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Title: Coordination Chemistry and f-Element Complexation by Diethylenetriamine-N,N"bis(acetylglycine)-N,N',N"-triacetic Acid

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1]
  1. Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Dept.
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Here, potentiometric and spectroscopic techniques were used to evaluate the coordination behavior and thermodynamic features of trivalent f-element complexation by diethylenetriamine-N,N"-bis(acetylglycine)-N,N',N"-triacetic acid (DTTA-DAG) and its di(acetylglycine ethyl ester) analogue [diethylenetriamine-N,N"-bis(acetylglycine ethyl ester)-N,N',N"-triacetic acid (DTTA-DAGEE)]. Protonation constants and stability constants of trivalent lanthanide complexes (except Pm3+) were determined by potentiometry. Six protonation sites and three metal–ligand complexes [ML2–, MHL–, and MH2L(aq)] were quantified for DTTA-DAG. Four protonation sites and one metal–ligand complex [ML(aq)] were observed for DTTA-DAGEE, consistent with the presence of two ester groups. Absorption spectroscopy was utilized to measure the stability constants for complexation of trivalent neodymium and americium by DTTA-DAG and trivalent neodymium by DTTA-DAGEE. The coordination environment of trivalent europium in the presence of DTTA-DAG was investigated at various acidities by luminescence lifetime measurements. Decay constants indicate one water molecule in the inner coordination sphere across the 1.0 < pH < 5.5 range, presumably due to octadentate coordination by DTTA-DAG. A trans-lanthanide pattern of complex stabilities for DTTA-DAG was found to be analogous to that observed for DTPA, with a ~106 reduction of the complex stability. The lessened strength of complexation, relative to DTPA, was attributed to significant reduction of the total ligand basicity for DTTA-DAG due to the electronic influence of amide functionalization. When DTTA-DAG is used as an aqueous holdback complexant in liquid–liquid distribution experiments, the preferential coordination of Am3+ in the aqueous environment offers efficient An/Ln differentiation. The separation extends to pH 2 conditions, where the kinetics of phase transfer in such liquid–liquid systems are aided by the acid-catalyzed dissociation of a metal/aminopolycarboxylate complex.

Research Organization:
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
AC07-05ID14517
OSTI ID:
1407422
Report Number(s):
INL/JOU-16-39809
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 21; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

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Cited By (2)

Prediction of trivalent actinide amino(poly)carboxylate complex stability constants using linear free energy relationships with the lanthanide series journal November 2017
Influence of a Pre‐organized N‐Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant journal January 2019

Figures / Tables (12)

Table 1(p. 17)table Table 1
Table 2(p. 18)table Table 2
Table 3(p. 19)table Table 3
Figure 1(p. 22)figure Figure 1
Figure 2(p. 22)figure Figure 2
Figure 3(p. 23)figure Figure 3
Figure 4(p. 24)figure Figure 4
Figure 5(p. 25)figure Figure 5
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Figure 7(p. 26)figure Figure 7
Figure 8(p. 26)figure Figure 8
Figure 9(p. 27)figure Figure 9

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Actinide
ALSEP
Complexes
Coordination
DTPA
Lanthanide
Separations
TALSPEAK