Exploring Soft Donor Character of the N-2-Pyrazinylmethyl Group by Coordinating Trivalent Actinides and Lanthanides Using Aminopolycarboxylates
Abstract
The trivalent f-element coordination chemistry of a novel aminopolycarboxylate complexant was investigated. The novel reagent is an octadentate complexant that resembles diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA), but a single N-acetate pendant arm was substituted with a N-2-pyrazinylmethyl functional group. Thermodynamic studies of ligand protonation and trivalent lanthanide, americium and curium, complexation by N-2-pyrazinylmethyldiethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-PzM) emphasize the strong electron withdrawing influence of the N-2-pyrazinylmethyl group. Particularly, DTTA-PzM is more acidic compared to a N-2-pyridinylmethyl-substituted structural equivalent, DTTA-PyM, with a substantial lowering of pK7, corresponding to the protonation of a second aliphatic amine site. The participation of the pyrizyl nitrogen in the metal ion coordination sphere is observed from the fluorescence lifetime decay measurements of metal hydration and the interpretation of the stability constants for ML– and MHL(aq) complexes. The overall conditional stability constants for the trivalent f-element complexation by DTTA-PzM complexes decrease, relative to DTTA-PyM, as expected based on the lower basicity of pyrazine in water relative to pyridine. Replacement of the N-2-pyridinylmethyl group with N-2-pyrazinylmethyl, while enhancing the total acidity of DTTA-PzM, also reduces its softness, as manifested by a small lowering of β101Am/Nd and liquid–liquid separation of trivalent lanthanides from trivalent americium. Despite this, the 4f/5f separation is doubled whenmore »
- Authors:
-
[1];
[1];
[2];
[2];
[2];
[1]
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Idaho National Lab. (INL), Idaho Falls, ID (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)
- OSTI Identifier:
- 1591637
- Alternate Identifier(s):
- OSTI ID: 1564174
- Report Number(s):
- INL/JOU-19-55470-Rev000
Journal ID: ISSN 0020-1669; TRN: US2101860
- Grant/Contract Number:
- AC07-05ID14517; AC02-05CH11231; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 1; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; 12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; aminopolycarboxylates; actinides; lanthanides; metal chelators; aqueous separations
Citation Formats
Grimes, Travis S., Heathman, Colt R., Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., and Zalupski, Peter R. Exploring Soft Donor Character of the N-2-Pyrazinylmethyl Group by Coordinating Trivalent Actinides and Lanthanides Using Aminopolycarboxylates. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b01427.
Grimes, Travis S., Heathman, Colt R., Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., & Zalupski, Peter R. Exploring Soft Donor Character of the N-2-Pyrazinylmethyl Group by Coordinating Trivalent Actinides and Lanthanides Using Aminopolycarboxylates. United States. https://doi.org/10.1021/acs.inorgchem.9b01427
Grimes, Travis S., Heathman, Colt R., Jansone-Popova, Santa, Ivanov, Alexander S., Bryantsev, Vyacheslav S., and Zalupski, Peter R. Tue .
"Exploring Soft Donor Character of the N-2-Pyrazinylmethyl Group by Coordinating Trivalent Actinides and Lanthanides Using Aminopolycarboxylates". United States. https://doi.org/10.1021/acs.inorgchem.9b01427. https://www.osti.gov/servlets/purl/1591637.
@article{osti_1591637,
title = {Exploring Soft Donor Character of the N-2-Pyrazinylmethyl Group by Coordinating Trivalent Actinides and Lanthanides Using Aminopolycarboxylates},
author = {Grimes, Travis S. and Heathman, Colt R. and Jansone-Popova, Santa and Ivanov, Alexander S. and Bryantsev, Vyacheslav S. and Zalupski, Peter R.},
abstractNote = {The trivalent f-element coordination chemistry of a novel aminopolycarboxylate complexant was investigated. The novel reagent is an octadentate complexant that resembles diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA), but a single N-acetate pendant arm was substituted with a N-2-pyrazinylmethyl functional group. Thermodynamic studies of ligand protonation and trivalent lanthanide, americium and curium, complexation by N-2-pyrazinylmethyldiethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-PzM) emphasize the strong electron withdrawing influence of the N-2-pyrazinylmethyl group. Particularly, DTTA-PzM is more acidic compared to a N-2-pyridinylmethyl-substituted structural equivalent, DTTA-PyM, with a substantial lowering of pK7, corresponding to the protonation of a second aliphatic amine site. The participation of the pyrizyl nitrogen in the metal ion coordination sphere is observed from the fluorescence lifetime decay measurements of metal hydration and the interpretation of the stability constants for ML– and MHL(aq) complexes. The overall conditional stability constants for the trivalent f-element complexation by DTTA-PzM complexes decrease, relative to DTTA-PyM, as expected based on the lower basicity of pyrazine in water relative to pyridine. Replacement of the N-2-pyridinylmethyl group with N-2-pyrazinylmethyl, while enhancing the total acidity of DTTA-PzM, also reduces its softness, as manifested by a small lowering of β101Am/Nd and liquid–liquid separation of trivalent lanthanides from trivalent americium. Despite this, the 4f/5f separation is doubled when DTTA-PzM replaces DTPA as an aqueous complexant in solvent extraction.},
doi = {10.1021/acs.inorgchem.9b01427},
journal = {Inorganic Chemistry},
number = 1,
volume = 59,
place = {United States},
year = {2019},
month = {8}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
A REVIEW OF THE BASIC CHEMISTRY AND RECENT DEVELOPMENTS IN TRIVALENT f-ELEMENTS SEPARATIONS
journal, May 1993
- Nash, Kenneth L.
