = {Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH3 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 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.},

  doi          = {10.1021/jacs.7b00002},

  url          = {https://www.osti.gov/biblio/1491705},
  journal      = {Journal of the American Chemical Society},

  issn         = {0002-7863},

  number       = 8,

  volume       = 139,

  place        = {United States},

  year         = {2017},

  month        = {2}

}

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https://doi.org/10.1021/jacs.7b00002

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

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Citation Formats

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