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Title: 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(H 2O) xCl y] 4-y (x=4-7, y=2-4) or AnCl 6 2- 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 PuCl 6 2-, and U residing somewhere in between, crystallizing both as U-aquo-chloro and UCl 6 2- monomeric units. Reports of An-H 2O-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];  [1];  [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1]
  1. Georgetown Univ., Washington, D.C. (United States)
  2. Florida State Univ., Tallahassee, FL (United States)
  3. 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]
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. 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., and Knope, Karah E. Wed . "From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry". United States. doi:10.1021/acs.inorgchem.9b01279.
@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}
}

Journal Article:
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This content will become publicly available on June 12, 2020
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