Synthesis of New Azidoalanes With Heterocyclic Molecular Structures

Abstract

The synthesis of the tetrameric azidoalanes [(CFtyClAl^fo (1) and [(CH3)BrAlN3]4 (2) with heterocyclic cyclooctane-like structures has been demonstrated. X-ray structural determinations reveal that 1 and 2 consist of AI4N4 eight-membered rings in which the Al atoms are bridged by the α nitrogens of the azide groups.[(CH3)C1AIN^]4 (1) crystallizes in the tetragonal space group P2jC with a = 11.077(4) , c = 8.662(4) , V = 1062.9(8) and Ζ = 8. [(Ch^BrAlN^k (2) crystallizes in the monoclinic space group P2.with a = 8.6702(12) ,6= 11.1311(15) c = 11.7501(16) , α = 90°, β = 97.913(2)°, γ= 90°, V = 1123.23(3)3 and Ζ = 8. The reaction of AlH3»N(CH3)3with HN3 resulted in formation of an azidoalane with composition close to A1H2N3»N(CH3)3 (3). This compound is unstable with respect to loss of H2 and N(CH3)3 at room temperature.

Synthesis and structures of M(Me3SiNCHNSiMe3)3 (M = Al, Ga) via reactions of M‐hydrides with Me3SiNCNSiMe3

“…The lithium salt was readily isolated in substantial yields and identified by its IR spectrum which matched exactly previously published data. 4 Furthermore, its combustion analysis for C, H, and N as well as the 7 Li NMR spectrum was consistent with the LiNCNSiMe 3 formula.…”

“…The solid was filtered and dried in vacuum and was identified by 7 Li NMR, IR and elemental analysis to be LiNCNSiMe 3 …”

Density functional theory study on (F2AlN3) n (n = 1–4) clusters

“…When n = 4, four stable structures (4A-4D) were obtained, possessing C s , S 4 , C i and C 2 symmetry with Al 4 N 4 core structures (the N 2 portion of the N 3 group also omitted for clarity reasons), respectively. Among them, the S 4 symmetry structure with the N 3 alternatively up and down has been suggested for the tetramers [(CH 3 )ClAlN 3 ] 4 and [(CH 3 )BrAlN 3 ] 4 [6] of the aluminum azides, and the other three structures have not been found except that we have reported [18]. Obviously, when n = 2-4, the Al-N a bonds form easily, and Al-Al and N a -N a bonds are not found.…”

“…Their excellent physical and chemical properties as high thermal-conductivity, low thermal-inflate coefficient, chemical inertness, and large energy gap make it an advanced ceramic material and a suitable dielectric for optical or optoelectronic devices [1][2][3]. New azides were synthesized to be used as single-source precursors for the CVD of nitrides [4][5][6][7][8][9][10][11]. A single-source precursor already contains the elements of interest in a single molecule, often directly bound together.…”

“…Organoaluminum azides have been synthesized and used as single-source precursors for aluminum nitride [4][5][6][7][8][9][10][11], however, the product formed has a high degree of carbon contamination due to pyrolysis of the organic substituent and is not suitable for commercial use. To eliminate the possibility of carbon inclusion, McMurran reported several related routes for GaN synthesis utilizing a new class of inorganic azide compounds that incorporate hydrogen and halide ligands [12][13][14][15][16] instead of organic groups.…”