Abstract
The reactivity of dihydro-dialane with organic azides is described. Treatment of the hybrid ligand-based dialane [(DNI{H}Al)(2)] (I) (DNI = [3,3-dimethyl-2-2-methyl-2-(2,6-diisopropylaniline)ethenyl]-3H-indolenine) with TMSN(3) (TMS = trimethylsilyl) at room temperature gives the first diazido-dialane [(DNI{N(3)}Al)(2)] (1). The transformation from here to a more stable aluminium-tetrazole [DNIAl(NTMS)(2)N(2)] (2) is established. The reaction of other RN(3) gives [(DNI{H}Al)(2)(κ(2)-N(3)R)] (R = Benzyl in 3 and 1-Adamantyl in 4) with the azide in a μ-bridging position between two aluminium atoms. Using (1)H NOESY/EXSY NMR spectroscopy, a positional exchange of the two TMS groups (2) via rotation of the tetrazole unit is observed. In contrast, compound 3 exhibits a pendulum-clock-like dynamic, with N(α) oscillating between the two aluminium atoms in solution. The reaction of dialane I with DippN(3) (Dipp = 2,6-(i)Pr(2)-C(6)H(3)) gives the dialuminium amine [{DNI(H)Al}(2)(μ-NDipp)] (5).