Synthesis, Solid‐State Structure, and Bonding Analysis of a Homoleptic Beryllium Azide

[Ph4P]2[Be(N3)4] (1) and [PNP]2[Be(N3)4] (2; PNP=Ph3PNPPh3) were synthesized by reacting Be(N3)2 with [Ph4P]N3 and [PNP]N3. Compound 1 represents the first structurally characterized homoleptic beryllium azide. The electronic structure and bonding situation in the tetraazidoberyllate dianion [Be(N3)4]2− were investigated by quantum‐chemical calculations (NPA, ELF, LOL). Nitrogen‐rich salts: Be(N3)2 reacts with two equivalents of [Ph4P]N3 and [PNP]N3 (PNP=Ph3PNPPh3) to give [Ph4P]2[Be(N3)4] (1) and [PNP]2[Be(N3)4] (2), which contain the tetraazidoberyllate dianion. Compound 1 was characterized by single‐crystal X‐ray analysis, and its electronic structure was studied by quantum‐chemical calculations. The solution structure of 2 was determined by heteronuclear NMR spectroscopy.