Chlorination of Pu and U Metal Using GaCl3

Carpenter, Stephanie Hope; Klamm, Bonnie Ellen; Fetrow, Taylor Victoria; Scott, Brian Lindley; Gaunt, Andrew James; Anderson, Nickolas H.; Tondreau, Aaron M.

doi:10.1021/acs.inorgchem.3c00522

Title: Chlorination of Pu and U Metal Using GaCl₃

Journal Article · Tue May 23 00:00:00 EDT 2023 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.3c00522· OSTI ID:1975651

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

The oxidative chlorination of the plutonium metal was achieved through a reaction with gallium(III) chloride (GaCl₃). In DME (DME = 1,2-dimethoxyethane) as the solvent, substoichiometric (2.8 equiv) amounts of GaCl₃ were added, which consumed roughly 60% of the plutonium metal over the course of 10 days. The salt species [PuCl₂(dme)₃][GaCl₄] was isolated as pale-purple crystals, and both solid-state and solution UV–vis–NIR spectroscopies were consistent with the formation of a trivalent plutonium complex. The analogous reaction was performed with uranium metal, generating a dicationic trivalent uranium complex crystallized as the [UCl(dme)₃][GaCl₄]₂ salt. The extraction of [UCl(dme)₃][GaCl₄]₂ in DME at 70 °C followed by crystallization produced [{U(dme)₃}₂(μ-Cl₃)][GaCl₄]₃, a product arising from the loss of GaCl₃. Finally, this method of halogenation worked on a small scale for plutonium and uranium, providing a route to cationic Pu³⁺ and dicationic U³⁺ complexes using GaCl₃ in DME.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC). Office of Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; AC52-06NA25396; 2020LANLE372

OSTI ID:: 1975651

Alternate ID(s):: OSTI ID: 1974820

Report Number(s):: LA-UR-23-21567

Journal Information:: Inorganic Chemistry, Vol. 62, Issue 22; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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