Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy
Abstract
Abstract The possibility that the relative reactivity of complexes of actinide metals in the +2 and +3 oxidation states could be investigated by examining reactions between An III and An II species of Th and U with rare‐earth metal reagents that provide EPR confirmation of electron transfer reactivity has been explored. Neither Cp’’ 3 Th III nor Cp’’ 3 U III will reduce Cp’’ 3 La III or Cp’ 3 Y III (Cp’=C 5 H 4 SiMe 3 , Cp’’=C 5 H 3 (SiMe 3 ) 2 ). However, both [K(2.2.2‐cryptand)][Cp’’ 3 Th II ] and [K(2.2.2‐cryptand)][Cp’’ 3 U II ] reduce Cp’’ 3 La III and Cp’ 3 Y III to form [Cp’’ 3 La II ] 1− and [Cp’ 3 Y II ] 1− , respectively, which were identified by EPR spectroscopy. The reverse reactions also occur which indicates that the reduction potentials are similar. [Cp’’ 3 La II ] 1− reduces Cp’ 3 Y III and the reverse Y II /La III combination also occurs. In both cases, the reactions generate EPR spectra indicative of multiple species in the mixtures of La II and Y II , which is consistent with ligand exchange and demonstrates that numerousmore »
- Authors:
-
[1];
[1]
- Department of Chemistry University of California, Irvine 1102 Natural Sciences II Irvine CA 92697-2025 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1593494
- Grant/Contract Number:
- SC0004739
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 26 Journal Issue: 7; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Moehring, Samuel A., and Evans, William J. Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy. Germany: N. p., 2020.
Web. doi:10.1002/chem.201905581.
Moehring, Samuel A., & Evans, William J. Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy. Germany. https://doi.org/10.1002/chem.201905581
Moehring, Samuel A., and Evans, William J. Thu .
"Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy". Germany. https://doi.org/10.1002/chem.201905581.
@article{osti_1593494,
title = {Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy},
author = {Moehring, Samuel A. and Evans, William J.},
abstractNote = {Abstract The possibility that the relative reactivity of complexes of actinide metals in the +2 and +3 oxidation states could be investigated by examining reactions between An III and An II species of Th and U with rare‐earth metal reagents that provide EPR confirmation of electron transfer reactivity has been explored. Neither Cp’’ 3 Th III nor Cp’’ 3 U III will reduce Cp’’ 3 La III or Cp’ 3 Y III (Cp’=C 5 H 4 SiMe 3 , Cp’’=C 5 H 3 (SiMe 3 ) 2 ). However, both [K(2.2.2‐cryptand)][Cp’’ 3 Th II ] and [K(2.2.2‐cryptand)][Cp’’ 3 U II ] reduce Cp’’ 3 La III and Cp’ 3 Y III to form [Cp’’ 3 La II ] 1− and [Cp’ 3 Y II ] 1− , respectively, which were identified by EPR spectroscopy. The reverse reactions also occur which indicates that the reduction potentials are similar. [Cp’’ 3 La II ] 1− reduces Cp’ 3 Y III and the reverse Y II /La III combination also occurs. In both cases, the reactions generate EPR spectra indicative of multiple species in the mixtures of La II and Y II , which is consistent with ligand exchange and demonstrates that numerous heteroleptic complexes of these Ln II ions exist.},
doi = {10.1002/chem.201905581},
journal = {Chemistry - A European Journal},
number = 7,
volume = 26,
place = {Germany},
year = {2020},
month = {1}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/chem.201905581
https://doi.org/10.1002/chem.201905581
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 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:
Solution Synthesis, Structure, and CO 2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe 3 ) 2 ] 3 } −
journal, January 2017
- Woen, David H.; Chen, Guo P.; Ziller, Joseph W.
- Angewandte Chemie International Edition, Vol. 56, Issue 8
Rare‐Earth Metal(II) Aryloxides: Structure, Synthesis, and EPR Spectroscopy of [K(2.2.2‐cryptand)][Sc(OC 6 H 2 t Bu 2 ‐2,6‐Me‐4) 3 ]
journal, November 2018
- Moehring, Samuel A.; Beltrán‐Leiva, María J.; Páez‐Hernández, Dayán
- Chemistry – A European Journal, Vol. 24, Issue 68
Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II)
journal, May 2012
- MacDonald, Matthew R.; Bates, Jefferson E.; Fieser, Megan E.
