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

Knope, Karah E.; Skanthakumar, S.; Soderholm, L.

doi:10.1021/acs.inorgchem.5b01242

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

Journal Article · Tue Oct 13 00:00:00 EDT 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b01242· OSTI ID:1244249

Knope, Karah E. ^[1]; Skanthakumar, S. ^[1]; Soderholm, L. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division

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

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1244249

Journal Information:: Inorganic Chemistry, Vol. 54, Issue 21; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Actinide
hydrolysis
hydroxo-bridged dimers
metal-oxide clusters
plutonium

CSD 1788753: Experimental Crystal Structure Determination: ICSD 239107 : ICSD Structure : H₁₄ N₆ O₂₆ Pu₂ Knope, Karah E.; Skanthakumar, S.; Soderholm, L. https://doi.org/10.25505/fiz.icsd.cc1y1bq1 The current record is supplemented by this dataset	dataset	February 2018
CSD 1787056: Experimental Crystal Structure Determination: ICSD 239107 : ICSD Structure : H₁₄ N₆ O₂₆ Pu₂ Knope, Karah E.; Skanthakumar, S.; Soderholm, L. https://doi.org/10.25505/fiz.icsd.cc1xzkzf The current record is supplemented by this dataset	dataset	February 2018