From the reaction of uranium hexafluoride UF6 with dry liquid ammonia, the [UF7(NH3)]3- anion and the [UF4(NH3)4] molecule were isolated and identified for the first time. They are found in signal-green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH4]3[UF7(NH3)].NH3) and emerald-green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF4(NH3)4].NH3). [NH4]3[UF7(NH3)].NH3 features discrete [UF7(NH3)]3- anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U(IV) compounds. The emerald-green [UF4(NH3)4].NH3 contains discrete tetraammine tetrafluorouranium(IV) [UF4(NH3)4] molecules. [UF4(NH3)4].NH3 is not stable at room temperature and forms pastel-green [UF4(NH3)4] as a powder that is surprisingly stable up to 147 degrees C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides.
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