Aluminum dihydride from E(iv) precursors (E = Si, Ge) and its bond-activation reactivities

Abstract

A distinctive synthetic route has been demonstrated in which the aminotroponiminato (ATI)-stabilized aluminum dihydride complex [(ATI)AlH₂] was prepared from a [(ATI)SiHCl₂] precursor. [(ATI)AlH₂] was also isolated from aluminum(III) dichloride [(ATI)AlCl₂] via salt-metathesis reaction. Subsequent reaction with the ATIH ligand enabled the isolation of the N-tetracoordinated (ATI)Al(III)-complex via aluminum monohydride [(ATI)AlH(ATI)] intermediate. The dihydride compound was found to activate CS (in CS₂) and PSe (in Ph₃PSe) bonds yielding the aluminum(III) μ-sulphide and μ-selenide dimer [(ATI)Al(μ-S)]₂ and [(ATI)Al(μ-Se)]₂, respectively. All compounds were characterized using multinuclear NMR spectroscopy and single-crystal X-ray diffraction.