DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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)22-OH)2(NO3)4], where An = UVI, NpVI, and PuVI. 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.

Authors:
 [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1509993
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 5; 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

Citation Formats

Autillo, Matthieu, and Wilson, Richard E. Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me4N]2[(AnO2)2(OH)2(NO3)4]. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.8b03304.
Autillo, Matthieu, & Wilson, Richard E. Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me4N]2[(AnO2)2(OH)2(NO3)4]. United States. https://doi.org/10.1021/acs.inorgchem.8b03304
Autillo, Matthieu, and Wilson, Richard E. Tue . "Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me4N]2[(AnO2)2(OH)2(NO3)4]". United States. https://doi.org/10.1021/acs.inorgchem.8b03304. https://www.osti.gov/servlets/purl/1509993.
@article{osti_1509993,
title = {Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [Me4N]2[(AnO2)2(OH)2(NO3)4]},
author = {Autillo, Matthieu and Wilson, Richard E.},
abstractNote = {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 = UVI, NpVI, and PuVI. 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.},
doi = {10.1021/acs.inorgchem.8b03304},
journal = {Inorganic Chemistry},
number = 5,
volume = 58,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Lanthanide and Actinide Contractions: Relativistic and Shell Structure Effects
journal, June 1995

  • Seth, Michael; Dolg, Michael; Fulde, Peter
  • Journal of the American Chemical Society, Vol. 117, Issue 24
  • DOI: 10.1021/ja00129a026

Actinide Environmental Chemistry
journal, December 1995


Hydrolysis of Plutonium(VI) : Acidity Measurements in Perchlorate Solutions
journal, May 1972


Soluble intermediates in the hydrolysis of neptunium(VI) and comparison with other actinides(VI)
journal, March 1972

  • Cassol, A.; Magon, L.; Tomat, G.
  • Inorganic Chemistry, Vol. 11, Issue 3
  • DOI: 10.1021/ic50109a018

Raman spectroscopy of neptunyl and plutonyl in aqueous solutions: hydrolysis of Np(VI) and Pu(VI) and disproportionation of Pu(V)
journal, February 1984


Pu(VI) Hydrolysis:  Further Evidence for a Dimeric Plutonyl Hydroxide and Contrasts with U(VI) Chemistry
journal, February 2006

  • Reilly, Sean D.; Neu, Mary P.
  • Inorganic Chemistry, Vol. 45, Issue 4
  • DOI: 10.1021/ic051760j

Infrared and Raman spectra of uranyl(VI) oxo-hydroxo complexes in acid aqueous solutions: a chemometric study
journal, June 2000


Hydrolysis of Uranyl(VI) in Acidic and Basic Aqueous Solutions Using a Noncomplexing Organic Base: A Multivariate Spectroscopic and Statistical Study
journal, April 2011

  • Quilès, Fabienne; Nguyen-Trung, Chinh; Carteret, Cédric
  • Inorganic Chemistry, Vol. 50, Issue 7
  • DOI: 10.1021/ic101953q

Capturing Hydrolysis Products in the Solid State: Effects of pH on Uranyl Squarates under Ambient Conditions
journal, October 2010

  • Rowland, Clare E.; Cahill, Christopher L.
  • Inorganic Chemistry, Vol. 49, Issue 19
  • DOI: 10.1021/ic1000792

Stoichiometry and Structure of Uranyl(VI) Hydroxo Dimer and Trimer Complexes in Aqueous Solution
journal, December 2007

  • Tsushima, Satoru; Rossberg, André; Ikeda, Atsushi
  • Inorganic Chemistry, Vol. 46, Issue 25
  • DOI: 10.1021/ic701607e

The hydrolysis of dioxouranium(VI) investigated using EXAFS and 17O-NMR
journal, January 2000


Spectral Analysis of the Uranyl Squarate and Croconate System: Evaluating Differences between the Solution and Solid-State Phases
journal, September 2017


Crystal Structures of Molecular Adducts between Uranyl Nitrate and 2,2  : 6 ,2  -Terpyridine or 2,2′-Bipyridyl
journal, July 2004


Synthesis, Characterization, and Crystal Structure of New Complex, Based on Proton Transfer to Uranium(VI) Complex
journal, June 2015

  • Saravani, Hamideh; Mozafaripoor, Farima
  • Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, Vol. 45, Issue 11
  • DOI: 10.1080/15533174.2013.872127

Understanding the Ligand-Directed Assembly of a Hexanuclear Th IV Molecular Cluster in Aqueous Solution
journal, July 2013

  • Hu, Yung-Jin; Knope, Karah E.; Skanthakumar, S.
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 24
  • DOI: 10.1002/ejic.201300805

The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14−
journal, January 2008

  • Soderholm, L.; Almond, Philip M.; Skanthakumar, S.
  • Angewandte Chemie International Edition, Vol. 47, Issue 2
  • DOI: 10.1002/anie.200704420

Structures of Dimeric Hydrolysis Products of Thorium
journal, April 2007

  • Wilson, Richard E.; Skanthakumar, S.; Sigmon, Ginger
  • Inorganic Chemistry, Vol. 46, Issue 7
  • DOI: 10.1021/ic0617691

Separation of Plutonium Oxide Nanoparticles and Colloids
journal, September 2011

  • Wilson, Richard E.; Skanthakumar, S.; Soderholm, L.
  • Angewandte Chemie International Edition, Vol. 50, Issue 47
  • DOI: 10.1002/anie.201105624

Structures and Energetics of Erbium Chloride Complexes in Aqueous Solution
journal, June 2009

  • Soderholm, L.; Skanthakumar, S.; Wilson, Richard E.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 22
  • DOI: 10.1021/jp9012366

Structural Correspondence between Uranyl Chloride Complexes in Solution and Their Stability Constants
journal, May 2011

  • Soderholm, L.; Skanthakumar, S.; Wilson, Richard E.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 19
  • DOI: 10.1021/jp111551t

Structural Studies Coupling X-ray Diffraction and High-Energy X-ray Scattering in the UO 2 2+ –HBr aq System
journal, November 2011

  • Wilson, Richard E.; Skanthakumar, S.; Cahill, C. L.
  • Inorganic Chemistry, Vol. 50, Issue 21
  • DOI: 10.1021/ic201265s

The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
journal, March 1974


Infrared Spectra and Structure of Uranyl and Transuranium ( V ) and ( VI ) Ions in Aqueous Perchloric Acid Solution
journal, March 1953

  • Jones, Llewellyn H.; Penneman, Robert A.
  • The Journal of Chemical Physics, Vol. 21, Issue 3
  • DOI: 10.1063/1.1698941

Structural and Vibrational Properties of U(VI)O 2 Cl 4 2- and Pu(VI)O 2 Cl 4 2- Complexes
journal, November 2013

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 52, Issue 24
  • DOI: 10.1021/ic401991n

Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO 2 Cl 4 2–
journal, September 2014

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic501553m

Synthesis, Structure, and Vibrational Properties of [Ph 4 P] 2 NpO 2 Cl 4 and [Ph 4 P] 2 PuO 2 Cl 4 Complexes
journal, March 2018


Raman spectra of uranyl ion and its hydrolysis products in aqueous nitric acid
journal, March 1981

  • Toth, L. M.; Begun, G. M.
  • The Journal of Physical Chemistry, Vol. 85, Issue 5
  • DOI: 10.1021/j150605a018

The Crystal Structure of [(UO2)2(OH)2Cl2(H2O)4].
journal, January 1969


A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930