Syntheses and structures of triazides of heavy group 15 elements

Abstract

Synthesis of group 15-triazides E(N(3))(3) (E = Sb 1, Bi 2) and Py(2)-Bi(N(3))(3)3 (Py = pyridine). Single crystals of 1 were in situ grown by an IR-laser-assisted technique on the diffractometer. The structure of 3, which represents the first structurally characterized neutral Bi-triazide, is influenced by crystal packing effects according to DFT calculations.

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

“…Two well-resolved 14 N NMR resonances are found in each spectrum (recorded in [D 6 ]DMSO) [21] at 300 K. As expected, the 14 N spectra for both the [As] and [Sb] compounds show a sharp signal at d = À135 ppm (As: Dn = 29 Hz) or d = À135 ppm (Sb: Dn = 37 Hz), which corresponds to the N b atoms, and a mediumsharp resonance at d = À239 ppm (As: Dn = 440 Hz) or d = À250 ppm (Sb: Dn = 350 Hz), which corresponds to the N g atoms; these values are in accord with known literature values for covalently bound azide groups. [1,5,6] Interestingly, only the resonance of the N g atoms is sensitive to the substitution pattern of the pnictogen atom. The d N g value increases in the order [As]…”

“…À , [12] [As V (N 3 ) 6 ] À , [13] and [Sb V (N 3 ) 6 ] À ; [10] no experimentally determined structural data are available for Group 15 azides of the type [E III (N 3 ) 5 ] 2À (E = P, As, Sb, Bi) and [E III (N 3 ) 4 ] À (E = P, As, Sb). [19] Following our interest in Group 15-element/nitrogen compounds with a high nitrogen content, [6,20] herein, we report the synthesis and full characterization of [E III (N 3 ) 4 ] À (E = As, Sb) and the isolation of the pentaazide [Bi III (N 3 ) 5 ] 2À stabilized as its DMSO adduct.…”

“…[19] Following our interest in Group 15-element/nitrogen compounds with a high nitrogen content, [6,20] herein, we report the synthesis and full characterization of [E III (N 3 ) 4 ] À (E = As, Sb) and the isolation of the pentaazide [Bi III (N 3 ) 5 ] 2À stabilized as its DMSO adduct.…”

“…[1] Classification of binary azides of Group 15 elements can be carried out with respect to the oxidation state (+III versus +V) and the charge of the element (cationic, neutral, or anionic), respectively. According to their oxidation state, these azides can be grouped as follows: E III compounds E(N 3 ) 3 (E = P, [2] As, [3] Sb, [3c, 4, 5] and Bi [5][6][7] ), [E(N 3 ) 4 ]…”

Solid‐State Structure of Bromine Azide

“…[9] However, the gas-phase structure of BrN 3 , which adopts a trans-bent structure, could be determined by electron diffraction, [9] and the experimental structure parameters agreed well with those obtained from quantum-chemical calculations. [10] We became interested in the synthesis of covalent azides only recently, and reported on the solid-state structures of Group 15 triazides (Sb(N 3 ) 3 , Pyr 2 Bi(N 3 ) 3 ), [11] a novel pentaazidoantimonite dianion (Sb(N 3 ) 5 2À ), [12] and organoantimony diazides RSb(N 3 ) 2 .…”