Benjamin Lyhs

Solid‐State Structure of Bromine Azide

Covalent azides have been investigated for more than hundred years. Hydrazoic acid (HN3) for instance was synthesized for the first time by Curtius in 1890. Since then, its molecular structure was investigated by use of IR and microwave spectroscopy as well as electron diffraction. Only very recently, Klapçtke et al. reported on the solid-state structure of the compound, which was determined by singlecrystal X-ray diffraction, showing that HN3 crystallizes in a two-layer structure in which almost planar layers, formed by intermolecular hydrogen bonds between the HN3 molecules, are stacked parallel to (001) with an ABA stacking sequence. Aside from HN3, the halogen azides XN3 (X = F, Cl, Br, I) are the simplest azides. They have been investigated experimentally and theoretically, in particular in respect to their bonding situation. IN3 was found to be monomeric in CFCl3 solution and forms a trans-bent structure in the gas phase. In contrast, in the solid state, IN3 adopts a polymeric structure, with disordered azide groups with almost identical I N bond distances (2.264(23), 2.30(3) ). Unfortunately, only IN3 has been structurally characterized by single-crystal Xray diffraction to date. The growth of suitable single crystals of halogen azides in general is difficult owing to their extreme sensitivity towards small pressure variations. For instance, bromine azide was reported to explode when Dp 0.05 Torr, and also upon crystallization. However, the gas-phase structure of BrN3, which adopts a trans-bent structure, could be determined by electron diffraction, and the experimental structure parameters agreed well with those obtained from quantum-chemical calculations. We became interested in the synthesis of covalent azides only recently, and reported on the solid-state structures of Group 15 triazides (Sb(N3)3, Pyr2Bi(N3)3), [11] a novel pentaazidoantimonite dianion (Sb(N3)5 2 ), and organoantimony diazides RSb(N3)2. [13] Herein, we expand these studies on the synthesis of halogen azides and present the single-crystal Xray structure of bromine azide, BrN3 (1). BrN3 (1) was prepared by reaction of NaN3 with bromine (Scheme 1). The N NMR spectrum of a solution of 1 in

Synthesis and structure of base-stabilized germanium(II) diazide IPrGe(N3)2.

Coordination of a strong σ-base has been shown to be an effective method for the stabilization of low valent main group element complexes. This general method was now used for the synthesis of the divalent germanium diazide. IPrGe(N3)21 represents the first neutral homoleptic germanium diazide that could be structurally characterized.

First Structural Characterization of Neutral, Base-Stabilized Group 15-Pentaazides: Single Crystal X-ray Structures of dmap-As(N3)5 and dmap-Sb(N3)5

Two neutral group 15-pentaazides dmap-As(N(3))(5) (1) and dmap-Sb(N(3))(5) (2) were synthesized and structurally characterized for the first time (dmap = 4-dimethylaminopyridine). Base-stabilization was confirmed to be very suitable for the kinetic stabilization of highly explosive covalent main group polyazides.

Synthesis, Solid State Structure and Bonding Analysis of the first Homoleptic Beryllium Azide

[Ph4 P]2 [Be(N3 )4 ] (1) and [PNP]2 [Be(N3 )4 ] (2; PNP=Ph3 PNPPh3 ) were synthesized by reacting Be(N3 )2 with [Ph4 P]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).