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Title: 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 » heteroleptic complexes of these Ln II ions exist.« less

Authors:
ORCiD logo [1]; ORCiD logo [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}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1002/chem.201905581

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Cited by: 8 works
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