ic7b03238_si_001.pdf (1.79 MB)
Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure
journal contribution
posted on 2018-03-23, 13:48 authored by Alex McSkimming, Jing Su, Thibault Cheisson, Michael R. Gau, Patrick J. Carroll, Enrique R. Batista, Ping Yang, Eric J. SchelterSeparations 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.
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pyridyl-hydroxylamine ligandchemical oxidationElectrochemical studiesf-block elementsStrongly-Donating HydroxylamineU V cationstorage methodsstabilizationRedox PropertiesCoordination Chemistryoxidation statesRedox-based separations offer promiseligand typeshomoleptic complexeswaste processingElectronic Structure Separationshigh-valent actinidesThseparation techniquesU complexesone-electron oxidationdata support assignment
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