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Title: Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation

We report the room temperature synthesis and structural characterization of a μ2-hydroxobridged PuIV dimer obtained from an acidic, nitric acid solution. The discrete Pu 2(OH) 2(NO 3) 6(H 2O) 4 moiety crystallized with two distinct crystal structures, (1) [Pu 2(OH) 2(NO 3) 6(H 2O) 4] 2·11H 2O and (2) Pu 2(OH) 2(NO 3) 6(H 2O) 4·2H 2O, 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 PuO 2. 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:
 [1] ;  [1] ;  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357
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)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Actinide; hydrolysis; hydroxo-bridged dimers; metal-oxide clusters; plutonium
OSTI Identifier:
1244249

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., 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. doi:10.1021/acs.inorgchem.5b01242.
Knope, Karah E., Skanthakumar, S., and Soderholm, L.. 2015. "Two Dihydroxo-Bridged Plutonium(IV) Nitrate Dimers and Their Relevance to Trends in Tetravalent Ion Hydrolysis and Condensation". United States. doi: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 = {2015},
month = {10}
}