The Vanadium(V) Oxoazides [VO(N 3 ) 3 ], [(bipy)VO(N 3 ) 3 ], and [VO(N 3 ) 5 ] 2−

Vanadium(V) oxoazide [VO(N 3 ) 3 ] was prepared through a fluoride–azide exchange reaction between [VOF 3 ] and Me 3 SiN 3 in acetonitrile solution. When the highly impact‐ and friction‐sensitive compound [VO(N 3 ) 3 ] was reacted with 2,2′‐bipyridine, the adduct [(bipy)VO(N 3 ) 3 ] was isolated. The reaction of [VO(N 3 ) 3 ] with [PPh 4 ]N 3 resulted in the formation and isolation of the salt [PPh 4 ] 2 [VO(N 3 ) 5 ]. The adduct [(bipy)VO(N 3 ) 3 ] and the salt [PPh 4 ] 23 [VO(N 3 ) 5 ] were characterized by vibrational spectroscopy and single‐crystal X‐ray structure determination, making these compounds the first structurally characterized vanadium(V) azides.