- Solvent Extraction and Ion Exchange, Vol. 11, Issue 4
Separation of trivalent actinides and lanthanides using various ‘N’, ‘S’ and mixed ‘N,O’ donor ligands: a review
journal, September 2019
- Bhattacharyya, Arunasis; Mohapatra, Prasanta K.
- Radiochimica Acta, Vol. 107, Issue 9-11
A NEW VALENCE STATE OF AMERICIUM, AM(VI) 1
journal, March 1950
- Asprey, L. B.; Stephanou, S. E.; Penneman, R. A.
- Journal of the American Chemical Society, Vol. 72, Issue 3
Hexavalent Americium 1
journal, December 1951
- Asprey, L. B.; Stephanou, S. E.; Penneman, R. A.
- Journal of the American Chemical Society, Vol. 73, Issue 12
Redox-Based Separation of Americium from Lanthanides in Sulfate Media
journal, July 2010
- Shehee, Thomas; Martin, Leigh R.; Zalupski, Peter R.
- Separation Science and Technology, Vol. 45, Issue 12-13
Tributylphosphate Extraction Behavior of Bismuthate-Oxidized Americium
journal, August 2008
- Mincher, Bruce J.; Martin, Leigh R.; Schmitt, Nicholas C.
- Inorganic Chemistry, Vol. 47, Issue 15
Diamylamylphosphonate Solvent Extraction of Am(VI) from Nuclear Fuel Raffinate Simulant Solution
journal, August 2012
- Mincher, Bruce J.; Martin, Leigh R.; Schmitt, Nicholas C.
- Solvent Extraction and Ion Exchange, Vol. 30, Issue 5
Characterizing Diamylamylphosphonate (DAAP) as an Americium Ligand for Nuclear Fuel-Cycle Applications
journal, January 2014
- Mincher, Bruce J.; Schmitt, Nicholas C.; Tillotson, Richard D.
- Solvent Extraction and Ion Exchange, Vol. 32, Issue 2
Oxidation and extraction of Am(VI) using a monoamidic extractant in 3D printed centrifugal contactors
journal, August 2018
- Law, Jack D.; Mincher, Bruce J.; Tillotson, Richard D.
- Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 1
Americium(III) oxidation by copper(III) periodate in nitric acid solution as compared with the action of Bi(V) compounds of sodium, lithium, and potassium
journal, January 2015
- Sinkov, Sergey I.; Lumetta, Gregg J.
- Radiochimica Acta, Vol. 103, Issue 8
Hexavalent Americium Recovery Using Copper(III) Periodate
journal, October 2016
- McCann, Kevin; Brigham, Derek M.; Morrison, Samuel
- Inorganic Chemistry, Vol. 55, Issue 22
Hexavalent Actinide Extraction Using N , N -Dialkyl Amides
journal, May 2017
- McCann, Kevin; Mincher, Bruce J.; Schmitt, Nicholas C.
- Industrial & Engineering Chemistry Research, Vol. 56, Issue 22
Kinetics of the Autoreduction of Hexavalent Americium in Aqueous Nitric Acid
journal, June 2017
- Grimes, Travis S.; Horne, Gregory P.; Dares, Christopher J.
- Inorganic Chemistry, Vol. 56, Issue 14
The self-reduction of americium(V) and (VI) and the disproportionation of americium(V) in aqueous solution
journal, January 1957
- Hall, G. R.; Markin, T. L.
- Journal of Inorganic and Nuclear Chemistry, Vol. 4, Issue 5-6
The Kinetics of the Disproportionation of Americium(V)
journal, February 1963
- Coleman, James S.
- Inorganic Chemistry, Vol. 2, Issue 1
Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations
journal, September 2011
- Runde, Wolfgang H.; Mincher, Bruce J.
- Chemical Reviews, Vol. 111, Issue 9
The Separation of Americium and Curium from the Rare Earth Elements
journal, June 1950
- Street, Kenneth; Seaborg, Glenn T.
