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Title: Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW 9O 34] 9-, [AsW 9O 34] 9-, [SiW 9O 34] 10- and [GeW 9O 34] 10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO 2} 2+, {NpO 2} +, {NpO 2} 2+ & {PuO 2} 2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na +, K + or NH 4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH 4) 13 [Na(NpO 2) 2(A-α- PW 9O 34) 2]·12H 2O. The anion in this complex, [Na(NpO 2) 2(PW 9O 34) 2] 13-, contains one Na + cation and two {NpO 2} 2+ cations held between two [PW 9O 34] 9- anions – with an additional partial occupancy NH 4 + or {NpO 2} 2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH 4Cl in the parentmore » solution, it was previously shown that [(NH 4) 2(U VIO 2) 2(A-PW 9O 34) 2] 12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO 2} 2+/[PW 9O 34] 9- and {UO 2} 2+/[PW 9O 34] 9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
LA-UR-14-27690
Journal ID: ISSN 0020-1669
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 9; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; 12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
OSTI Identifier:
1239107

Berg, John M., Gaunt, Andrew J., May, Iain, Pugmire, Alison L., Reilly, Sean D., Scott, Brian L., and Wilkerson, Marianne P.. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes. United States: N. p., Web. doi:10.1021/ic5024345.
Berg, John M., Gaunt, Andrew J., May, Iain, Pugmire, Alison L., Reilly, Sean D., Scott, Brian L., & Wilkerson, Marianne P.. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes. United States. doi:10.1021/ic5024345.
Berg, John M., Gaunt, Andrew J., May, Iain, Pugmire, Alison L., Reilly, Sean D., Scott, Brian L., and Wilkerson, Marianne P.. 2015. "Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes". United States. doi:10.1021/ic5024345. https://www.osti.gov/servlets/purl/1239107.
@article{osti_1239107,
title = {Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes},
author = {Berg, John M. and Gaunt, Andrew J. and May, Iain and Pugmire, Alison L. and Reilly, Sean D. and Scott, Brian L. and Wilkerson, Marianne P.},
abstractNote = {A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW9O34]9-, [AsW9O34]9-, [SiW9O34]10- and [GeW9O34]10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO2}2+, {NpO2}+, {NpO2}2+ & {PuO2}2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na+, K+ or NH4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH4)13 [Na(NpO2)2(A-α- PW9O34)2]·12H2O. The anion in this complex, [Na(NpO2)2(PW9O34)2]13-, contains one Na+ cation and two {NpO2}2+ cations held between two [PW9O34]9- anions – with an additional partial occupancy NH4 + or {NpO2}2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH4Cl in the parent solution, it was previously shown that [(NH4)2(UVIO2)2(A-PW9O34)2]12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO2}2+/[PW9O34]9- and {UO2}2+/[PW9O34]9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.},
doi = {10.1021/ic5024345},
journal = {Inorganic Chemistry},
number = 9,
volume = 54,
place = {United States},
year = {2015},
month = {4}
}