Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes
Abstract
Here, the synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et4N]4[PuIV(NCS)8], [Et4N]4[ThIV(NCS)8], and [Et4N]4[CeIII(NCS)7(H2O)] are reported. Thiocyanate was found to rapidly reduce plutonium to PuIII in acidic solutions (pH<1) in the presence of NCS–. The optical spectrum of [Et4N][SCN] containing PuIII solution was indistinguishable from that of aquated PuIII suggesting that inner-sphere complexation with [Et4N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et4N]4[PuIV(NCS)8] was crystallized when a large excess of [Et4N][NCS] was present. This compound, along with its UIV analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced AnIV–NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1237917
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 21; Journal Issue: 44; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; actinoids; coordination chemistry; plutonium; thiocyanates
Citation Formats
Carter, Tyler J., and Wilson, Richard E. Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes. United States: N. p., 2015.
Web. doi:10.1002/chem.201502770.
Carter, Tyler J., & Wilson, Richard E. Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes. United States. https://doi.org/10.1002/chem.201502770
Carter, Tyler J., and Wilson, Richard E. Thu .
"Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes". United States. https://doi.org/10.1002/chem.201502770. https://www.osti.gov/servlets/purl/1237917.
@article{osti_1237917,
title = {Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes},
author = {Carter, Tyler J. and Wilson, Richard E.},
abstractNote = {Here, the synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et4N]4[PuIV(NCS)8], [Et4N]4[ThIV(NCS)8], and [Et4N]4[CeIII(NCS)7(H2O)] are reported. Thiocyanate was found to rapidly reduce plutonium to PuIII in acidic solutions (pH<1) in the presence of NCS–. The optical spectrum of [Et4N][SCN] containing PuIII solution was indistinguishable from that of aquated PuIII suggesting that inner-sphere complexation with [Et4N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et4N]4[PuIV(NCS)8] was crystallized when a large excess of [Et4N][NCS] was present. This compound, along with its UIV analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced AnIV–NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.},
doi = {10.1002/chem.201502770},
journal = {Chemistry - A European Journal},
number = 44,
volume = 21,
place = {United States},
year = {Thu Sep 10 00:00:00 EDT 2015},
month = {Thu Sep 10 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 9 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
How Hydrogen Bonds Affect the Growth of Reverse Micelles around Coordinating Metal Ions
journal, March 2014
- Qiao, Baofu; Demars, Thomas; Olvera de la Cruz, Monica
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
Covalency in f-element bonds
journal, October 2002
- Choppin, Gregory R.
- Journal of Alloys and Compounds, Vol. 344, Issue 1-2
Fundamental Investigations of Separations Science for Radioactive Materials
journal, July 2000
- Nash, Kenneth L.; Barrans, Richard E.; Chiarizia, Renato
- Solvent Extraction and Ion Exchange, Vol. 18, Issue 4
The absorption spectra of plutonium ions in perchloric acid solutions
journal, March 1961
- Cohen, Donald
- Journal of Inorganic and Nuclear Chemistry, Vol. 18
Comparison of the solution chemistry of the actinides and lanthanides
journal, September 1983
- Choppin, Gregory R.
- Journal of the Less Common Metals, Vol. 93, Issue 2
The Curium Aqua Ion
journal, April 2007
- Skanthakumar, S.; Antonio, Mark R.; Wilson, Richard E.
- Inorganic Chemistry, Vol. 46, Issue 9
The Synthesis, and the Crystal and Molecular Structures of Tetraethylammonium [Aquaheptakis(thiocyanato)lanthanoidate(III)], [(C 2 H 5 ) 4 N] 4 [M(SCN) 7 (H 2 O)], (M=La, Ce, Pr; Nd, Dy, Er): The Complexes in a Cubic Octa-Coordination Geometry
journal, August 1988
- Tateyama, Yoshikuni; Kuniyasu, Yasumitsu; Suzuki, Yasuo
- Bulletin of the Chemical Society of Japan, Vol. 61, Issue 8
Comparative solution chemistry of the 4f and 5f elements
journal, June 1995
- Choppin, Gregory R.
