Intriguing Reactivity of a 1,2‐Dihydrodialumane Towards Organic Azides – From a Terminal Diazido–Dialumane to <i>Pendulum‐Clock‐Like</i> Azide Bridging

Abstract

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 ).