A series of aluminum and gallium complexes of β-diketiminato and β-ketiminato ligands are reported. Complex 3 is generated in an unexpected reaction where an aluminum atom is coordinated to a monoanionic β-diketiminato ligand and its dianionic form at the same time. The dianionic ligand may be generated via hydrogen atom transfer from the aluminum atom to the ligand backbone which is the first of its kind in the literature. The β-diketiminato-amidoaluminum-monohydride (6) is synthesized by the reaction of corresponding aluminum-dihydride with LiN(SiMe3)2via LiH elimination