Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me4N]2[(AnO2)2(OH)2(NO3)4]

Autillo, Matthieu; Wilson, Richard E.

doi:10.1021/acs.inorgchem.8b03304

Title: Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me₄N]₂[(AnO₂)₂(OH)₂(NO₃)₄]

Journal Article · Tue Feb 12 00:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b03304· OSTI ID:1509993

Autillo, Matthieu ^[1];

^[1]

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

The synthesis of a series of molecular actinyl(VI), namely, uranium(VI), neptunium(VI), and plutonium(VI), hydroxo-bridged dimers is reported here. These complexes were isolated from an aqueous nitrate solution by titration with tetramethylammonium hydroxide. The solid-state structures were determined using single-crystal X-ray diffraction, revealing molecular complexes with the formula [Me₄N]₂[(AnO₂)₂(μ₂-OH)₂(NO₃)₄], where An = U^VI, Np^VI, and Pu^VI. Spectroscopic data—UV–vis–near-IR absorption, IR, and Raman—were collected on the solutions and solid-state complexes where available and compared to those of the aqueous solutions from which the crystals formed. These data provide structural evidence for higher-order polynuclear complexes of actinyl(VI) complexes upon a pH increase in the aqueous solution, confirming earlier thermodynamic models.

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

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1509993

Journal Information:: Inorganic Chemistry, Vol. 58, Issue 5; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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CCDC 1870502: Experimental Crystal Structure Determination Autillo, Matthieu; Wilson, Richard E. https://doi.org/10.5517/ccdc.csd.cc20sds0 The current record is supplemented by this dataset	dataset	January 2019
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Title: Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me4N]2[(AnO2)2(OH)2(NO3)4]

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Title: Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me₄N]₂[(AnO₂)₂(OH)₂(NO₃)₄]