Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations
Abstract
Extended–coordination sphere interactions between dissolved metals and other ions, including electrolyte cations, are not known to perturb the electrochemical behavior of metal cations in water. Herein, we report the stabilization of higher–oxidation state Np dioxocations in aqueous chloride solutions by hydrophobic tetra-nalkylammonium (TAA+) cations—an effect not exerted by fully hydrated Li+ cations under similar conditions. Experimental and molecular dynamics simulation results indicate that TAA+ cations not only drive enhanced coordination of anionic Cl– ligands to NpV/VI but also associate with the resulting Np complexes via non-covalent interactions, which together decrease the electrode potential of the NpVI/NpV couple by up to 220 mV (ΔΔG = –22.2 kJ mol–1). Understanding the solvation–dependent interplay between electrolyte cations and metal–oxo species opens an avenue for controlling the formation and redox properties of metal complexes in solution. As a result, it also provides valuable mechanistic insights into actinide separation processes that widely use quaternary ammonium cations as extractants or in room temperature ionic liquids.
- Authors:
-
[1];
[2];
[3]
- Argonne National Lab. (ANL), Argonne, IL (United States); Clemson Univ., Anderson, SC (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); 3M Corporate Research Analytical Lab., St. Paul, MN (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1494551
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Estes, Shanna L., Qiao, Baofu, and Jin, Geng Bang. Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations. United States: N. p., 2019.
Web. doi:10.1038/s41467-018-07982-5.
Estes, Shanna L., Qiao, Baofu, & Jin, Geng Bang. Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations. United States. https://doi.org/10.1038/s41467-018-07982-5
Estes, Shanna L., Qiao, Baofu, and Jin, Geng Bang. Fri .
"Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations". United States. https://doi.org/10.1038/s41467-018-07982-5. https://www.osti.gov/servlets/purl/1494551.
@article{osti_1494551,
title = {Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations},
author = {Estes, Shanna L. and Qiao, Baofu and Jin, Geng Bang},
abstractNote = {Extended–coordination sphere interactions between dissolved metals and other ions, including electrolyte cations, are not known to perturb the electrochemical behavior of metal cations in water. Herein, we report the stabilization of higher–oxidation state Np dioxocations in aqueous chloride solutions by hydrophobic tetra-nalkylammonium (TAA+) cations—an effect not exerted by fully hydrated Li+ cations under similar conditions. Experimental and molecular dynamics simulation results indicate that TAA+ cations not only drive enhanced coordination of anionic Cl– ligands to NpV/VI but also associate with the resulting Np complexes via non-covalent interactions, which together decrease the electrode potential of the NpVI/NpV couple by up to 220 mV (ΔΔG = –22.2 kJ mol–1). Understanding the solvation–dependent interplay between electrolyte cations and metal–oxo species opens an avenue for controlling the formation and redox properties of metal complexes in solution. As a result, it also provides valuable mechanistic insights into actinide separation processes that widely use quaternary ammonium cations as extractants or in room temperature ionic liquids.},
doi = {10.1038/s41467-018-07982-5},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}
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Figures / Tables:
Fig. 1: Effect of Li+ vs. [NMe4]+ on the NpVI/NpV couple. Currentnormalized cyclic voltammetry data for solutions of 5 mM NpV dissolved in 5M NMe4Cl or 5 M LiCl at pH ≈ 1.3. The arrow indicates the initial scan direction. Initial and cathodic switching potential= 400/550mV; anodic switching potential= 1000/1150mV;more »
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Works referenced in this record:
The electrochemical behavior of cerium(III/IV) complexes: Thermodynamics, kinetics and applications in synthesis
journal, February 2014
- Piro, Nicholas A.; Robinson, Jerome R.; Walsh, Patrick J.
- Coordination Chemistry Reviews, Vol. 260
Development and application of effective pairwise potentials for UO2n+, NpO2n+, PuO2n+, and AmO2n+ (n = 1, 2) ions with water
journal, January 2013
- Pomogaev, Vladimir; Tiwari, Surya Prakash; Rai, Neeraj
- Physical Chemistry Chemical Physics, Vol. 15, Issue 38
Intensities in the Spectra of Actinyl Ions
journal, December 2000
- Matsika, Spiridoula; Pitzer, Russell M.; Reed, Donald T.
- The Journal of Physical Chemistry A, Vol. 104, Issue 51
The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
journal, March 1974
- Basile, L. J.; Sullivan, J. C.; Ferraro, J. R.
- Applied Spectroscopy, Vol. 28, Issue 2
The Determination of Consecutive Formation Constants of Complex Ions from Polarographic Data
journal, November 1951
- DeFord, Donald D.; Hume, David N.
- Journal of the American Chemical Society, Vol. 73, Issue 11
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Theoretical and experimental study of the vibrational frequencies of UO2 2+ and NpO2 2+ in highly concentrated chloride solutions
journal, July 2014
- Fujii, Toshiyuki; Uehara, Akihiro; Kitatsuji, Yoshihiro
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 303, Issue 1
A Comparison of Neptunyl(V) and Neptunyl(VI) Solution Coordination: The Stability of Cation−Cation Interactions
journal, June 2008
- Skanthakumar, S.; Antonio, Mark R.; Soderholm, L.
