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Title: Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

Abstract

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO)4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The salt [U(pyNO)4]+ was isolated by chemical oxidation of [U(pyNO)4]; spectroscopic and computational data support assignment as a UV cation.

Authors:
 [1];  [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1438120
Report Number(s):
LA-UR-17-31496
Journal ID: ISSN 0020-1669; TRN: US1900405
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 8; 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

McSkimming, Alex, Su, Jing, Cheisson, Thibault, Gau, Michael R., Carroll, Patrick J., Batista, Enrique R., Yang, Ping, and Schelter, Eric J. Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b03238.
McSkimming, Alex, Su, Jing, Cheisson, Thibault, Gau, Michael R., Carroll, Patrick J., Batista, Enrique R., Yang, Ping, & Schelter, Eric J. Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure. United States. doi:10.1021/acs.inorgchem.7b03238.
McSkimming, Alex, Su, Jing, Cheisson, Thibault, Gau, Michael R., Carroll, Patrick J., Batista, Enrique R., Yang, Ping, and Schelter, Eric J. Fri . "Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure". United States. doi:10.1021/acs.inorgchem.7b03238. https://www.osti.gov/servlets/purl/1438120.
@article{osti_1438120,
title = {Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure},
author = {McSkimming, Alex and Su, Jing and Cheisson, Thibault and Gau, Michael R. and Carroll, Patrick J. and Batista, Enrique R. and Yang, Ping and Schelter, Eric J.},
abstractNote = {Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO)4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The salt [U(pyNO)4]+ was isolated by chemical oxidation of [U(pyNO)4]; spectroscopic and computational data support assignment as a UV cation.},
doi = {10.1021/acs.inorgchem.7b03238},
journal = {Inorganic Chemistry},
number = 8,
volume = 57,
place = {United States},
year = {2018},
month = {3}
}

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Figures / Tables:

Figure 1 Figure 1: Simplified depiction of [M(pyNO)4]. Heteroatoms are highlighted for clarity.

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Works referencing / citing this record:

CCDC 1813273: Experimental Crystal Structure Determination: ZEWQIE : tetrakis((t-butyl(pyridin-2-yl)amino)oxido)-thorium(iv)
dataset, December 2017


CCDC 1813275: Experimental Crystal Structure Determination: FEZKAZ : tetrakis[N-t-butyl-N-(hydroxy)pyridin-2-aminato]-uranium(iv)
dataset, December 2017


Halide anion discrimination by a tripodal hydroxylamine ligand in gas and condensed phases
journal, January 2019

  • Cheisson, Thibault; Jian, Jiwen; Su, Jing
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 36
  • DOI: 10.1039/c9cp03764k

Tetranuclear oxido-bridged thorium( iv ) clusters obtained using tridentate Schiff bases
journal, January 2019

  • Tsantis, Sokratis T.; Lagou-Rekka, Aimilia; Konidaris, Konstantis F.
  • Dalton Transactions, Vol. 48, Issue 41
  • DOI: 10.1039/c9dt03189h

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex
journal, May 2018


Halide anion discrimination by a tripodal hydroxylamine ligand in gas and condensed phases
journal, January 2019

  • Cheisson, Thibault; Jian, Jiwen; Su, Jing
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 36
  • DOI: 10.1039/c9cp03764k

Tetranuclear oxido-bridged thorium( iv ) clusters obtained using tridentate Schiff bases
journal, January 2019

  • Tsantis, Sokratis T.; Lagou-Rekka, Aimilia; Konidaris, Konstantis F.
  • Dalton Transactions, Vol. 48, Issue 41
  • DOI: 10.1039/c9dt03189h

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex
journal, May 2018


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