- Journal of the American Chemical Society, Vol. 134, Issue 20
Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment
journal, January 2017
- Fieser, Megan E.; Palumbo, Chad T.; La Pierre, Henry S.
- Chem. Sci., Vol. 8, Issue 11
Ligand Effects in the Synthesis of Ln 2+ Complexes by Reduction of Tris(cyclopentadienyl) Precursors Including C–H Bond Activation of an Indenyl Anion
journal, May 2015
- Corbey, Jordan F.; Woen, David H.; Palumbo, Chad T.
- Organometallics, Vol. 34, Issue 15
Synthesis and structure of mono-THF solvates of bis(cyclopentadienyl)samarium(II) complexes: (C5Me5)2 Sm(THF) and [C5H2(SiMe 3)3][C5H3(SiMe3)2]Sm(THF)
journal, February 1993
- Evans, William J.; Kociok-Köhn, Gabriele; Foster, Samuel E.
- Journal of Organometallic Chemistry, Vol. 444, Issue 1-2
Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe 3 ) 2 } 3 ] 1− Complexes of the Non-traditional +2 Lanthanide Ions
journal, May 2018
- Ryan, Austin J.; Darago, Lucy E.; Balasubramani, Sree Ganesh
- Chemistry - A European Journal, Vol. 24, Issue 30
Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich
journal, November 2017
- Kelly, Rory P.; Maron, Laurent; Scopelliti, Rosario
- Angewandte Chemie International Edition, Vol. 56, Issue 49
Reactivity of Decamethylsamarocene with Polycyclic Aromatic Hydrocarbons
journal, March 1994
- Evans, William J.; Gonzales, Shirley L.; Ziller, Joseph W.
- Journal of the American Chemical Society, Vol. 116, Issue 6
Reactivity of Ln(II) Complexes Supported by (C 5 H 4 Me) 1– Ligands with THF and PhSiH 3 : Isolation of Ring-Opened, Bridging Alkoxyalkyl, Hydride, and Silyl Products
journal, August 2018
- Woen, David H.; Huh, Daniel N.; Ziller, Joseph W.
- Organometallics, Vol. 37, Issue 18
Tetramethylcyclopentadienyl Ligands Allow Isolation of Ln(II) Ions across the Lanthanide Series in [K(2.2.2-cryptand)][(C 5 Me 4 H) 3 Ln] Complexes
journal, October 2018
- Jenkins, Tener F.; Woen, David H.; Mohanam, Luke N.
- Organometallics, Vol. 37, Issue 21
Reactivity of the Ln 2+ Complexes [K(2.2.2-cryptand)][(C 5 H 4 SiMe 3 ) 3 Ln]: Reduction of Naphthalene and Biphenyl
journal, November 2014
- Kotyk, Christopher M.; MacDonald, Matthew R.; Ziller, Joseph W.
- Organometallics, Vol. 34, Issue 11
Electrocatalytic H 2 O Reduction with f-Elements: Mechanistic Insight and Overpotential Tuning in a Series of Lanthanide Complexes
journal, February 2018
- Halter, Dominik P.; Palumbo, Chad T.; Ziller, Joseph W.
- Journal of the American Chemical Society, Vol. 140, Issue 7
Synthesis and Characterization of Organolanthanidocene(III) (Ln = La, Ce, Pr, Nd) Complexes Containing the 1,4-Cyclohexa-2,5-dienyl Ligand (Benzene 1,4-Dianion): Structures of [K([18]-crown-6)][Ln{η 5 -C 5 H 3 (SiMe 3 ) 2 -1,3} 2 (C 6 H 6 )] [Cp‘ ‘ = η 5 -C 5 H 3 (SiMe 3 ) 2 -1,3; Ln = La, Ce, Nd]
journal, December 1999
- Cassani, M. Cristina; Gun'ko, Yurii K.; Hitchcock, Peter B.
