Erste strukturelle Charakterisierung eines binären P‐N‐Moleküls: die hochenergetische Verbindung P₃N₂₁

Abstract

Explosive Mischung: Das erste Beispiel einer strukturellen Charakterisierung von binären, aus den Elementen Phosphor und Stickstoff aufgebauten Molekülen liegt mit der Einkristallstrukturanalyse des Phosphorazides P3N21 vor (siehe Molekülstruktur; orange P, blau N). Die mithilfe einer neuen Synthesestrategie als Reinsubstanz erhaltene Verbindung wurde zudem sowohl in Lösung als auch in der Gasphase charakterisiert.

Binary Pnictogen Azides—An Experimental and Theoretical Study: [As(N3)4]−, [Sb(N3)4]−, and [Bi(N3)5(dmso)]2−

“…[18] Furthermore the photoelectron spectrum of P(N 3 ) 3 was recently reported by Zeng et al [2d] Albeit heavier binary Group 15 azides have been well characterized by IR and Raman spectroscopy, information on their structures in the solid state is still rather scarce. Crystal structures are only known of As III (N 3 ) 3 , [3c] Sb III (N 3 ) 3 , [3c] [Bi III (N 3 ) 4 ] À , [6] and [Bi III (N 3 ) 6 ] 3À , [6] and of [P V (N 3 ) 6 ]…”

A New Route to Metal Azides

“…In this work Mn(N 3 ) 2 , Sn(N 3 ) 2 , and Eu(N 3 ) 2 , as well as their ammonia complexes were synthesized for the first time through lowtemperature methods. As(N 3 ) 5 , Sb(N 3 ) 3 , [4] Bi(N 3 ) 3 , [5] (P 3 N)(N 3 ) 3 , [6] or Te(N 3 ) 4 ). At room temperature and the respective vapor pressure of NH 3 , it became possible to grow single crystals of the dinuclear holmium azide [Ho 2 (m-NH 2 ) 3 -(NH 3 ) 10 ](N 3 ) 3 ·1.25 NH 3 .…”

“…As(N 3 ) 5 , Sb(N 3 ) 3 , [4] Bi(N 3 ) 3 , [5] (P 3 N)(N 3 ) 3 , [6] or Te(N 3 ) 4 ). As(N 3 ) 5 , Sb(N 3 ) 3 , [4] Bi(N 3 ) 3 , [5] (P 3 N)(N 3 ) 3 , [6] or Te(N 3 ) 4 ).…”

“…[1] However, it was only in the mid-1960s that chemists began to look at HN 3 and its derivative compounds in more detail. As(N 3 ) 5 , Sb(N 3 ) 3 , [4] Bi(N 3 ) 3 , [5] (P 3 N)(N 3 ) 3 , [6] or Te(N 3 ) 4 ). [1] More recently, azides have moved into research targeting high-energy density materials (HEDM), thus exhibiting an expanding field of applications and a promising potential for chemical syntheses.…”

Azide Chemistry – An Inorganic Perspective, Part I Metal ­Azides: Overview, General Trends and Recent Developments

“…“PN 23 ” ≡ N 5 [P(N 3 ) 6 ], N 5 [B(N 3 ) 4 ]) have been obtained whose nitrogen contents exceed 90 wt.‐ % 73. “P 3 N 21 ” consisting of a nearly planar six‐membered P 3 N 3 ring with three equatorial and three axial P‐bonded azide groups each was the first structurally characterized binary P–N molecule 74. Theoretical extrapolations on further homopolyatomic nitrogen compounds N n ( n = 6, 8, 10)75 including N 5 + N 3 – (and N 5 + N 5 – ) showed that these high energy forms of elementary dinitrogen are unstable with respect to spontaneous decomposition to N 3 and N 2 , and “will probably never be isolated“ 76,77.…”