Dehydrogenative Access to Aluminyl Metalloligands

<jats:p> Molecular dihydridoaluminates are widely used as hydride donors, yet their controlled conversion into low-valent aluminium metalloligands remains unexplored. Here we show that a dipyrromethene–diphosphine dihydridoaluminate acts as a masked aluminyl ligand upon reaction with group 10 metal precursors, undergoing dehydrogenation with H <jats:sub>2</jats:sub> release, and affording well-defined Al(I)–M(II) complexes. In contrast, Ni(0) precursors undergo partial dehydrogenation via LiH extrusion to give hydridobridged Al–Ni aggregates, revealing an oxidation-state dependence. These findings establish dihydridoaluminates as versatile precursors to low-valent Al metalloligands and provide a platform for developing unique heterobimetallic systems. </jats:p>