Cocrystallization of Plutonium(III) and Plutonium(IV) Diglycolamides with Pu(III) and Pu(IV) Hexanitrato Anions: A Route to Redox Variants of [Pu III,IV (DGA) 3 ] x .

-tetramethyl diglycolamide (TMDGA), a methylated variant of the diglycolamide extractants being proposed as curium holdback reagents in advanced used nuclear fuel reprocessing technologies, has been crystallized with plutonium, a transuranic actinide that has multiple accessible oxidation states. Two plutonium TMDGA complexes, [Pu(TMDGA)][Pu(NO)] and[Pu(TMDGA)][Pu(NO)]·0.75MeOH, were crystallized through solvent diffusion of a reaction mixture containing plutonium(III) nitrate and TMDGA. The sample was then partially oxidized by air to yield [Pu(TMDGA)][Pu(NO)]·0.75MeOH. Single-crystal X-ray diffraction reveals that the multinuclear systems crystallize with hexanitrato anionic species, providing insight into the first solid-state isolation of the elusive trivalent plutonium hexanitrato species. Crystallography data show a change in geometry around the TMDGA metal center from Pu to Pu, with the symmetry increasing approximately from to . These complexes provide a rare opportunity to investigate the bond metrics of plutonium in two different oxidation states with similar coordination environments. Further, these new structures provide insight into the potential chemical and structural differences arising from the radiation-induced formation of transient tetravalent curium oxidation states in used nuclear fuel reprocessing streams.