High‐Energy‐Density Materials: Synthesis and Characterization of N₅⁺[P(N₃)₆]⁻, N₅⁺ [B(N₃)₄]⁻, N₅⁺ [HF₂]⁻⋅n HF, N₅⁺ [BF₄]⁻, N₅⁺ [PF₆]⁻, and N₅⁺ [SO₃F]⁻

Abstract

23 nitrogens and only one phosphorus: The N5+ ion is combined with energetic anions in the form of N5+ [P(N3)6]− and N5+ [B(N3)4]− (see scheme), containing 91 and 96 wt %, respectively, of nitrogen. Also, the thermally unstable compound N5HF2⋅n HF is prepared by metathesis from N5SbF6 and CsHF2. Its usefulness as a reagent for the synthesis of new N5+ salts is demonstrated with the preparation of N5PF6, N5BF4, and N5SO3F.

Synthesis of AgN5 and its extended 3D energetic framework

“…However, the reported N 5 + and cyclo -N 5 ˉ complexes generally contain non-energetic counter ions or groups to enhance their stabilities. For example, SbF 6 ˉ or SnF 6 2 ˉ are non-energetic counter ions in N 5 + salts 13,14 , and H 2 O, Clˉ, NH 4 + , and H 3 O + are used to stabilize the cyclo -N 5 ˉ anion 1 . These non-energetic components impact their energetic properties, such as heat of formation and detonation parameters.…”

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

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During the last decade, there has been much interest in inorganic polyazide chemistry. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Because of the energetic nature of the azido group, polyazides are highly endothermic compounds, the energy content of which increases with an increasing number of azido ligands. It is, therefore, not surprising that the synthesis of molecules with a high number of azido groups is very challenging owing to their explosive nature and shock sensitivity.A significant number of pentavalent binary azido compounds of the heavier Group 5 elements have been prepared and characterized, namely Nb(N 3 ) 5 [14,15] However, the situation is different for vanadium for which only trivalent binary azides were known.

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Synthesis, Structures and DFT Calculations on Alkaline‐Earth Metal Azide‐Crown Ether Complexes

“…The alkaline-earth metal azides Ca(N 3 ) 2 , Sr(N 3 ) 2 and Ba(N 3 ) 2 ·H 2 O were made [14] by distilling excess dilute aqueous HN 3 directly onto slurries of MCO 3 or M(OH) 2 in water (see Experimental Section). The strontium and barium compounds were readily obtained, but as previously reported, [14] the calcium compound is prone to hydrolysis and excess HN 3 and cautious precipitation with alcohol is necessary to obtain a reasonably pure sample and the yield is poorer.…”

“…Also, we have explored both direct reaction of the crown ether with M(N 3 ) 2 and metathesis routes to introduce the azides. Literature examples of complexes of alkaline-earth metal azides are very few, but include [M{N-A C H T U N G T R E N N U N G (CH 2 CH 2 OH) 3 } 2 ](N 3 ) 2, (M = Ca or Sr) [9] in which the metal is eight-coordinate (bonded to two nitrogens and six oxygens in the NA C H T U N G T R E N N U N G (CH 2 CH 2 OH) 3 units) and azide counter-anions, [CaA C H T U N G T R E N N U N G (dmf) 2 (N 3 ) 2 ] which is polymeric with the calcium O-coordinated to the dmf and to four bridging azides, [10] and [Ca(N 3 ) 2 NNN bridges, the first example of this type in main group chemistry. The structures obtained have been compared with molecular structures computed by density functional theory (DFT).…”