Design and reactivity of pentapyridyl metal complexes for ammonia oxidation

Johnson, Samantha I.; Heins, Spencer P.; Klug, Christina M.; Wiedner, Eric S.; Bullock, R. Morris; Raugei, Simone

doi:10.1039/c9cc01249d

Design and reactivity of pentapyridyl metal complexes for ammonia oxidation

Journal Article · Mon Apr 08 00:00:00 EDT 2019 · ChemComm

DOI:https://doi.org/10.1039/c9cc01249d· OSTI ID:1542624

^[1]; Heins, Spencer P. ^[1]; Klug, Christina M. ^[1]; ^[1]; ^[1]; ^[1]

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

In this work, 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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1542624

Alternate ID(s):: OSTI ID: 1506718
OSTI ID: 1526032

Journal Information:: ChemComm, Journal Name: ChemComm Journal Issue: 35 Vol. 55; ISSN CHCOFS; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer Bezdek, Máté J.; Chirik, Paul J. Angewandte Chemie, Vol. 130, Issue 8 https://doi.org/10.1002/ange.201708406	journal	January 2018
Nitrogen-Based Fuels: A Power-to-Fuel-to-Power Analysis Grinberg Dana, Alon; Elishav, Oren; Bardow, André Angewandte Chemie International Edition, Vol. 55, Issue 31 https://doi.org/10.1002/anie.201510618	journal	June 2016
Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer Bezdek, Máté J.; Chirik, Paul J. Angewandte Chemie International Edition, Vol. 57, Issue 8 https://doi.org/10.1002/anie.201708406	journal	January 2018
Cationic Charges Leading to an Inverse Free-Energy Relationship for N−N Bond Formation by Mn ^VI Nitrides Chantarojsiri, Teera; Reath, Alexander H.; Yang, Jenny Y. Angewandte Chemie International Edition, Vol. 57, Issue 43 https://doi.org/10.1002/anie.201805832	journal	October 2018
Towards Catalytic Ammonia Oxidation to Dinitrogen: A Synthetic Cycle by Using a Simple Manganese Complex Keener, Megan; Peterson, Madeline; Hernández Sánchez, Raúl Chemistry - A European Journal, Vol. 23, Issue 48 https://doi.org/10.1002/chem.201703153	journal	August 2017
NBO 6.0 : Natural bond orbital analysis program Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank Journal of Computational Chemistry, Vol. 34, Issue 16 https://doi.org/10.1002/jcc.23266	journal	March 2013
Nitrido and imido transition metal complexes of Groups 6–8 Eikey, R. Coordination Chemistry Reviews, Vol. 243, Issue 1-2 https://doi.org/10.1016/S0010-8545(03)00048-1	journal	August 2003
Metal–Polypyridyl Catalysts for Electro- and Photochemical Reduction of Water to Hydrogen Zee, David Z.; Chantarojsiri, Teera; Long, Jeffrey R. Accounts of Chemical Research, Vol. 48, Issue 7 https://doi.org/10.1021/acs.accounts.5b00082	journal	June 2015
Water-Soluble Iron(IV)-Oxo Complexes Supported by Pentapyridine Ligands: Axial Ligand Effects on Hydrogen Atom and Oxygen Atom Transfer Reactivity Chantarojsiri, Teera; Sun, Yujie; Long, Jeffrey R. Inorganic Chemistry, Vol. 54, Issue 12 https://doi.org/10.1021/acs.inorgchem.5b00658	journal	May 2015
Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species Scheibel, Markus G.; Abbenseth, Josh; Kinauer, Markus Inorganic Chemistry, Vol. 54, Issue 19 https://doi.org/10.1021/acs.inorgchem.5b00829	journal	July 2015
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100085k	journal	December 2010
Nitrogen Cycle Electrocatalysis Rosca, Victor; Duca, Matteo; de Groot, Matheus T. Chemical Reviews, Vol. 109, Issue 6 https://doi.org/10.1021/cr8003696	journal	June 2009
Oxidation of Ammonia in Osmium Polypyridyl Complexes Coia, George M.; Demadis, Konstantinos D.; Meyer, Thomas J. Inorganic Chemistry, Vol. 39, Issue 10 https://doi.org/10.1021/ic0000505	journal	May 2000
Substitution-induced nitrogen-nitrogen coupling for nitride coordinated to osmium(VI) Ware, David C.; Taube, Henry. Inorganic Chemistry, Vol. 30, Issue 24 https://doi.org/10.1021/ic00024a029	journal	November 1991
Polar Effects in Nitride Coupling Reactions Seymore, Sean B.; Brown, Seth N. Inorganic Chemistry, Vol. 41, Issue 3 https://doi.org/10.1021/ic010844z	journal	February 2002
The Remarkable Reactivity of High Oxidation State Ruthenium and Osmium Polypyridyl Complexes Meyer, Thomas J.; Huynh, My Hang V. Inorganic Chemistry, Vol. 42, Issue 25 https://doi.org/10.1021/ic020731v	journal	December 2003
Dinitrogen Formation by Oxidative Intramolecular N---N Coupling in cis,cis- [(bpy) ₂ (NH ₃ )RuORu(NH ₃ )(bpy) ₂ ] ⁴⁺ Ishitani, Osamu; Ando, Emiko; Meyer, Thomas J. Inorganic Chemistry, Vol. 42, Issue 5 https://doi.org/10.1021/ic026096a	journal	March 2003
Reversible interconversion between a nitrido complex of osmium(VI) and an ammine complex of osmium(II) Pipes, David W.; Bakir, Mohammed; Vitols, S. E. Journal of the American Chemical Society, Vol. 112, Issue 14 https://doi.org/10.1021/ja00170a014	journal	July 1990
On the Origin of Selective Nitrous Oxide N−N Bond Cleavage by Three-Coordinate Molybdenum(III) Complexes Cherry, John-Paul F.; Johnson, Adam R.; Baraldo, Luis M. Journal of the American Chemical Society, Vol. 123, Issue 30 https://doi.org/10.1021/ja0031063	journal	August 2001
