In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators.
J Synchrotron Radiat
; 29(Pt 2): 315-322, 2022 Mar 01.
Article
in En
| MEDLINE
| ID: mdl-35254293
ABSTRACT
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-OHOPO bond distances of 2.498â
(5) and 2.415â
(2)â
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 5f covalency and heterogeneity across the actinide series.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Plutonium
/
Coordination Complexes
Language:
En
Journal:
J Synchrotron Radiat
Journal subject:
RADIOLOGIA
Year:
2022
Document type:
Article
Affiliation country:
United States