From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry
Abstract
A series of eighteen actinide (IV) compounds were synthesized from acidic aqueous media containing thorium, uranium, or plutonium. The metal cation adopts a variety of different structural units with the general formula [An(H2O)xCly]4-y (x=4-7, y=2-4) or AnCl62- charge balanced by protonated nitrogen-containing heterocycles. Compound identities were classified by single crystal X-ray diffraction and subsequently characterized by Raman, IR, and optical absorption spectroscopies. Discrepancies across the early actinides were observed in this family of An(IV)-chlorides, with Th adopting exclusively Th-aquo-chloro species, Pu forming only PuCl62-, and U residing somewhere in between, crystallizing both as U-aquo-chloro and UCl62- monomeric units. Reports of An-H2O-Cl species are largely absent from tetravalent An solid state discussions despite their identification in chloride solutions. Here, the isolation of unique An(IV)-chlorides may be attributed to nonbonding interactions provided by outer coordination sphere counter-ions that could play a role in stabilizing these structural units. Differences in the structural chemistry of Th, U, and Pu also demonstrate a break in the series despite their common oxidation state and nearly identical synthetic procedures.
- Authors:
-
[1];
[1]
- Georgetown Univ., Washington, D.C. (United States)
- Florida State Univ., Tallahassee, FL (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1572959
- Report Number(s):
- PNNL-SA-143237
Journal ID: ISSN 0020-1669; TRN: US2001209
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 16; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wacker, Jennifer N., Han, Sae Young, Murray, Aphra V., Vanagas, Nicole A., Bertke, Jeffery A., Sperling, Joseph M., Surbella, III, Robert G., and Knope, Karah E. From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b01279.
Wacker, Jennifer N., Han, Sae Young, Murray, Aphra V., Vanagas, Nicole A., Bertke, Jeffery A., Sperling, Joseph M., Surbella, III, Robert G., & Knope, Karah E. From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry. United States. https://doi.org/10.1021/acs.inorgchem.9b01279
Wacker, Jennifer N., Han, Sae Young, Murray, Aphra V., Vanagas, Nicole A., Bertke, Jeffery A., Sperling, Joseph M., Surbella, III, Robert G., and Knope, Karah E. Wed .
"From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry". United States. https://doi.org/10.1021/acs.inorgchem.9b01279. https://www.osti.gov/servlets/purl/1572959.
@article{osti_1572959,
title = {From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry},
author = {Wacker, Jennifer N. and Han, Sae Young and Murray, Aphra V. and Vanagas, Nicole A. and Bertke, Jeffery A. and Sperling, Joseph M. and Surbella, III, Robert G. and Knope, Karah E.},
abstractNote = {A series of eighteen actinide (IV) compounds were synthesized from acidic aqueous media containing thorium, uranium, or plutonium. The metal cation adopts a variety of different structural units with the general formula [An(H2O)xCly]4-y (x=4-7, y=2-4) or AnCl62- charge balanced by protonated nitrogen-containing heterocycles. Compound identities were classified by single crystal X-ray diffraction and subsequently characterized by Raman, IR, and optical absorption spectroscopies. Discrepancies across the early actinides were observed in this family of An(IV)-chlorides, with Th adopting exclusively Th-aquo-chloro species, Pu forming only PuCl62-, and U residing somewhere in between, crystallizing both as U-aquo-chloro and UCl62- monomeric units. Reports of An-H2O-Cl species are largely absent from tetravalent An solid state discussions despite their identification in chloride solutions. Here, the isolation of unique An(IV)-chlorides may be attributed to nonbonding interactions provided by outer coordination sphere counter-ions that could play a role in stabilizing these structural units. Differences in the structural chemistry of Th, U, and Pu also demonstrate a break in the series despite their common oxidation state and nearly identical synthetic procedures.},
doi = {10.1021/acs.inorgchem.9b01279},
journal = {Inorganic Chemistry},
number = 16,
volume = 58,
place = {United States},
year = {2019},
month = {6}
}
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