Polyazide Chemistry: The First Binary Group 6 Azides, Mo(N₃)₆, W(N₃)₆, [Mo(N₃)₇]⁻, and [W(N₃)₇]⁻, and the [NW(N₃)₄]⁻ and [NMo(N₃)₄]⁻ Ions

Abstract

Bang on target: The highly explosive Group 6 azides Mo(N3)6 and W(N3)6 are prepared by the reaction of Me3SiN3 with MoF6 and WF6, respectively. The structure of W(N3)6 has perfect rhombohedral C3 symmetry (see picture). The reaction of Mo(N3)6 and W(N3)6 with ionic azides leads to the formation of [Mo(N3)7]− and [W(N3)7]−, respectively, the first binary heptaazides. Controlled decomposition of these anions produces [NMo(N3)4]− and [NW(N3)4]−.

Synthesis of AgN5 and its extended 3D energetic framework

“…Polynitrogen compounds hold great promise due to their fast energy release and eco-friendly decomposition products 4–7 . Major advances in this area have been made during the past two decades, the two most remarkable new species discovered in this field are the pentazenium cation, N 5 + , 6–8 and the pentazolate anion, cyclo -N 5 ˉ 9–12 .…”

Homoleptic manganese(II)–azide layer: Synthesis, structural characterization and magnetic properties

“…Particular interest has been focused on the azido ligand for its diversity in coordination modes and efficiency in magnetic coupling, and a large number of azido-bridged complexes with different dimensionalities and various topologies have been reported in the literature [4][5][6]. These complexes can be divided into two classes besides the neutral binary metal azides [7,8]: (i) heteroleptic complexes with coligands [9][10][11][12][13][14][15][16] and (ii) homoleptic anionic ones with charge-balancing cations that may act as templates for the anionic metal-azide substructures [17][18][19][20][21][22]. Considerable progress has been made in the synthesis and characterization of the former class, but the latter class has been relatively rarely explored.…”

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2− (M=Mo, W)

“…[4] Theoxidation potential of ametal oxohalide or metal dioxohalide is lower than that of the corresponding oxygen-free metal halide with the metal in the same oxidation state.T he binary polyazides Mo(N 3 ) 6 7 ]h ave been described as very treacherous,e xtremely shock-and temperature-sensitive compounds that explode violently when warmed toward room temperature. [5] Theo nly structurally characterized polyazides of molybdenum and tungsten are W(N 3 ) 6 and [NMo(N 3 ) 4 ] À . [5,6] To the best of our knowledge,no molybdenum(VI) or tungsten(VI) oxopolyazide have been structurally characterized so far.…”

“…[5] Theo nly structurally characterized polyazides of molybdenum and tungsten are W(N 3 ) 6 and [NMo(N 3 ) 4 ] À . [5,6] To the best of our knowledge,no molybdenum(VI) or tungsten(VI) oxopolyazide have been structurally characterized so far.…”