- Journal of the American Chemical Society, Vol. 72, Issue 6
An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides 1
journal, March 1954
- Diamond, R. M.; Street, K.; Seaborg, G. T.
- Journal of the American Chemical Society, Vol. 76, Issue 6
Complexation and Separation of Lanthanides(III) and Actinides(III) by Heterocyclic N-Donors in Solutions
journal, October 2008
- Kolarik, Zdenek
- Chemical Reviews, Vol. 108, Issue 10
An overview and historical look back at the solvent extraction using nitrogen donor ligands to extract and separate An(III) from Ln(III)
journal, January 2008
- Ekberg, Christian; Fermvik, Anna; Retegan, Teodora
- Radiochimica Acta, Vol. 96, Issue 4-5
Complexation and Extraction of Trivalent Actinides and Lanthanides by Triazinylpyridine N -Donor Ligands
journal, October 2012
- Panak, Petra J.; Geist, Andreas
- Chemical Reviews, Vol. 113, Issue 2
Actinide(III)/Lanthanide(III) Separation Via Selective Aqueous Complexation of Actinides(III) using a Hydrophilic 2,6-Bis(1,2,4-Triazin-3-Yl)-Pyridine in Nitric Acid
journal, August 2012
- Geist, Andreas; Müllich, Udo; Magnusson, Daniel
- Solvent Extraction and Ion Exchange, Vol. 30, Issue 5
Preferential extraction of lanthanides over trivalent actinides by monoacidic organophosphates from carboxylic acids and from mixtures of carboxylic and aminopolyacetic acids
journal, January 1968
- Weaver, Boyd; Kappelmann, F. A.
- Journal of Inorganic and Nuclear Chemistry, Vol. 30, Issue 1
The Chemistry of TALSPEAK: A Review of the Science
journal, December 2014
- Nash, Kenneth L.
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 1
Systematic Investigation of Thorium(IV)– and Uranium(IV)–Ligand Bonding in Dithiophosphonate, Thioselenophosphinate, and Diselenophosphonate Complexes
journal, August 2013
- Behrle, Andrew C.; Barnes, Charles L.; Kaltsoyannis, Nikolas
- Inorganic Chemistry, Vol. 52, Issue 18
Uncovering f-element bonding differences and electronic structure in a series of 1 : 3 and 1 : 4 complexes with a diselenophosphinate ligand
journal, January 2013
- Jones, Matthew B.; Gaunt, Andrew J.; Gordon, John C.
- Chemical Science, Vol. 4, Issue 3
Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N ′-di(acetylglycine)- N,N ′-diacetic Acid
journal, March 2016
- Heathman, Colt R.; Grimes, Travis S.; Zalupski, Peter R.
- Inorganic Chemistry, Vol. 55, Issue 6
Coordination Chemistry and f-Element Complexation by Diethylenetriamine- N , N ″-bis(acetylglycine)- N , N ′, N ″-triacetic Acid
journal, October 2016
- Heathman, Colt R.; Grimes, Travis S.; Zalupski, Peter R.
- Inorganic Chemistry, Vol. 55, Issue 21
Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N -butyl-2-acetamide-diethylenetriamine- N , N ′, N ′′, N ′′-tetraacetic acid
journal, January 2018
- Heathman, Colt R.; Grimes, Travis S.; Jansone-Popova, Santa
- Dalton Transactions, Vol. 47, Issue 4
Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ′, N ″, N ″-tetraacetic Acid
journal, January 2017
- Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa
- Inorganic Chemistry, Vol. 56, Issue 3
Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants
journal, January 2018
- Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa
- Inorganic Chemistry, Vol. 57, Issue 3
Comparison of Two Tetrapodal N,O Ligands: Impact of the Softness of the Heterocyclic N-Donors Pyridine and Pyrazine on the Selectivity for Am(III) over Eu(III)
journal, January 2009
- Heitzmann, Marie; Bravard, Florence; Gateau, Christelle
- Inorganic Chemistry, Vol. 48, Issue 1
Water-soluble tetrapodal N,O ligands incorporating soft N-heterocycles for the selective complexation of Am(iii) over Ln(iii)
journal, January 2010
- Heitzmann, Marie; Gateau, Christelle; Chareyre, Laurence
- New J. Chem., Vol. 34, Issue 1
Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs
journal, October 1996
- Gans, P.; Sabatini, A.; Vacca, A.
- Talanta, Vol. 43, Issue 10
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004
- Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
- Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
Energy-adjusted pseudopotentials for the rare earth elements
journal, January 1989
- Dolg, M.; Stoll, H.; Savin, A.
