Uranium Chemistry in liquid Ammonia: Compounds obtained by adventitious Presence of Moisture or Air

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UCl 4 , UBr 4 , UBr 5 , or UO 2 Cl 2 reacted with excess liquid ammonia – in adventitious presence of moisture and/or air – and formed some peculiar uranium compounds of which we present the crystal structures. [(NH 3 ) 7 (N 3 )U(μ‐O)U(NH 3 ) 8 ]Cl 5 ⋅ 7NH 3 contains a dinuclear μ‐O‐bridged uranium(IV) cation, [{(NH 3 ) 4 UO 2 } 2 (μ‐O)]Cl 2 ⋅ 4NH 3 features a dinuclear μ‐O‐bridged uranyl(VI) cation, while the compounds [(U(VI)O 2 ) 2 (U(V)O 2 ) 2 (μ 3 ‐O) 2 (NH 3 ) 12 ]Br 2 ⋅ 6NH 3 and [(U(VI)O 2 ) 4 (U(V)O 2 ) 4 (μ 3 ‐O) 4 (NH 3 ) 22 ]Br 4 ⋅ 16NH 3 are mixed‐valent containing uranyl(V)‐uranyl(VI) units. For these tetra‐ and octanuclear complex cations we observed that the O atoms of the uranyl(V) units can be μ 2 ‐ and even μ 3 ‐bridging to uranyl(VI) units, while the O atoms of the latter are acting as terminal ligands only. [(NH 3 ) 8 U(μ‐N)U(NH 3 ) 5 (μ‐N)UO 2 (NH 3 ) 4 ]Br 6 ⋅ 18NH 3 presents the first example of a compound where the isoelectronic species UO 2 2+ and UN 2 formed a complex with the NUN unit bridging to the U atom of the uranyl(VI) cation. As it is can be difficult to distinguish between N and O atoms with X‐ray diffraction, quantum‐chemical calculations at the DFT‐PBE0/TZVP level of theory were carried out which unequivocally confirmed the atom assignments in the crystal structures. The chemical bonding in the complex cations was studied using intrinsic bonding orbitals and allowed for an additional discrimination of the U(V) and U(VI) atoms in the mixed‐valent compounds.