- Inorganic Chemistry, Vol. 47, Issue 11
The Mechanism of Water Exchange in AmO 2 (H 2 O) 5 2+ and in the Isoelectronic UO 2 (H 2 O) 5 + and NpO 2 (H 2 O) 5 2+ Complexes as Studied by Quantum Chemical Methods
journal, June 2004
- Vallet, Valérie; Privalov, Timofei; Wahlgren, Ulf
- Journal of the American Chemical Society, Vol. 126, Issue 25
Lanthanides and Actinides in Ionic Liquids
journal, June 2007
- Binnemans, Koen
- Chemical Reviews, Vol. 107, Issue 6
GROMACS 4: Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
journal, February 2008
- Hess, Berk; Kutzner, Carsten; van der Spoel, David
- Journal of Chemical Theory and Computation, Vol. 4, Issue 3
Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters
journal, March 2013
- Tsui, Emily Y.; Tran, Rosalie; Yano, Junko
- Nature Chemistry, Vol. 5, Issue 4
Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example
journal, November 2017
- Jin, Geng Bang; Lin, Jian; Estes, Shanna L.
- Journal of the American Chemical Society, Vol. 139, Issue 49
Cation–cation interactions between NpO2+ and UO22+ at different temperatures and ionic strengths
journal, January 2012
- Xian, Liang; Tian, Guoxin; Zheng, Weifang
- Dalton Transactions, Vol. 41, Issue 28
Specific Interaction between Np(V) and U(VI) in Aqueous Perchloric Acid Media 1
journal, August 1961
- Sullivan, J. C.; Hindman, J. C.; Zielen, A. J.
- Journal of the American Chemical Society, Vol. 83, Issue 16
Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods
journal, November 2012
- Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar
- The Journal of Physical Chemistry A, Vol. 116, Issue 50
Uranyl to Uranium(IV) Conversion through Manipulation of Axial and Equatorial Ligands
journal, February 2018
- Bell, Nicola L.; Shaw, Brian; Arnold, Polly L.
- Journal of the American Chemical Society, Vol. 140, Issue 9
Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions
journal, March 1982
- Guillaume, B.; Begun, G. M.; Hahn, R. L.
- Inorganic Chemistry, Vol. 21, Issue 3
Uranium and manganese assembled in a wheel-shaped nanoscale single-molecule magnet with high spin-reversal barrier
journal, November 2012
- Mougel, Victor; Chatelain, Lucile; Pécaut, Jacques
- Nature Chemistry, Vol. 4, Issue 12
Ion Pairing
journal, November 2006
- Marcus, Yizhak; Hefter, Glenn
- Chemical Reviews, Vol. 106, Issue 11
Electron-Transfer Kinetics of Np[sup 3+]∕Np[sup 4+], NpO[sub 2][sup +]∕NpO[sub 2][sup 2+], V[sup 2+]∕V[sup 3+], and VO[sup 2+]∕VO[sub 2][sup +] at Carbon Electrodes
journal, January 2005
- Yamamura, Tomoo; Watanabe, Nobutaka; Yano, Takashi
- Journal of The Electrochemical Society, Vol. 152, Issue 4
Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands
journal, December 1992
- Nguyen Trung, Chinh; Begun, G. M.; Palmer, Donald A.
- Inorganic Chemistry, Vol. 31, Issue 25
Cation−Cation Interactions between Uranyl Cations in a Polar Open-Framework Uranyl Periodate
journal, March 2004
- Sullens, Tyler A.; Jensen, Rebecca A.; Shvareva, Tatiana Y.
- Journal of the American Chemical Society, Vol. 126, Issue 9
Neptunium Carbonato Complexes in Aqueous Solution: An Electrochemical, Spectroscopic, and Quantum Chemical Study
journal, December 2009
- Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro
- Inorganic Chemistry, Vol. 48, Issue 24
Three New Sodium Neptunyl(V) Selenate Hydrates: Structures, Raman Spectroscopy, and Magnetism
journal, February 2012
- Jin, Geng Bang; Skanthakumar, S.; Soderholm, L.
- Inorganic Chemistry, Vol. 51, Issue 5
Pentavalent Neptunyl ([O≡Np≡O]+) Cation–Cation Interactions in Aqueous/Polar Organic Mixed-Solvent Media
journal, June 2017
- Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.
- Journal of Solution Chemistry, Vol. 46, Issue 6
Synthesis and single crystal X-ray diffraction study of U(VI), Np(VI), and Pu(VI) perchlorate hydrates
journal, August 2010
- Grigor’ev, M. S.; Krot, N. N.
