In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Carter, Korey P.; Wacker, Jennifer N.; Smith, Kurt F.; Deblonde, Gauthier J. -P.; Moreau, Liane M.; Rees, Julian A.; Booth, Corwin H.; Abergel, Rebecca J.

doi:10.1107/S1600577522000200

Title: In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Journal Article · Fri Feb 25 00:00:00 EST 2022 · Journal of Synchrotron Radiation (Online)

DOI:https://doi.org/10.1107/S1600577522000200· OSTI ID:1846473

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; Smith, Kurt F.;

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The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An—O _HOPO bond distances of 2.498 (5) and 2.415 (2) Å for Pu and Bk, respectively, which match well with bond distances obtained for trivalent actinides and 343-HOPO via density functional theory calculations. Pu(III)- and Bk(III)-343-HOPO data also provide initial insight into actinide periodicity as they can be compared with previous results with Am(III)-, Cm(III)-, Cf(III)-, and Es(III)-343-HOPO, which indicate there is likely an increase in 5 f covalency and heterogeneity across the actinide series.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1846473

Alternate ID(s):: OSTI ID: 1891303

Journal Information:: Journal of Synchrotron Radiation (Online), Journal Name: Journal of Synchrotron Radiation (Online) Vol. 29 Journal Issue: 2; ISSN 1600-5775

Publisher:: International Union of Crystallography (IUCr)Copyright Statement

Country of Publication:: Denmark

Language:: English

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73 NUCLEAR PHYSICS AND RADIATION PHYSICS
plutonium
berkelium
coordination complexes
X-ray absorption spectroscopy
periodicity

Title: In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

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