- Journal of Alloys and Compounds, Vol. 223, Issue 2
New Approach to Separation of Trivalent Actinide Elements from Lanthanide Elements. Selective Liquid-Liquid Extraction with Tricaprylmethylammonium Thiocyanate.
journal, October 1964
- Moore, F. L.
- Analytical Chemistry, Vol. 36, Issue 11
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
The Structure and Synthesis of Plutonium(III) Chlorides from Aqueous Solution
journal, October 2006
- Wilson, Richard E.; Almond, Philip M.; Burns, Peter C.
- Inorganic Chemistry, Vol. 45, Issue 21
The Raman spectrum of [U(NCS)8]4? and configuration of the ion in solution
journal, January 1986
- Griffith, William P.; Mockford, M. Jane
- Journal of the Chemical Society, Dalton Transactions, Issue 5
Syntheses, and Crystal and Molecular Structures of Tetramethylammonium[Aquamethanolhexakis(isothiocyanato)lanthanoidates(III)], [(CH 3 ) 4 N] 3 [M(NCS) 6 (CH 3 OH)(H 2 O)] (M=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er), and Tetramethylammonium [Heptakis(isothiocyanato)lanthanoidates(III)], [(CH 3 ) 4 N] 4 [M(NCS) 7 ](M=Dy, Er, Yb)
journal, June 1989
- Matsumoto, Fumiko; Matsumura, Naomi; Ouchi, Akira
- Bulletin of the Chemical Society of Japan, Vol. 62, Issue 6
Structure and stereochemistry in 'f-block' complexes of high coordination number. VIII. The [M(unidentate)9] system. Crystal structures of [M(OH2)9] [CF3SO3]3, M = La, Gd, Lu, Y
journal, January 1983
- Harrowfield, Jm; Kepert, Dl; Patrick, Jm
- Australian Journal of Chemistry, Vol. 36, Issue 3
Crystal structure versus solution for two new lutetium thiocyanato complexes
journal, January 2011
- Lozano-Rodriguez, M. J.; Copping, R.; Petit, S.
- New Journal of Chemistry, Vol. 35, Issue 12
[An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory
journal, August 2010
- Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola
- Angewandte Chemie, Vol. 122, Issue 36
Solution coordination chemistry of actinides: Thermodynamics, structure and reaction mechanisms
journal, April 2006
- Szabo, Z.; Toraishi, T.; Vallet, V.
- Coordination Chemistry Reviews, Vol. 250, Issue 7-8
Das “nichtkoordinierende” Anion Tf2N−, koordiniert an Yb2+: ein strukturell charakterisierter Tf2N−-Komplex aus der ionischen Flüssigkeit [mppyr][Tf2N]
journal, August 2005
- Mudring, Anja-Verena; Babai, Arash; Arenz, Sven
- Angewandte Chemie, Vol. 117, Issue 34
Covalency in f-element complexes
journal, January 2013
- Neidig, Michael L.; Clark, David L.; Martin, Richard L.
- Coordination Chemistry Reviews, Vol. 257, Issue 2
Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides
journal, June 2012
- Hudson, Michael J.; Harwood, Laurence M.; Laventine, Dominic M.
- Inorganic Chemistry, Vol. 52, Issue 7
Liquid anion exchange of thiocyanate-nitrate actinide and lanthanide complexes
journal, October 1973
- Chiarizia, R.; Danesi, P. R.; Scibona, G.
- Journal of Inorganic and Nuclear Chemistry, Vol. 35, Issue 10
Inner versus outer sphere complexation of f-elements
journal, March 1997
- Choppin, Gregory R.
- Journal of Alloys and Compounds, Vol. 249, Issue 1-2
THERMODYNAMICS OF EXTRACTION OF Am(III) AND Eu(III) FROM NITRATE AND THIOCYANATE MEDIA WITH OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE
journal, November 1998
- Mathur, J. N.; Nash, K. L.
