First Structural Characterization of Binary As^IIIand Sb^IIIAzides

Abstract

The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects.

The Binary Group 4 Azides [Ti(N3)4], [P(C6H5)4][Ti(N3)5], and [P(C6H5)4]2[Ti(N3)6] and on Linear TiNNN Coordination

“…All the characterized covalent binary azide species possess bent MÀ NÀNN angles. [9] Herein, we report the synthesis, isolation, and characterization of the first binary Group , and provide explanations for the observed and predicted TiÀNÀNN bond angles.…”

Preparation and Characterization of the Binary Group 13 Azides M(N3)3 and M(N3)3⋅CH3CN (M=Ga, In, Tl), [Ga(N3)5]2−, and [M(N3)6]3− (M=In, Tl)

“…As found for other binary polyazides, [8][9][10][11][12][13][14][15][19][20][21] the neutral polyazides can be stabilized either by the formation of donoracceptor adducts with Lewis bases or by anion formation, which increases the ionicity of the azido groups. Because an ionic azide group possesses two double bonds while a covalent azido group has a single and a triple bond, increasing the ionicity of the existing azido ligands by further azide addition makes the breaking of an N À N bond more difficult and enhances the activation energy barrier toward catastrophic N 2 elimination.…”

Electronic Structure of Binary Phosphoric and Arsenic Triazides

“…However, the most stable conformer previously reported by using second-order perturbation theory (MP2), which had C 1 symmetry with two azido ligands adopting an anti orientation and the third azido ligand in a gauche-like orientation, [11] was calculated to be not a real local minimum at the B3LYP/6-311++G(3df) level of theory, and the relative energies for the two less stable conformers a and c here were calculated to be 2.06 and 0.94 kcal mol -1 higher than conformer b, including the zero-point energy (ZPE) corrections.…”

“…The B3LYP is a hybrid functional method based on Becke's three-parameter nonlocal exchange functional, [26] with Lee et al's nonlocal correlation. [27] For the arsenic triazide, geometry optimization was carried out according to the reported stable conformers [11] at the same level of theory. To assign the PES bands of both triazides, OVGF calculations were performed for those three stable conformers of P(N 3 ) 3 and As(N 3 ) 3 using the 6-311G(d) basis set based on optimized structures.…”

“…[8,9] For arsenic azides, much research has been devoted to the preparation and characterization of these compounds: [10] the first preparation of As(N 3 ) 3 and As(N 3 ) 4 + was reported by [10a,10c] the crystal structure of As(N 3 ) 3 was determined by ; [11] and the crystal structure of As(N 3 ) 6 -was determined by Klapötke et The electronic and molecular structures of many azides (unstable molecules) have been studied with theoretical and spectroscopic methods. [12] Recently, photoelectron spectroscopy in combination with high-level quantum chemical calculations has been successfully performed for elucidating many interesting aspects of monoazides [13] and diazides.…”