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The Syntheses and Structure of the Vanadium(IV) and Vanadium(V) Binary Azides V(N3)4, [V(N3)6]2−, and [V(N3)6]


  • This work was funded by the Air Force Office of Scientific Research, the Office of Naval Research, the Defense Threat Reduction Agency, and the National Science Foundation. We thank Profs. G. Olah and S. Prakash for their steady support, and Drs. W. Wilson and R. Wagner for their help and stimulating discussions. Grants of computer time from the Department of Defense High Performance Computing Modernization Program at the Engineer Research and Development (ERDC) and Navy Department of Defense Supercomputing Centers are gratefully acknowledged.


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Shock-sensitive and highly explosive V(N3)4 was prepared from VF4 and Me3SiN3 by fluoride–azide exchange. Salts of the [V(N3)6]2− anion (see picture) were obtained by treatment of the neutral tetraazide with ionic azides. Vanadium(V) azide, the only binary vanadium(V) compound known apart from VF5, VF6, and V2O5, was successfully prepared from the VF6 anion.