- Solvent Extraction and Ion Exchange, Vol. 16, Issue 6
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
Thermochromic properties of low-melting ionic uranyl isothiocyanate complexes
journal, January 2011
- Aoyagi, Noboru; Shimojo, Kojiro; Brooks, Neil R.
- Chemical Communications, Vol. 47, Issue 15
Thermodynamics of thiocyanate complexes of trivalent actinides and lanthanides
journal, April 1980
- Khopkar, P. K.; Mathur, Jagdish N.
- Thermochimica Acta, Vol. 37, Issue 1
An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides 1
journal, March 1954
- Diamond, R. M.; Street, K.; Seaborg, G. T.
- Journal of the American Chemical Society, Vol. 76, Issue 6
Octathiocyanato- and octaselenocyanato-complexes of the tetravalent actinide elements
journal, January 1972
- Al-Kazzaz, Z. M. S.; Bagnall, K. W.; Brown, D.
- Journal of the Chemical Society, Dalton Transactions, Issue 20
Thiocyanate complexing of Np(IV) and Pu(III)
journal, January 1978
- Vasudeva Rao, P. R.; Bagawde, S. V.; Ramakrishna, V. V.
- Journal of Inorganic and Nuclear Chemistry, Vol. 40, Issue 2
Lanthanide(III) trifluoromethanesulfonate complexes in anhydrous acetonitrile
journal, May 1993
- Di Bernardo, Plinio; Choppin, Gregory R.; Portanova, Roberto
- Inorganica Chimica Acta, Vol. 207, Issue 1
Tetraalkylammonium Uranyl Isothiocyanates
journal, October 2012
- Rowland, Clare E.; Kanatzidis, Mercouri G.; Soderholm, L.
- Inorganic Chemistry, Vol. 51, Issue 21
Structure and stereochemistry in f-block complexes of high co-ordination number. Part 3. The [M(bidentate ligand) 2 (unidentate ligand) 4 ] system : crystal structures of tetrakis(isothiocyanato)bis(octamethylpyrophosphoramide-OO″)uranium( IV ) and tetrachlorobis(octamethylpyrophosphoramide-OO″)thorium( IV )
journal, January 1983
- Kepert, David L.; Patrick, Jennifer M.; White, Allan H.
- J. Chem. Soc., Dalton Trans., Issue 3
Am(III) AND Eu(III) EXTRACTION BY ALIQUAT-336 AND BENZYL SUBSTITUTED QUATERNARY AMMONIUM SALTS FROM NITRATE AND THIOCYANATE SOLUTIONS*
journal, July 1995
- Chiarizia, R.; Gatrone, R. C.; Horwitz, E. P.
- Solvent Extraction and Ion Exchange, Vol. 13, Issue 4
A REVIEW OF THE BASIC CHEMISTRY AND RECENT DEVELOPMENTS IN TRIVALENT f-ELEMENTS SEPARATIONS
journal, May 1993
- Nash, Kenneth L.
- Solvent Extraction and Ion Exchange, Vol. 11, Issue 4
Europium-Based Ionic Liquids as Luminescent Soft Materials
journal, September 2008
- Tang, Sifu; Babai, Arash; Mudring, Anja-Verena
- Angewandte Chemie International Edition, Vol. 47, Issue 40
Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures
journal, March 2008
- Macrae, Clare F.; Bruno, Ian J.; Chisholm, James A.
- Journal of Applied Crystallography, Vol. 41, Issue 2
Structure of a cubic form of tetraethylammonium octakis(thiocyanato-N)thorate(IV), [N(C2H5)4]4[Th(NCS)8]
journal, February 1983
- Charpin, P.; Lance, M.; Navaza, A.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 39, Issue 2
Thiocyanate Complexes of Uranium in Multiple Oxidation States: A Combined Structural, Magnetic, Spectroscopic, Spectroelectrochemical, and Theoretical Study
journal, July 2014
- Hashem, Emtithal; Platts, James A.; Hartl, František
- Inorganic Chemistry, Vol. 53, Issue 16
Structures of Dysprosium(III) Triflates in Water, Methanol, and 2-Propanol As Studied by 17O and 19F NMR Spectroscopy
journal, May 1999
- van Loon, Arjen M.; van Bekkum, Herman; Peters, Joop A.
