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Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [2];  [2];  [1];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Nuclear Engineering
+ Show Author Affiliations
The chemistry of trivalent transplutonium ions (Am3+, Cm3+, Bk3+, Cf3+, Es3+…) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. We present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest-neighbor bond lengths in the case of Cf3+. Corroborating those results, density functional theory calculations, extended to Es3+, suggest that the shorter Cf-O and Es-O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [MIIIDTPA(H2O)]2- (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.
Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515; AC52-06NA25396
OSTI ID:
1477677
Alternate ID(s):
OSTI ID: 1513796
OSTI ID: 1426318
OSTI ID: 22696162
Report Number(s):
LA-UR--17-27807
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 17 Vol. 57; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (5)

Ultra-selective ligand-driven separation of strategic actinides journal June 2019
Contemporary Chemistry of Berkelium and Californium journal June 2019
Revisiting complexation thermodynamics of transplutonium elements up to einsteinium journal January 2018
Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand journal January 2018
Combinatorial design of multimeric chelating peptoids for selective metal coordination journal January 2019

Figures / Tables (5)

Scheme 1(p. 3)figure Scheme 1
Figure 1(p. 4)figure Figure 1
Figure 2(p. 5)figure Figure 2
Table 1(p. 5)table Table 1
Table 2(p. 6)table Table 2

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
EXAFS spectroscopy
actinides
berkelium
californium
chelates