Abstract
The pyrophoric compound Rb2[U(NH2)6] was obtained as a grey to black powder from the reaction of more than three equivalents of RbNH2 with UI3 in anhydrous liquid ammonia. During the process, UIII is oxidized to UIV and ammonia is reduced under evolution of H2. Rb2[U(NH2)6] crystallizes in the cubic crystal system, space group Fm3m, with the lattice parameter a = 9.7870(12) Å, V = 937.4(2) Å3, Z = 4 at T = 293 K. It is isotypic to K2PtCl6. The compound contains the unprecedented hexaamidouranate(IV) anion [U(NH2)6]2–.
Highlights
Our investigations on the reactions of uranium halides with anhydrous liquid ammonia and dissolved amides[1,2,3] were driven by the desire to obtain uranium nitrides such as UN under comparingly mild conditions
Choosing UI3 and RbNH2 dissolved in anhydrous liquid ammonia as starting materials for the synthesis of uranium nitrides is reasonable
Previous reports that employed other alkali metal amides claimed that UN would directly precipitate.[4]
Summary
Our investigations on the reactions of uranium halides with anhydrous liquid ammonia and dissolved amides[1,2,3] were driven by the desire to obtain uranium nitrides such as UN under comparingly mild conditions. The solutions become blue due to solvated electrons upon addition of, for example, a suitable alkali metal compound such as KI.[17,18,19] A reduction of potassium amide by UBr3 was suspected by Bergstrom.[19] The reaction of UI3 with RbNH2 in ammonia can be described by Equation (1), we will comment in more detail below.
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