Chlorination of Pu and U Metal Using GaCl.

The oxidative chlorination of the plutonium metal was achieved through a reaction with gallium(III) chloride (GaCl). In DME (DME = 1,2-dimethoxyethane) as the solvent, substoichiometric (2.8 equiv) amounts of GaCl were added, which consumed roughly 60% of the plutonium metal over the course of 10 days. The salt species 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 salt. The extraction of in DME at 70 °C followed by crystallization produced , a product arising from the loss of GaCl. This method of halogenation worked on a small scale for plutonium and uranium, providing a route to cationic Pu and dicationic U complexes using GaCl in DME.