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

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

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1244249

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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{Np ₃₈ } clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides Martin, Nicolas P.; Volkringer, Christophe; Roussel, Pascal Chemical Communications, Vol. 54, Issue 72 https://doi.org/10.1039/c8cc03744b	journal	January 2018

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

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