Chlorination of Pu and U Metal Using GaCl3
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...
Saved in:
Published in | Inorganic chemistry Vol. 62; no. 22; pp. 8462 - 8466 |
---|---|
Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
05.06.2023
American Chemical Society (ACS) |
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | 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 [PuCl 2 (dme) 3 ][GaCl 4 ] 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 ][GaCl 4 ] 2 salt. The extraction of [UCl(dme) 3 ][GaCl 4 ] 2 in DME at 70 °C followed by crystallization produced [{U(dme) 3 } 2 (μ-Cl 3 )][GaCl 4 ] 3 , a product arising from the loss of GaCl3. 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. |
---|---|
Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 89233218CNA000001; AC52-06NA25396; 2020LANLE372 USDOE Office of Science (SC). Office of Basic Energy Sciences (BES) USDOE Office of Science (SC), Basic Energy Sciences (BES) LA-UR-23-21567 USDOE National Nuclear Security Administration (NNSA) |
ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/acs.inorgchem.3c00522 |