- Organometallics, Vol. 18, Issue 26
Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State
journal, February 2008
- Hitchcock, Peter B.; Lappert, Michael F.; Maron, Laurent
- Angewandte Chemie International Edition, Vol. 47, Issue 8
Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu II [C 5 H 3 (SiMe 3 ) 2 ] 3 } −
journal, March 2017
- Windorff, Cory J.; Chen, Guo P.; Cross, Justin N.
- Journal of the American Chemical Society, Vol. 139, Issue 11
Organoactinide electrochemistry. A cyclic voltammetric and coulometric study of (C5Me5)2UCl2, [(C5Me5)2UCl2· THF]−Na+, (C5Me5)2UCl · THF and (C5Me5ThCl2
journal, April 1982
- Finke, Richard G.; Gaughan, Glen; Voegeli, Richard
- Journal of Organometallic Chemistry, Vol. 229, Issue 2
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ Backbonding
journal, May 2014
- La Pierre, Henry S.; Scheurer, Andreas; Heinemann, Frank W.
- Angewandte Chemie International Edition, Vol. 53, Issue 28
The experimental determination of Th( iv )/Th( iii ) redox potentials in organometallic thorium complexes
journal, January 2019
- Inman, Christopher J.; Cloke, F. Geoffrey N.
- Dalton Transactions, Vol. 48, Issue 29
Trimethylsilyl versus Bis(trimethylsilyl) Substitution in Tris(cyclopentadienyl) Complexes of La, Ce, and Pr: Comparison of Structure, Magnetic Properties, and Reactivity
journal, February 2018
- Palumbo, Chad T.; Darago, Lucy E.; Windorff, Cory J.
- Organometallics, Vol. 37, Issue 6
Identification of the Formal +2 Oxidation State of Neptunium: Synthesis and Structural Characterization of {Np II [C 5 H 3 (SiMe 3 ) 2 ] 3 } 1–
journal, May 2018
- Su, Jing; Windorff, Cory J.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 140, Issue 24
Synthesis, properties and structures of the tris(cyclopentadienyl)thorium(III) complexes [Th{η5-C5H3(SiMe2R)2-1,3}3] (R=Me or tBu)
journal, November 2001
- Blake, Paul C.; Edelstein, Norman M.; Hitchcock, Peter B.
- Journal of Organometallic Chemistry, Vol. 636, Issue 1-2
Synthetic Aspects of (C 5 H 4 SiMe 3 ) 3 Ln Rare-Earth Chemistry: Formation of (C 5 H 4 SiMe 3 ) 3 Lu via [(C 5 H 4 SiMe 3 ) 2 Ln] + Metallocene Precursors
journal, April 2013
- Peterson, Jeffrey K.; MacDonald, Matthew R.; Ziller, Joseph W.
- Organometallics, Vol. 32, Issue 9
Synthesis, Arrangement, and Reactivity of Arene−Lanthanide Compounds
journal, June 2002
- Bochkarev, Mikhail N.
- Chemical Reviews, Vol. 102, Issue 6
Solution Synthesis, Structure, and CO 2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe 3 ) 2 ] 3 } −
journal, January 2017
- Woen, David H.; Chen, Guo P.; Ziller, Joseph W.
- Angewandte Chemie, Vol. 129, Issue 8
Defluorination of perfluoroolefins by divalent lanthanoid reagents: activating carbon-fluorine bonds
journal, July 1990
- Watson, Patricia L.; Tulip, Thomas H.; Williams, Ian
- Organometallics, Vol. 9, Issue 7
Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln 2+ Ions in the [K(2.2.2-cryptand)][(C 5 H 4 SiMe 3 ) 3 Ln] Complexes: The Variable Nature of Dy 2+ and Nd 2+
journal, December 2014
- Fieser, Megan E.; MacDonald, Matthew R.; Krull, Brandon T.
- Journal of the American Chemical Society, Vol. 137, Issue 1
Synthesis, structure, and reactivity of crystalline molecular complexes of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 Th} 1− anion containing thorium in the formal +2 oxidation state
journal, January 2015
- Langeslay, Ryan R.; Fieser, Megan E.; Ziller, Joseph W.