- Radiochemistry, Vol. 52, Issue 4
Reduction and selective oxo group silylation of the uranyl dication
journal, January 2008
- Arnold, Polly L.; Patel, Dipti; Wilson, Claire
- Nature, Vol. 451, Issue 7176
A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2 ·M] 4+ Cation–Cation Complexes
journal, April 2017
- Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.
- Inorganic Chemistry, Vol. 56, Issue 9
Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer
journal, July 2010
- Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki
- Nature Chemistry, Vol. 2, Issue 9
Three-Dimensional Network of Cation–Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies
journal, February 2016
- Jin, Geng Bang
- Inorganic Chemistry, Vol. 55, Issue 5
Mixed-Valent Neptunium(IV/V) Compound with Cation–Cation-Bound Six-Membered Neptunyl Rings
journal, October 2013
- Jin, Geng Bang
- Inorganic Chemistry, Vol. 52, Issue 21
Spectrophotometry of Neptunium in Perchloric Acid Solutions 1
journal, April 1951
- Sjoblom, R.; Hindman, J. C.
- Journal of the American Chemical Society, Vol. 73, Issue 4
Control of cerium oxidation state through metal complex secondary structures
journal, January 2015
- Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.
- Chemical Science, Vol. 6, Issue 12
Redox Energetics and Kinetics of Uranyl Coordination Complexes in Aqueous Solution
journal, July 2002
- Morris, David E.
- Inorganic Chemistry, Vol. 41, Issue 13
Energetics and hydration of the constituent ion pairs of tetramethylammonium chloride
journal, March 1989
- Buckner, J. Kathleen; Jorgensen, William L.
- Journal of the American Chemical Society, Vol. 111, Issue 7
XANES Spectroelectrochemistry: A New Method for Determining Formal Potentials
journal, October 1999
- Soderholm, L.; Antonio, Mark R.; Williams, Clayton
- Analytical Chemistry, Vol. 71, Issue 20
A simple empirical model describing the thermodynamics of hydration of ions of widely varying charges, sizes, and shapes
journal, August 1994
- Marcus, Yizhak
- Biophysical Chemistry, Vol. 51, Issue 2-3
Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007
- Denning, Robert G.
- The Journal of Physical Chemistry A, Vol. 111, Issue 20
Thermodynamics of Neptunium(Y) in Concentrated Salt Solutions: Chloride Complexation and Ion Interaction (Pitzer) Parameters for the NpO+2 Ion
journal, January 1995
- Neck, V.; Fanghänel, Th.; Rudolph, G.
- Radiochimica Acta, Vol. 69, Issue 1
The geometric structures, vibrational frequencies and redox properties of the actinyl coordination complexes ([AnO2(L)n]m; An = U, Pu, Np; L = H2O, Cl−, CO32−, CH3CO2−, OH−) in aqueous solution, studied by density functional theory methods
journal, January 2009
- Austin, Jonathan P.; Sundararajan, Mahesh; Vincent, Mark A.
- Dalton Transactions, Issue 30
Exploring the Effects of Reduction or Lewis Acid Coordination on the UO Bond of the Uranyl Moiety
journal, April 2009
- Hayton, Trevor W.; Wu, Guang
- Inorganic Chemistry, Vol. 48, Issue 7
Solvation of Uranyl(II), Europium(III) and Europium(II) Cations in“Basic” Room-Temperature Ionic Liquids: A Theoretical Study
journal, August 2004
- Chaumont, Alain; Wipff, Georges
- Chemistry - A European Journal, Vol. 10, Issue 16
Role of the Uranyl Oxo Group as a Hydrogen Bond Acceptor
journal, March 2011
- Watson, Lori A.; Hay, Benjamin P.
- Inorganic Chemistry, Vol. 50, Issue 6
The Sulfate Coordination of Np(IV), Np(V), and Np(VI) in Aqueous Solution
journal, June 2009
- Hennig, Christoph; Ikeda-Ohno, Atsushi; Tsushima, Satoru
- Inorganic Chemistry, Vol. 48, Issue 12
Investigation of Aquo and Chloro Complexes of UO 2 2+ , NpO 2 + , Np 4+ , and Pu 3+ by X-ray Absorption Fine Structure Spectroscopy
journal, October 1997
- Allen, P. G.; Bucher, J. J.; Shuh, D. K.
- Inorganic Chemistry, Vol. 36, Issue 21
The Mechanism of Water Exchange in AmO2(H2O)52+ and in the Isoelectronic UO2(H2O)5+ and NpO2(H2O)52+ Complexes as Studied by Quantum Chemical Methods.
journal, September 2004
- Vallet, Valerie; Privalov, Timofei; Wahlgren, Ulf
- ChemInform, Vol. 35, Issue 36
Works referencing / citing this record:
Impacts of hydrogen bonding interactions with Np( v / vi )O 2 Cl 4 complexes: vibrational spectroscopy, redox behavior, and computational analysis
journal, January 2020
- Pyrch, Mikaela M.; Bjorklund, Jennifer L.; Williams, James M.
- Dalton Transactions, Vol. 49, Issue 20
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