Oxidation of coordinated ammonia to nitrate Thompson, Mark S.; Meyer, Thomas J. Journal of the American Chemical Society, Vol. 103, Issue 18 https://doi.org/10.1021/ja00408a054	journal	September 1981
Computational and Experimental Study of the Mechanism of Hydrogen Generation from Water by a Molecular Molybdenum-Oxo Electrocatalyst Sundstrom, Eric J.; Yang, Xinzheng; Thoi, V. Sara Journal of the American Chemical Society, Vol. 134, Issue 11 https://doi.org/10.1021/ja210949r	journal	March 2012
C–N Bond Cleavage of Anilines by a (Salen)ruthenium(VI) Nitrido Complex Man, Wai-Lun; Xie, Jianhui; Pan, Yi Journal of the American Chemical Society, Vol. 135, Issue 15 https://doi.org/10.1021/ja401553d	journal	April 2013
Tuning Electronic Structure To Control Manganese Nitride Activation Clarke, Ryan M.; Storr, Tim Journal of the American Chemical Society, Vol. 138, Issue 47 https://doi.org/10.1021/jacs.6b09576	journal	November 2016
Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH ₃ Complex Bhattacharya, Papri; Heiden, Zachariah M.; Wiedner, Eric S. Journal of the American Chemical Society, Vol. 139, Issue 8 https://doi.org/10.1021/jacs.7b00002	journal	February 2017
Nitrogen Activation via Three-Coordinate Molybdenum Complexes: Comparison of Density Functional Theory Performance with Wave Function Based Methods Graham, David C.; Beran, Gregory J. O.; Head-Gordon, Martin The Journal of Physical Chemistry A, Vol. 109, Issue 30 https://doi.org/10.1021/jp044217h	journal	August 2005
A molecular molybdenum-oxo catalyst for generating hydrogen from water Karunadasa, Hemamala I.; Chang, Christopher J.; Long, Jeffrey R. Nature, Vol. 464, Issue 7293 https://doi.org/10.1038/nature08969	journal	April 2010
Powering the planet with solar fuel Gray, Harry B. Nature Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/nchem.141	journal	April 2009
Structural selectivity of supported Pd nanoparticles for catalytic NH3 oxidation resolved using combined operando spectroscopy Dann, Ellie K.; Gibson, Emma K.; Blackmore, Rachel H. Nature Catalysis, Vol. 2, Issue 2 https://doi.org/10.1038/s41929-018-0213-3	journal	January 2019
Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition Schüth, F.; Palkovits, R.; Schlögl, R. Energy Environ. Sci., Vol. 5, Issue 4 https://doi.org/10.1039/C2EE02865D	journal	January 2012
Reactivity of a Ru( iii )–hydroxo complex in substrate oxidation in water Ohzu, Shingo; Ishizuka, Tomoya; Kotani, Hiroaki Chem. Commun., Vol. 50, Issue 95 https://doi.org/10.1039/C4CC07488B	journal	January 2014
Coupling of terminal iridium nitrido complexes Abbenseth, Josh; Finger, Markus; Würtele, Christian Inorganic Chemistry Frontiers, Vol. 3, Issue 4 https://doi.org/10.1039/C5QI00267B	journal	January 2016
Carbon-free energy: a review of ammonia- and hydrazine-based electrochemical fuel cells Rees, Neil V.; Compton, Richard G. Energy & Environmental Science, Vol. 4, Issue 4 https://doi.org/10.1039/c0ee00809e	journal	January 2011
Electrochemical generation of hydrogen from acetic acid using a molecular molybdenum–oxo catalyst Thoi, V. Sara; Karunadasa, Hemamala I.; Surendranath, Yogesh Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21519e	journal	January 2012
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Homogeneous electrocatalytic oxidation of ammonia to N ₂ under mild conditions Habibzadeh, Faezeh; Miller, Susanne L.; Hamann, Thomas W. Proceedings of the National Academy of Sciences, Vol. 116, Issue 8 https://doi.org/10.1073/pnas.1813368116	journal	January 2019
Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex Laplaza, C. E.; Cummins, C. C. Science, Vol. 268, Issue 5212 https://doi.org/10.1126/science.268.5212.861	journal	May 1995
Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex Bezdek, Máté J.; Guo, Sheng; Chirik, Paul J. Science, Vol. 354, Issue 6313 https://doi.org/10.1126/science.aag0246	journal	November 2016
Nitrogen-Based Fuels: A Power-to-Fuel-to-Power Analysis Alon, Grinberg Dana,; Oren, Elishav,; André, Bardow, ETH Zurich https://doi.org/10.3929/ethz-b-000427352	text	January 2016

Cited By (1)

Triple hydrogen atom abstraction from Mn–NH 3 complexes results in cyclophosphazenium cations Cook, Brian J.; Johnson, Samantha I.; Chambers, Geoffrey M. Chemical Communications, Vol. 55, Issue 93 https://doi.org/10.1039/c9cc06915a	journal	January 2019

Similar Records

Design and reactivity of pentapyridyl metal complexes for ammonia oxidation

Journal Article · Tue May 07 00:00:00 EDT 2019 · Chemical Communications · OSTI ID:1526032

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 · OSTI ID:1491705

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Design and reactivity of pentapyridyl metal complexes for ammonia oxidation

Citation Formats

References (38)

Cited By (1)

Similar Records

Related Subjects