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)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.
- Authors:
-
- 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 = {Tue Feb 12 00:00:00 EST 2019},
month = {Tue Feb 12 00:00:00 EST 2019}
}
Web of Science
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
Actinide Environmental Chemistry
journal, December 1995
- Silva, R. J.; Nitsche, H.
- Radiochimica Acta, Vol. 70-71, Issue s1
Hydrolysis of Plutonium(VI) : Acidity Measurements in Perchlorate Solutions
journal, May 1972
- Cassol, A.; Magon, L.; Portanova, R.
- ract, Vol. 17, Issue 1
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
Raman spectroscopy of neptunyl and plutonyl in aqueous solutions: hydrolysis of Np(VI) and Pu(VI) and disproportionation of Pu(V)
journal, February 1984
- Madic, C.; Begun, G. M.; Hobart, D. E.
- Inorganica Chimica Acta, Vol. 94, Issue 1-3
Raman spectroscopy of neptunyl and plutonyl ions in aqueous solution: hydrolysis of neptunium(VI) and plutonium(VI) and disproportionation of plutonium(V)
journal, June 1984
- Madic, C.; Begun, G. M.; Hobart, D. E.
- Inorganic Chemistry, Vol. 23, Issue 13
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
Hydrolysis of Plutonium(VI) at Variable Temperatures (283-343 K)
journal, August 2011
- Rao, Linfeng; Tian, Guoxin; Di Bernardo, Plinio
- Chemistry - A European Journal, Vol. 17, Issue 39
Infrared and Raman spectra of uranyl(VI) oxo-hydroxo complexes in acid aqueous solutions: a chemometric study
journal, June 2000
- Quilès, F.; Burneau, A.
- Vibrational Spectroscopy, Vol. 23, Issue 2
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
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
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
The hydrolysis of dioxouranium(VI) investigated using EXAFS and 17O-NMR
journal, January 2000
- Moll, H.; Reich, T.; Szabó, Z.
- Radiochimica Acta, Vol. 88, Issue 7
Spectral Analysis of the Uranyl Squarate and Croconate System: Evaluating Differences between the Solution and Solid-State Phases
journal, September 2017
- Basile, M.; Unruh, D. K.; Streicher, L.
- Crystal Growth & Design, Vol. 17, Issue 10
Crystal Structures of Molecular Adducts between Uranyl Nitrate and 2,2 : 6 ,2 -Terpyridine or 2,2′-Bipyridyl
journal, July 2004
- Charushnikova, I. A.; Den Auwer, C.
- Russian Journal of Coordination Chemistry, Vol. 30, Issue 7
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
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
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
Structures of Dimeric Hydrolysis Products of Thorium
journal, April 2007
- Wilson, Richard E.; Skanthakumar, S.; Sigmon, Ginger
- Inorganic Chemistry, Vol. 46, Issue 7
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
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
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
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
The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
journal, March 1974
- Basile, L. J.; Sullivan, J. C.; Ferraro, J. R.
- Applied Spectroscopy, Vol. 28, Issue 2
Infrared Spectra and Structure of the Crystalline Sodium Acetate Complexes of U(VI), Np(VI), Pu(VI), and Am(VI). A Comparison of Metal‐Oxygen Bond Distance and Bond Force Constant in this Series
journal, November 1955
- Jones, Llewellyn H.
- The Journal of Chemical Physics, Vol. 23, Issue 11
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
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
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
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
- Schnaars, David D.; Wilson, Richard E.
- Inorganic Chemistry, Vol. 57, Issue 6
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
The Crystal Structure of [(UO2)2(OH)2Cl2(H2O)4].
journal, January 1969
- Åberg, Märtha; Nilson, Leif; Larsen, Charles
- Acta Chemica Scandinavica, Vol. 23
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