Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation
Abstract
We report the room temperature synthesis and structural characterization of a μ2-hydroxobridged PuIV dimer obtained from an acidic, nitric acid solution. The discrete Pu2(OH)2(NO3)6(H2O)4 moiety crystallized with two distinct crystal structures, (1) [Pu2(OH)2(NO3)6(H2O)4]2·11H2O and (2) Pu2(OH)2(NO3)6(H2O)4·2H2O, which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(10) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridged distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent-metal-ion condensation
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1244249
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 21; 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; Actinide; hydrolysis; hydroxo-bridged dimers; metal-oxide clusters; plutonium
Citation Formats
Knope, Karah E., Skanthakumar, S., and Soderholm, L. Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation. United States: N. p., 2015.
Web. doi:10.1021/acs.inorgchem.5b01242.
Knope, Karah E., Skanthakumar, S., & Soderholm, L. Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation. United States. https://doi.org/10.1021/acs.inorgchem.5b01242
Knope, Karah E., Skanthakumar, S., and Soderholm, L. Tue .
"Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation". United States. https://doi.org/10.1021/acs.inorgchem.5b01242. https://www.osti.gov/servlets/purl/1244249.
@article{osti_1244249,
title = {Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation},
author = {Knope, Karah E. and Skanthakumar, S. and Soderholm, L.},
abstractNote = {We report the room temperature synthesis and structural characterization of a μ2-hydroxobridged PuIV dimer obtained from an acidic, nitric acid solution. The discrete Pu2(OH)2(NO3)6(H2O)4 moiety crystallized with two distinct crystal structures, (1) [Pu2(OH)2(NO3)6(H2O)4]2·11H2O and (2) Pu2(OH)2(NO3)6(H2O)4·2H2O, which differ primarily in the number of incorporated water molecules. High-energy X-ray scattering (HEXS) data obtained from the mother liquor showed evidence of a correlation at 3.7(10) Å but only after concentration of the stock solution. This distance is consistent with the dihydroxo-bridged distance of 3.799(1) Å seen in the solid-state structure as well as with the known Pu-Pu distance in PuO2. The structural characterization of a dihydroxo-bridged Pu moiety is discussed in terms of its relevance to the underlying mechanisms of tetravalent-metal-ion condensation},
doi = {10.1021/acs.inorgchem.5b01242},
journal = {Inorganic Chemistry},
number = 21,
volume = 54,
place = {United States},
year = {Tue Oct 13 00:00:00 EDT 2015},
month = {Tue Oct 13 00:00:00 EDT 2015}
}
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Works referencing / citing this record:
Experimental and Quantum Mechanical Characterization of an Oxygen‐Bridged Plutonium(IV) Dimer
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