Actinyl-cation interactions: experimental and theoretical assessment of [Np(vi)O2Cl4]2– and [U(vi)O2Cl4]2– systems

Bjorklund, Jennifer L.; Pyrch, Mikaela M.; Basile, Madeline C.; Mason, Sara E.; Forbes, Tori Z.

doi:10.1039/c9dt01753d

Actinyl-cation interactions: experimental and theoretical assessment of [Np(vi)O₂Cl₄]^2– and [U(vi)O₂Cl₄]^2– systems

Journal Article · Tue May 21 00:00:00 EDT 2019 · Dalton Transactions

DOI:https://doi.org/10.1039/c9dt01753d· OSTI ID:1668729

Bjorklund, Jennifer L. ^[1]; Pyrch, Mikaela M. ^[2]; Basile, Madeline C. ^[2]; Mason, Sara E. ^[2]; ^[2]

University of Iowa, Iowa City, IA (United States); University of Iowa
University of Iowa, Iowa City, IA (United States)

The interaction of the actinyl (AnO₂²⁺) oxo group with low-valent cations influences the chemical and physical properties of hexavalent actinides, but the impact of these intermolecular interactions on the actinyl bond and their occurrence in solution and solid state phases remain unclear. In this study, we explore the coordination of alkali cations (Li⁺, Na⁺, K⁺) with the [NpO₂Cl₄]^2– coordination complexes using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory (DFT) calculations and compare to the related uranyl system. Three solid-state coordination compounds ([Li(12-crown-4)]₂[NpO₂Cl₄] (LiNp), [Na(18-crown-6)H₂O]₂[NpO₂Cl₄] (NaNp), and [K(18-crown-₆)]₂[NpO₂Cl₄] (KNp) have been synthesized and characterized using single-crystal X-ray diffraction and Raman spectroscopy. Only Li⁺ cations interact with the neptunyl oxo in the solid-state compounds and this results in a red-shift of the NpO₂²⁺ symmetric stretch (ν₁). Raman spectra of Np(VI) solutions containing lower Li⁺ concentrations display a single peak at ~854 cm^–1 and increasing the amount of Li⁺ results in the ingrowth of a second band at 807 cm^–1. DFT calculations and vibrational analysis indicate the lower frequency vibrational band is the result of interactions between the Li⁺ cation and the neptunyl oxo. Here, comparison to the related uranyl system shows similar interactions occur in the solid state, but subtle differences in the actinyl-cation modes in solution phase.

View Accepted Manuscript (DOE)

Research Organization:: University of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0013980

OSTI ID:: 1668729

Alternate ID(s):: OSTI ID: 1523299
OSTI ID: 1612056

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 24 Vol. 48; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1912314: Experimental Crystal Structure Determination L., Bjorklund, Jennifer; M., Pyrch, Mikaela; C., Basile, Madeline https://doi.org/10.5517/ccdc.csd.cc225xkr The current record is supplemented by this dataset	dataset	January 2019
CCDC 1912315: Experimental Crystal Structure Determination L., Bjorklund, Jennifer; M., Pyrch, Mikaela; C., Basile, Madeline https://doi.org/10.5517/ccdc.csd.cc225xls The current record is supplemented by this dataset	dataset	January 2019
CCDC 1912316: Experimental Crystal Structure Determination L., Bjorklund, Jennifer; M., Pyrch, Mikaela; C., Basile, Madeline https://doi.org/10.5517/ccdc.csd.cc225xmt The current record is supplemented by this dataset	dataset	January 2019