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

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 U V 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:
Report Number(s):
LA-UR-17-31496
Journal ID: ISSN 0020-1669
Grant/Contract Number:
AC52-06NA25396
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)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1438120

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., 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.. 2018. "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.
@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}
}