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

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

doi:10.1021/jacs.7b00002

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

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

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

Original language	English
Pages (from-to)	2916-2919
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	8
DOIs	https://doi.org/10.1021/jacs.7b00002
Publication status	Published - Mar 1 2017

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.7b00002

Fingerprint Dive into the research topics of 'Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH<sub>3</sub> Complex'. Together they form a unique fingerprint.

Cite this

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.

In: Journal of the American Chemical Society, Vol. 139, No. 8, 01.03.2017, p. 2916-2919.

Research output: Contribution to journal › Article › peer-review

@article{e04fdedc867040939db6fdc0b7d143ef,

title = "Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3 Complex",

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

author = "Papri Bhattacharya and Heiden, {Zachariah M.} and Wiedner, {Eric S.} and Simone Raugei and Piro, {Nicholas A.} and Kassel, {W. Scott} and Bullock, {R. Morris} and Mock, {Michael T.}",

note = "Funding Information: This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research 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 EPR and mass spectroscopy analysis, respectively. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. DOE. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = mar,

day = "1",

doi = "10.1021/jacs.7b00002",

language = "English",

volume = "139",

pages = "2916--2919",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3 Complex

AU - Bhattacharya, Papri

AU - Heiden, Zachariah M.

AU - Wiedner, Eric S.

AU - Raugei, Simone

AU - Piro, Nicholas A.

AU - Kassel, W. Scott

AU - Bullock, R. Morris

AU - Mock, Michael T.

N1 - Funding Information: This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research 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 EPR and mass spectroscopy analysis, respectively. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. DOE. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/3/1

Y1 - 2017/3/1

N2 - We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH3]+ complex using the 2,4,6-tri-tert-butylphenoxyl radical to yield a Mo-alkylimido ([MoNR]+) complex (R = 2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one). Chemical reduction of [MoNR]+ generates a terminal MoN nitride complex upon N-C bond cleavage, and a [MoNH]+ complex is formed by protonation of the nitride. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from [Mo-NH3]+ and formation of [MoNR]+

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

UR - http://www.scopus.com/inward/record.url?scp=85014275872&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85014275872&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b00002

DO - 10.1021/jacs.7b00002

M3 - Article

C2 - 28166403

AN - SCOPUS:85014275872

VL - 139

SP - 2916

EP - 2919

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 8