Azidotris(trifluoromethyl)germane, (CF₃)₃GeN₃:  Spectroscopic Characterization and Density Functional Computations

Abstract

Azidotris(trifluoromethyl)germane, (CF(3))(3)GeN(3), was prepared from activated silver azide and iodotris(trifluoromethyl)germane in a neat reaction or in dichloromethane or toluene solution, respectively. (CF(3))(3)GeN(3) is a colorless, highly volatile liquid (mp ca. -85 degrees C) which was identified from MS data. The new compound was characterized by multinuclear solution NMR ((13)C, (14)N, (19)F) and gas-phase IR spectroscopy. The structure and the vibrational spectrum of (CF(3))(3)GeN(3) were computed employing density functional theory calculations (DFT) at the self-consistent level with the nonlocal exchange functional of Becke (B) and the nonlocal correlation functional of Lee, Yang, and Parr (B-LYP). The results of the DFT calculation and experimentally obtained vibrational spectra are in good agreement. The DFT computation at the correlated level (B-LYP) predicts the vibrational modes reasonably well, and no scaling was required.

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

“…Xe(N 3 )F, Ge(N 3 )(CF 3 ) 3 , As(N 3 ) n (CF 3 ) 3– n ( n = 1, 2), SO 2 (N 3 ) 2 – have drawn special attention (see also 2) 94–97. It has been pointed out that by applying Haas' element displacement principle the radicals CF 3 ( parafluorine ) and Ge(CF 3 ) 3 (as well as As(CF 3 ) 2 ) ( first‐order derivative parabromine ) can be related to halogen atoms, the latter actually most closely to chlorine; so Ge(N 3 )(CF 3 ) 3 and, in particular, As(N 3 )(CF 3 ) 2 exhibit properties (tendency of formation, stability) very similar to those of ClN 3 95,98,17,18. In numerous cases, the electronic structures of mono‐, di‐ or triazides have been determined experimentally (e.g.…”

Liquid Azide Salts

“…Covalent and ionic azides have been prepared involving almost every single element from the periodic table. Only recently, the chemistry of simple main-group and transition-metal azides have provided another high point in azide chemistry. – However, so far, azides have found only limited use because of their violent, explosive character, toxic decomposition products, and the attendant danger in handling them. The lately discovered transition-metal azides are no exception to that tendency.…”