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Reactions of AIH3·NME3 with nitriles: Structural characterization and substitution reactions of hexameric aluminum imides
Reddy, N. Dastagiri,Roesky, Hebert W.,Noltemeyer, Mathias,Schmidt, Hans-Georg
, p. 2374 - 2378 (2002)
The reaction of AIH3·NMe3 with RCN proceeds with the evolution of trimethylamine and affords (HAINCH2R)6 (R = Ph (1), p-MeC6H4 (2), p-CF3C6H4 (3)). Compounds 1 and 3 are characterized by single-crystal structural analysis. Compound 1 reacts with Me3SiBr as well as with PhC≡CH to give (XAINCH2Ph)6 (X = Br (4), PhC≡C (5)). Structural data and other characterization data of compounds 4 and 5 show that all the hydridic hydrogen atoms in 1 have been replaced by bromine atoms and PhC≡C groups, respectively. Compounds 1-5 are potential precursors for the preparation of aluminum nitride. Crystals of 1 are rhombohedral, space group R3, with a = 15.7457(13) A, b = 15.7457(13) A, c = 14.949(2) A, V = 3209.8(5) A3, and Z = 3. Crystals of 3·3/4C7H8 are triclinic, space group P1, with a = 17.527(11) A, b = 18.894(12) A, c = 19.246(15) A, α = 96.11(7)°, β = 102.23(4)°, γ = 106.79(3)°, V= 5867(7) A3, and Z = 4. Compound 4 crystallizes in the monoclinic space group P21/c, with a = 14.175(4) A, b = 16.678(5) A, c = 10.731(3) A, β = 106.82(2)°, V = 2428.6(11) A3, and Z = 2. Compound 5·C7H8 crystallizes in the monoclinic space group C2/c, with a = 25.842(5) A, b = 15.443(3) A, c= 20.699(4) A, β = 105.88(3)°, V = 7945(3) A3, and Z = 4.
