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Title: Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant

Abstract

The thermodynamic influence of a pre-organized N-donor group on the coordination of trivalent actinides and lanthanides by an aqueous aminopolycarboxylate complexant has been investigated. The synthesized reagent, N-2-methylpicolinate-ethylenediamine- N,N',N'-triacetic acid (EDTA-Mpic), resembles ethylenediamine- N,N,N',N'-tetraacetic acid (EDTA) with a single acetate pendant arm replaced by a 6-carboxypyridin-2-ylmethyl group. The rigid N-donor picolinate functionality has a profound impact on ligand protonation and trivalent f element complexation equilibria, as demonstrated by potentiometric, spectroscopic, and liquid/liquid metal-partitioning studies as well as by molecular dynamics calculations. Relative to diethylenetriamine- N,N,N',N'',N''-pentaacetic acid (DTPA), the ability to preferentially bind trivalent actinides over trivalent lanthanides was moderately lowered due to the presence of the N-(6-carboxypyridin-2-ylmethyl) substituent. The structural modification substantially amplifies the total ligand acidity of EDTA-Mpic. As a result the complexant sustains the metal complexation and efficient An 3+/Ln 3+ differentiation in aqueous mixtures of unprecedented acidity for this class of reagents.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1564104
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 10; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English

Citation Formats

Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Roy, Santanu, Bryantsev, Vyacheslav S., and Zalupski, Peter R. Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant. United States: N. p., 2019. Web. doi:10.1002/chem.201804723.
Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Roy, Santanu, Bryantsev, Vyacheslav S., & Zalupski, Peter R. Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant. United States. doi:10.1002/chem.201804723.
Heathman, Colt R., Grimes, Travis S., Jansone-Popova, Santa, Roy, Santanu, Bryantsev, Vyacheslav S., and Zalupski, Peter R. Mon . "Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant". United States. doi:10.1002/chem.201804723.
@article{osti_1564104,
title = {Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant},
author = {Heathman, Colt R. and Grimes, Travis S. and Jansone-Popova, Santa and Roy, Santanu and Bryantsev, Vyacheslav S. and Zalupski, Peter R.},
abstractNote = {The thermodynamic influence of a pre-organized N-donor group on the coordination of trivalent actinides and lanthanides by an aqueous aminopolycarboxylate complexant has been investigated. The synthesized reagent, N-2-methylpicolinate-ethylenediamine-N,N',N'-triacetic acid (EDTA-Mpic), resembles ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) with a single acetate pendant arm replaced by a 6-carboxypyridin-2-ylmethyl group. The rigid N-donor picolinate functionality has a profound impact on ligand protonation and trivalent f element complexation equilibria, as demonstrated by potentiometric, spectroscopic, and liquid/liquid metal-partitioning studies as well as by molecular dynamics calculations. Relative to diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA), the ability to preferentially bind trivalent actinides over trivalent lanthanides was moderately lowered due to the presence of the N-(6-carboxypyridin-2-ylmethyl) substituent. The structural modification substantially amplifies the total ligand acidity of EDTA-Mpic. As a result the complexant sustains the metal complexation and efficient An3+/Ln3+ differentiation in aqueous mixtures of unprecedented acidity for this class of reagents.},
doi = {10.1002/chem.201804723},
journal = {Chemistry - A European Journal},
number = 10,
volume = 25,
place = {United States},
year = {2019},
month = {1}
}

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