Reducing hybrid ligand-based alane and chasing aluminium(i): dialane and unusual transient dialumene

The alane [DNIAlH 2 ] (1) was reduced by Jones's Mg( i ) and Roesky's Al( i ) to give the dialane [{DNI(H)Al} 2 ] (2). 1 with [ Dipp BDIAl:] gives intramolecular C(sp 2 )–H bond-activated 3. [DNINa] with [(Cp*Al) 4 ] gives C–N activated 5 with an Al 2 CN ring.