- Theoretica Chimica Acta, Vol. 75, Issue 3
A combination of quasirelativistic pseudopotential and ligand field calculations for lanthanoid compounds
journal, June 1993
- Dolg, M.; Stoll, H.; Preuss, H.
- Theoretica Chimica Acta, Vol. 85, Issue 6
Quasirelativistic energy-consistent 5f-in-core pseudopotentials for trivalent actinide elements
journal, November 2006
- Moritz, Anna; Cao, Xiaoyan; Dolg, Michael
- Theoretical Chemistry Accounts, Vol. 117, Issue 4
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994
- Küchle, W.; Dolg, M.; Stoll, H.
- The Journal of Chemical Physics, Vol. 100, Issue 10
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988
- Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
- Chemical Reviews, Vol. 88, Issue 6
Natural hybrid orbitals
journal, September 1980
- Foster, J. P.; Weinhold, F.
- Journal of the American Chemical Society, Vol. 102, Issue 24
Acid Dissociation Constants and Rare Earth Stability Constants for DTPA
journal, February 2014
- Grimes, Travis S.; Nash, Kenneth L.
- Journal of Solution Chemistry, Vol. 43, Issue 2
The interaction of rare earth ions with diethylenetriaminepentaacetic acid
journal, October 1959
- Harder, R.; Chaberek, S.
- Journal of Inorganic and Nuclear Chemistry, Vol. 11, Issue 3
Observations on the rare earths—LXXV(1)
journal, November 1962
- Moeller, T.; Thompson, L. C.
- Journal of Inorganic and Nuclear Chemistry, Vol. 24, Issue 5
Comparative study on the hydration states of Cm(III) and Eu(III) in solution and in cation exchange resin
journal, June 1998
- Kimura, Takaumi; Kato, Yoshiharu; Takeishi, Hideyo
- Journal of Alloys and Compounds, Vol. 271-273
Luminescence study on determination of the hydration number of Cm(III)
journal, October 1994
- Kimura, Takaumi; Choppin, Gregory R.
- Journal of Alloys and Compounds, Vol. 213-214
Acidic organophosphorus extractants—I Extraction of lanthanides by means of dialkyl phosphoric acids—effect of structure and size of alkyl group
journal, October 1966
- Kolařík, Z.; Pánková, H.
- Journal of Inorganic and Nuclear Chemistry, Vol. 28, Issue 10
Equilibrium and NMR studies on Gd III , Y III , Cu II and Zn II complexes of various DTPA–N,N″-bis(amide) ligands. Kinetic stabilities of the gadolinium( iii ) complexes
journal, January 2006
- Jászberényi, Zoltán; Bányai, István; Brücher, Ernö
- Dalton Trans., Issue 8
Aqueous complexation of trivalent lanthanide and actinide cations by N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine
journal, May 2000
- Jensen, Mark P.; Morss, Lester R.; Beitz, James V.
- Journal of Alloys and Compounds, Vol. 303-304
Complexation thermodynamics and structural aspects of actinide–aminopolycarboxylates
journal, April 2006
- Choppin, G.; Thakur, P.; Mathur, J.
- Coordination Chemistry Reviews, Vol. 250, Issue 7-8
A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides: A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides
journal, June 2016
- Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
- European Journal of Inorganic Chemistry, Vol. 2016, Issue 21
Misleading evidence for covalent bonding from EuIIIX and AmIIIX density functional theory bond lengths
journal, June 2014
- Dolg, Michael; Cao, Xiaoyan; Ciupka, Jan
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
Impact of the Kohn–Sham Delocalization Error on the 4f Shell Localization and Population in Lanthanide Complexes
journal, June 2016
- Duignan, Thomas J.; Autschbach, Jochen
- Journal of Chemical Theory and Computation, Vol. 12, Issue 7
Trans‐Lanthanide Extraction Studies in the TALSPEAK System: Investigating the Effect of Acidity and Temperature
journal, April 2009
- Nilsson, Mikael; Nash, Kenneth L.
- Solvent Extraction and Ion Exchange, Vol. 27, Issue 3
An Advanced TALSPEAK Concept Using 2-Ethylhexylphosphonic Acid Mono-2-Ethylhexyl Ester as the Extractant
journal, December 2014
- Lumetta, Gregg J.; Casella, Amanda J.; Rapko, Brian M.
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 3
Actinide Lanthanide Separation Process—ALSEP
journal, January 2014
- Gelis, Artem V.; Lumetta, Gregg J.
- Industrial & Engineering Chemistry Research, Vol. 53, Issue 4
Lanthanide(III) Complexes of Tripodal N-Donor Ligands: Structural Models for the Species Involved in Solvent Extraction of Actinides(III)
journal, December 1998
- Wietzke, Raphaël; Mazzanti, Marinella; Latour, Jean-Marc
- Inorganic Chemistry, Vol. 37, Issue 26