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Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series
Author(s) -
Deblonde Gauthier J.P.,
Kelley Morgan P.,
Su Jing,
Batista Enrique R.,
Yang Ping,
Booth Corwin H.,
Abergel Rebecca J.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201709183
Subject(s) - actinide , lanthanide , chemistry , extended x ray absorption fine structure , aqueous solution , density functional theory , chelation , molecule , metal , bond length , inorganic chemistry , ion , computational chemistry , absorption spectroscopy , organic chemistry , physics , quantum mechanics
Abstract The chemistry of trivalent transplutonium ions (Am 3+ , Cm 3+ , Bk 3+ , Cf 3+ , Es 3+ …) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. Herein, 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 Cf 3+ . Corroborating those results, density functional theory calculations, extended to Es 3+ , 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 [M III DTPA(H 2 O)] 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.