The Uranium(VI) Oxoazides [UO2(N3)2⋅CH3CN], [(bipy)2(UO2)2(N3)4], [(bipy)UO2(N3)3]−, [UO2(N3)4]2−, and [(UO2)2(N3)8]4−

AbstractThe reaction between [UO2F2] and an excess of Me3SiN3 in acetonitrile solution results in fluoride–azide exchange and the uranium(VI) dioxodiazide adduct [UO2(N3)2⋅CH3CN] was isolated in quantitative yield. The subsequent reaction of [UO2(N3)2⋅CH3CN] with 2,2′‐bipyridine (bipy) resulted in the formation of the azido‐bridged binuclear complex [(bipy)2(UO2)2(N3)4]. The triazido anion [(bipy)UO2(N3)3]− was obtained by the reaction of [UO2(N3)2⋅CH3CN] with stoichiometric amounts of bipy and the ionic azide [PPh4][N3]. The reaction of [UO2(N3)2] with two equivalents of the [PPh4][N3] resulted in the formation of the mononuclear tetraazido anion [UO2(N3)4]2− as well as the azido‐bridged binuclear anion [(UO2)2(N3)8]4−. The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy)2(UO2)2(N3)4]⋅CH3CN, [PPh4][(bipy)UO2(N3)3], [PPh4]2[UO2(N3)4], [PPh4]2[UO2(N3)4]⋅2CH3CN, and [PPh4]4[(UO2)2(N3)8]⋅4CH3CN by their X‐ray crystal structures.