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Title: Design and reactivity of pentapyridyl metal complexes for ammonia oxidation

Abstract

Oxidation of NH3 to N2 by pentapyridyl metal complexes via hydrogen atom abstraction was investigated computationally. Quantum chemical analysis reveals insights on orbital symmetry requirements for efficient NH3 oxidation. The most promising complex, [(PY5)Mo(NH3)]2+, was studied experimentally. It shows conversion of NH3 to N2 upon treatment with 2,4,6-tri-tert-butylphenoxyl radical.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Center for Molecular Electrocatalysis; Pacific Northwest National Laboratory; Richland; USA
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1542624
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 55; Journal Issue: 35; Journal ID: ISSN 1359-7345
Country of Publication:
United States
Language:
English

Citation Formats

Johnson, Samantha I., Heins, Spencer P., Klug, Christina M., Wiedner, Eric S., Bullock, R. Morris, and Raugei, Simone. Design and reactivity of pentapyridyl metal complexes for ammonia oxidation. United States: N. p., 2019. Web. doi:10.1039/c9cc01249d.
Johnson, Samantha I., Heins, Spencer P., Klug, Christina M., Wiedner, Eric S., Bullock, R. Morris, & Raugei, Simone. Design and reactivity of pentapyridyl metal complexes for ammonia oxidation. United States. https://doi.org/10.1039/c9cc01249d
Johnson, Samantha I., Heins, Spencer P., Klug, Christina M., Wiedner, Eric S., Bullock, R. Morris, and Raugei, Simone. Tue . "Design and reactivity of pentapyridyl metal complexes for ammonia oxidation". United States. https://doi.org/10.1039/c9cc01249d.
@article{osti_1542624,
title = {Design and reactivity of pentapyridyl metal complexes for ammonia oxidation},
author = {Johnson, Samantha I. and Heins, Spencer P. and Klug, Christina M. and Wiedner, Eric S. and Bullock, R. Morris and Raugei, Simone},
abstractNote = {Oxidation of NH3 to N2 by pentapyridyl metal complexes via hydrogen atom abstraction was investigated computationally. Quantum chemical analysis reveals insights on orbital symmetry requirements for efficient NH3 oxidation. The most promising complex, [(PY5)Mo(NH3)]2+, was studied experimentally. It shows conversion of NH3 to N2 upon treatment with 2,4,6-tri-tert-butylphenoxyl radical.},
doi = {10.1039/c9cc01249d},
url = {https://www.osti.gov/biblio/1542624}, journal = {ChemComm},
issn = {1359-7345},
number = 35,
volume = 55,
place = {United States},
year = {2019},
month = {1}
}

Works referenced in this record:

Powering the planet with solar fuel
journal, April 2009


Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006


Nitrogen-Based Fuels: A Power-to-Fuel-to-Power Analysis
journal, June 2016


Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition
journal, January 2012


Carbon-free energy: a review of ammonia- and hydrazine-based electrochemical fuel cells
journal, January 2011


Nitrogen Cycle Electrocatalysis
journal, June 2009


Structural selectivity of supported Pd nanoparticles for catalytic NH3 oxidation resolved using combined operando spectroscopy
journal, January 2019


Homogeneous electrocatalytic oxidation of ammonia to N 2 under mild conditions
journal, January 2019


Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex
journal, November 2016


Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer
journal, January 2018


Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex
journal, February 2017


Cationic Charges Leading to an Inverse Free-Energy Relationship for N−N Bond Formation by Mn VI Nitrides
journal, October 2018


Tuning Electronic Structure To Control Manganese Nitride Activation
journal, November 2016


Towards Catalytic Ammonia Oxidation to Dinitrogen: A Synthetic Cycle by Using a Simple Manganese Complex
journal, August 2017


C–N Bond Cleavage of Anilines by a (Salen)ruthenium(VI) Nitrido Complex
journal, April 2013


Dinitrogen Formation by Oxidative Intramolecular N---N Coupling in cis,cis- [(bpy) 2 (NH 3 )RuORu(NH 3 )(bpy) 2 ] 4+
journal, March 2003


Coupling of terminal iridium nitrido complexes
journal, January 2016


Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species
journal, July 2015


Oxidation of coordinated ammonia to nitrate
journal, September 1981


Reversible interconversion between a nitrido complex of osmium(VI) and an ammine complex of osmium(II)
journal, July 1990


Oxidation of Ammonia in Osmium Polypyridyl Complexes
journal, May 2000


The Remarkable Reactivity of High Oxidation State Ruthenium and Osmium Polypyridyl Complexes
journal, December 2003


Computational and Experimental Study of the Mechanism of Hydrogen Generation from Water by a Molecular Molybdenum-Oxo Electrocatalyst
journal, March 2012


A molecular molybdenum-oxo catalyst for generating hydrogen from water
journal, April 2010


Reactivity of a Ru( iii )–hydroxo complex in substrate oxidation in water
journal, January 2014


Electrochemical generation of hydrogen from acetic acid using a molecular molybdenum–oxo catalyst
journal, January 2012


Metal–Polypyridyl Catalysts for Electro- and Photochemical Reduction of Water to Hydrogen
journal, June 2015


Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010


NBO 6.0 : Natural bond orbital analysis program
journal, March 2013


On the Origin of Selective Nitrous Oxide N−N Bond Cleavage by Three-Coordinate Molybdenum(III) Complexes
journal, August 2001


Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex
journal, May 1995


Polar Effects in Nitride Coupling Reactions
journal, February 2002


Substitution-induced nitrogen-nitrogen coupling for nitride coordinated to osmium(VI)
journal, November 1991


Nitrido and imido transition metal complexes of Groups 6–8
journal, August 2003


Nitrogen Activation via Three-Coordinate Molybdenum Complexes: Comparison of Density Functional Theory Performance with Wave Function Based Methods
journal, August 2005