- Inorganic Chemistry, Vol. 38, Issue 13
The “Noncoordinating” Anion Tf2N− Coordinates to Yb2+: A Structurally Characterized Tf2N− Complex from the Ionic Liquid [mppyr][Tf2N]
journal, August 2005
- Mudring, Anja-Verena; Babai, Arash; Arenz, Sven
- Angewandte Chemie International Edition, Vol. 44, Issue 34
New amide complexes of uranium(IV) thiocyanate; the crystal structure of tetraisothiocyanatotris(NN,2-trimethylpropionamide-O)uranium(IV)
journal, January 1982
- Bagnall, Kenneth W.; Xing-fu, Li; Bombieri, Gabriella
- Journal of the Chemical Society, Dalton Transactions, Issue 1
Coordination Chemistry with f-Element Complexes for an Improved Understanding of Factors That Contribute to Extraction Selectivity
journal, June 2012
- Gorden, Anne E. V.; DeVore, Michael A.; Maynard, Branson A.
- Inorganic Chemistry, Vol. 52, Issue 7
Bei Raumtemperatur flüssige ionische Verbindungen auf Dysprosium-Basis mit starker Lumineszenz und Reaktion auf magnetische Felder
journal, September 2008
- Mallick, Bert; Balke, Benjamin; Felser, Claudia
- Angewandte Chemie, Vol. 120, Issue 40
Fingerprinting the oxidation state of U(iv) by emission spectroscopy
journal, January 2013
- Hashem, Emtithal; Lorusso, Giulia; Evangelisti, Marco
- Dalton Transactions, Vol. 42, Issue 41
Synthesis, characterization, and molecular structure of tetraethylammonium pentakis(isothiocyanato)bis(2,2'-bipyridine)uranate(IV)
journal, November 1980
- Wiley, R. O.; Von Dreele, R. B.; Brown, T. M.
- Inorganic Chemistry, Vol. 19, Issue 11
Thiocyanate complexing of some trivalent actinides and lanthanides
journal, December 1974
- Khopkar, P. K.; Mathur, J. N.
- Journal of Inorganic and Nuclear Chemistry, Vol. 36, Issue 12
Synthesis and structure of the six-coordinate hexaisothiocyanatolanthanide(III) complexes
journal, July 1968
- Martin, Joel L.; Thompson, Larry C.; Radonovich, Lewis J.
- Journal of the American Chemical Society, Vol. 90, Issue 16
Complexation-Induced Supramolecular Assembly Drives Metal-Ion Extraction
journal, August 2014
- Ellis, Ross J.; Meridiano, Yannick; Muller, Julie
- Chemistry - A European Journal, Vol. 20, Issue 40
Complexing of trivalent actinide ions by thiocyanate
journal, May 1974
- Kinard, W. F.; Choppin, G. R.
- Journal of Inorganic and Nuclear Chemistry, Vol. 36, Issue 5
Effect of ionic media on the stability constants of chloride, nitrate and thiocyanate complexes of americium(III) and europium(III)
journal, February 1971
- Khopkar, P. K.; Narayanankutty, P.
- Journal of Inorganic and Nuclear Chemistry, Vol. 33, Issue 2
Acidic Aqueous Decomposition of Thiocyanogen
journal, August 2004
- Barnett, Jon J.; McKee, Michael L.; Stanbury, David M.
- Inorganic Chemistry, Vol. 43, Issue 16
Aqueous complexation of trivalent lanthanide and actinide cations by N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine
journal, May 2000
- Jensen, Mark P.; Morss, Lester R.; Beitz, James V.
