Pentavalent neptunyl ([OΞNpΞO]+) cation–cation interactions in aqueous/polar organic mixed-solvent media

Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.

doi:10.1007/s10953-017-0647-2

Pentavalent neptunyl ([OΞNpΞO]⁺) cation–cation interactions in aqueous/polar organic mixed-solvent media

Journal Article · Sat Jun 17 00:00:00 EDT 2017 · Journal of Solution Chemistry

DOI:https://doi.org/10.1007/s10953-017-0647-2· OSTI ID:1366418

Burn, Adam G. ^[1]; Martin, Leigh R. ^[2]; Nash, Kenneth L. ^[1]

Washington State Univ., Pullman, WA (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O]⁺) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalent linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al³⁺, Sc³⁺, Cr³⁺, Fe³⁺, In³⁺ and UO²⁺₂) and the pentavalent neptunyl cation (NpO⁺₂, whose coordination chemistry is similar to that of AmO⁺₂ while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. As a result, the Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the NpO⁺₂ • Cr³⁺ complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1366418

Journal Information:: Journal of Solution Chemistry, Journal Name: Journal of Solution Chemistry Journal Issue: 6 Vol. 46; ISSN 0095-9782

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (4)

Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations Estes, Shanna L.; Qiao, Baofu; Jin, Geng Bang Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07982-5	journal	January 2019
Elucidating cation–cation interactions in neptunyl dications using multi-reference ab initio theory Łachmańska, Aleksandra; Tecmer, Paweł; Legeza, Örs Physical Chemistry Chemical Physics, Vol. 21, Issue 2 https://doi.org/10.1039/c8cp04267e	journal	January 2019
Impacts of hydrogen bonding interactions with Np( v / vi )O ₂ Cl ₄ complexes: vibrational spectroscopy, redox behavior, and computational analysis Pyrch, Mikaela M.; Bjorklund, Jennifer L.; Williams, James M. Dalton Transactions, Vol. 49, Issue 20 https://doi.org/10.1039/d0dt00848f	journal	January 2020
Elucidating cation--cation interactions in neptunyl dications using multireference ab initio theory Lachmanska, Aleksandra; Tecmer, Pawel; Legeza, Ors arXiv https://doi.org/10.48550/arxiv.1804.02241	text	January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cation–cation interactions
mixed-solvents
neptunyl