- Chemical Science, Vol. 6, Issue 1
Expanding the Chemistry of Molecular U 2+ Complexes: Synthesis, Characterization, and Reactivity of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 U} − Anion
journal, December 2015
- Windorff, Cory J.; MacDonald, Matthew R.; Meihaus, Katie R.
- Chemistry - A European Journal, Vol. 22, Issue 2
Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C 5 H 4 SiMe 3 ) 3 U]
journal, August 2013
- MacDonald, Matthew R.; Fieser, Megan E.; Bates, Jefferson E.
- Journal of the American Chemical Society, Vol. 135, Issue 36
Synthesis and Characterization of a Neutral U(II) Arene Sandwich Complex
journal, November 2018
- Billow, Brennan S.; Livesay, Brooke N.; Mokhtarzadeh, Charles C.
- Journal of the American Chemical Society, Vol. 140, Issue 50
Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich
journal, November 2017
- Kelly, Rory P.; Maron, Laurent; Scopelliti, Rosario
- Angewandte Chemie, Vol. 129, Issue 49
Organolanthanoids. 9. Electrochemical reduction of tris(cyclopentadienyl)samarium(III), -ytterbium(III), and -europium(III) compounds in tetrahydrofuran
journal, November 1986
- Bond, A. M.; Deacon, G. B.; Newnham, R. H.
- Organometallics, Vol. 5, Issue 11
Syntheses and Structures of the Crystalline, Highly Crowded 1,3-Bis(trimethylsilyl)cyclopentadienyls [MCp″ 3 ] (M = Y, Er, Yb), [PbCp″ 2 ], [{YCp″ 2 (μ-OH)} 2 ], [(ScCp″ 2 ) 2 (μ-η 2 :η 2 -C 2 H 4 )], [YbCp″ 2 Cl(μ-Cl)K(18-crown-6)], and [{KCp″} ∞ ]
journal, December 2011
- Coles, Martyn P.; Hitchcock, Peter B.; Lappert, Michael F.
- Organometallics, Vol. 31, Issue 7
Metal versus Ligand Reduction in Ln 3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand
journal, February 2018
- Palumbo, Chad T.; Halter, Dominik P.; Voora, Vamsee K.
- Inorganic Chemistry, Vol. 57, Issue 5
EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006
- Stoll, Stefan; Schweiger, Arthur
- Journal of Magnetic Resonance, Vol. 178, Issue 1, p. 42-55
First identification by EPR spectra of lanthanum(ii) organometallic intermediates (and E½ for La3+ → La2+) in the C–O bond activation of dimethoxyethane
journal, January 1997
- Cristina Cassani, M.; Lappert, Michael F.; Laschi, Franco
- Chemical Communications, Issue 16
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr 2+ , Gd 2+ , Tb 2+ , and Lu 2+
journal, May 2013
- MacDonald, Matthew R.; Bates, Jefferson E.; Ziller, Joseph W.
- Journal of the American Chemical Society, Vol. 135, Issue 26
Isolation of reactive Ln( ii ) complexes with C 5 H 4 Me ligands (Cp Me ) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-Cp Me )K(18-crown-6)][Cp Me 3 Ln II ] (Ln = Tb, Ho)
journal, January 2018
- Huh, Daniel N.; Ziller, Joseph W.; Evans, William J.
- Dalton Transactions, Vol. 47, Issue 48
Synthesis of a Crystalline Molecular Complex of Y 2+ , [(18-crown-6)K][(C 5 H 4 SiMe 3 ) 3 Y]
journal, October 2011
- MacDonald, Matthew R.; Ziller, Joseph W.; Evans, William J.
- Journal of the American Chemical Society, Vol. 133, Issue 40
Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State
journal, February 2008
- Hitchcock, Peter B.; Lappert, Michael F.; Maron, Laurent
- Angewandte Chemie, Vol. 120, Issue 8
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ Backbonding
journal, May 2014
- La Pierre, Henry S.; Scheurer, Andreas; Heinemann, Frank W.
- Angewandte Chemie, Vol. 126, Issue 28