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)

Abstract

Proceed with caution: The use of fluoride starting materials and SO2 as a solvent yields neat triazides M(N3)3 (M=Ga, In, Tl), thus firmly establishing the existence of thallium triazide. In CH3CN, the new M(N3)3⋅CH3CN donor–acceptor adducts were obtained. Reactions of the triazides with tetraphenylphosphonium azide in CH3CN yields exclusively the novel [Ga(N3)5]2−, [In(N3)6]3− and [Tl(N3)6]3− anions (see picture, M green, N blue).

Preparation and Characterization of Group 13 Cyanides

“…The reactions of InF 3 and TlF 3 with three equivalents of [PPh 4 ]CN and an excess of Me 3 SiCN in acetonitrile solution resulted in equimolar mixtures of [PPh 4 ]CN and [PPh 4 ] 2 [In(CN) 5 ] or [PPh 4 ] 2 [Tl(CN) 5 ], respectively. This contrasts with the chemistry of the corresponding Group 13 azides, for which formation of the penta‐ and hexasubstituted anions [Ga(N 3 ) 5 ] 2− , [In(N 3 ) 6 ] 3− , and [Tl(N 3 ) 6 ] 3− is clearly favored over the tetra‐ and pentasubstituted anions [Ga(N 3 ) 4 ] − , [In(N 3 ) 5 ] 2− , and [Tl(N 3 ) 5 ] 2− …”

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

“…Athird N 3 group (N16-N18) points at an angle of 638 8 steeply below the equatorial plane while the fourth azido group (N10-N12) points at an angle of only 108 8 slightly below this plane.Asimilar arrangement of the azido ligands is also found for the hexaazido anions [In(N 3 ) 6 ] 3À and [Tl(N 3 ) 6 ] 3À . [8] TheZr À Ndistances range from 2.132(2) to 2.178(3) and are significantly shorter than the ones found for [ZrCl 4 (N 3 ) 2 ] 2À (2.20(1) ) [3d] but are in good agreement with typical Zr À N bond lengths reported in the literature. [9] Themost interesting feature of the [Zr(N 3 ) 6 ] 2À structure,h owever,i st he fact that the axial azido ligands exhibit asignificantly enlarged average Zr-N-N bond angle of 167.1(2)8 8 while the four equatorial ligands (140.9(2)8 8)s how bond angles that are typical for covalent azides.…”

“…These relatively high decomposition onset temperatures and the insensitivity to friction and impact can be attributed to the increased ionic character of the azido groups due to anion formation as well as the presence of two large organic counter-ions per anion. [8] The hexaazidometallate salts were identified and characterized by their crystal structures,v ibrational and 14 NNMR spectra as well as the observed material balances.The experimental and calculated vibrational frequencies and intensities are given in the Supplementary Information. 6 ] 2À anion has ap seudo-octahedral coordination environment around the central zirconium atom (Figure 1) with ligand arrangement different than in the related anion [Ti(N 3 ) 6 ] 2À .…”

Preparation of the First Manganese(III) and Manganese(IV) Azides

“…To further establish the identity of Mn(N 3 ) 2 and to examine its stabilization by anion or adduct formation, the diazide was treated with two equivalents of PPh 4 4 ] and (bipy) 2 Mn(N 3 ) 2 were obtained as beige/brown and orange, respectively, and insensitive crystalline solids. They were characterized by their vibrational spectra and X-ray crystal structures, [14] as well as their decomposition temperatures, impact and friction sensitivities (see Supporting Information).…”