The Vanadium(V) Oxoazides [VO(N3)3], [(bipy)VO(N3)3], and [VO(N3)5](2-).

Vanadium(V) oxoazide [VO(N3)3] was prepared through a fluoride-azide exchange reaction between [VOF3] and Me3SiN3 in acetonitrile solution. When the highly impact- and friction-sensitive compound [VO(N3)3] was reacted with 2,2′-bipyridine, the adduct [(bipy)VO(N3)3] was isolated. The reaction of [VO(N3)3] with [PPh4]N3 resulted in the formation and isolation of the salt [PPh4]2[VO(N3)5]. The adduct [(bipy)VO(N3)3] and the salt [PPh4]23[VO(N3)5] were characterized by vibrational spectroscopy and single-crystal X-ray structure determination, making these compounds the first structurally characterized vanadium(V) azides.