- Journal of Alloys and Compounds, Vol. 303-304
Europium-basierte ionische Flüssigkeiten als lumineszierende weiche Materialien
journal, September 2008
- Tang, Sifu; Babai, Arash; Mudring, Anja-Verena
- Angewandte Chemie, Vol. 120, Issue 40
Mesoscopic Aspects of Phase Transitions in a Solvent Extraction System
journal, October 2012
- Ellis, Ross J.; Audras, Matthieu; Antonio, Mark R.
- Langmuir, Vol. 28, Issue 44
The crystal structure of tetraethylammonium octathiocyanato-n-uranate(IV), [(C2H5)4N]4[U(NCS)8]: An example of cubical 8-coordination
journal, July 1971
- Countryman, Rachel; McDonald, W. S.
- Journal of Inorganic and Nuclear Chemistry, Vol. 33, Issue 7
Complexing of californium(III) and other trivalent actinides by inorganic ligands
journal, January 1980
- Khopkar, P. K.; Mathur, Jagdish N.
- Journal of Inorganic and Nuclear Chemistry, Vol. 42, Issue 1
High-Yield Synthesis and Single-Crystal X-ray Structure of a Plutonium(III) Aquo Complex: [Pu(H 2 O) 9 ][CF 3 SO 3 ] 3
journal, June 2001
- Matonic, John H.; Scott, Brian L.; Neu, Mary P.
- Inorganic Chemistry, Vol. 40, Issue 12
Evaluating f-Element Bonding from Structure and Thermodynamics
journal, September 2011
- Minasian, Stefan G.; Krinsky, Jamin L.; Arnold, John
- Chemistry - A European Journal, Vol. 17, Issue 44
Synthetic Coordination Chemistry: Principles and Practice
book, September 1996
- Davies, J. A.; Hockensmith, C. M.; Kukushkin, V. Yu
Dysprosium Room-Temperature Ionic Liquids with Strong Luminescence and Response to Magnetic Fields
journal, September 2008
- Mallick, Bert; Balke, Benjamin; Felser, Claudia
- Angewandte Chemie International Edition, Vol. 47, Issue 40
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
Critical survey of stability constants of complexes of thiocyanate ion (Technical Report)
journal, January 1997
- Bahta, Abraha; Parker, G. A.; Tuck, D. G.
- Pure and Applied Chemistry, Vol. 69, Issue 7
Thiocyanate complexes of some trivalent lanthanide and actinide elements
journal, June 1965
- Choppin, G. R.; Ketels, J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 27, Issue 6
Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations
journal, August 2002
- Jensen, Mark P.; Bond, Andrew H.
- Journal of the American Chemical Society, Vol. 124, Issue 33
[An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory
journal, June 2010
- Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola
- Angewandte Chemie International Edition, Vol. 49, Issue 36
Complexation-Induced Supramolecular Assembly Drives Metal-Ion Extraction
journal, August 2014
- Ellis, Ross J.; Meridiano, Yannick; Muller, Julie
- Chemistry - A European Journal, Vol. 20, Issue 40
The Structure and Synthesis of Plutonium(III) Chlorides from Aqueous Solution.
journal, January 2007
- Wilson, Richard E.; Almond, Philip M.; Burns, Peter C.
- ChemInform, Vol. 38, Issue 2
Works referencing / citing this record:
Interaction of An VI with Isothiocyanate Ion in Water-Organic Media (An = U, Np, Pu) : Interaction of An
journal, November 2019
- Fedoseev, Aleksander; Charushnikova, Iraida; Budantseva, Nina
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 645, Issue 22
Stereochemistry of Bk, Cf, and Es in Oxygen-Containing Compounds
journal, September 2018
- Serezhkina, L. B.; Serezhkin, V. N.
- Radiochemistry, Vol. 60, Issue 5
A Structural and Spectroscopic Study of the First Uranyl Selenocyanate, [Et4N]3[UO2(NCSe)5]
journal, February 2016
- Nuzzo, Stefano; Browne, Michelle; Twamley, Brendan
- Inorganics, Vol. 4, Issue 1