Dedicated to Kilian Munizα-Diimine ligands have significantly shaped the coordination chemistry of most transition metal complexes. Among them, bis (imino)acenaphthene ligands (BIANs) have recently been matured to great versatility and applicability to catalytic reactions. Besides variations of the ligand periphery, the great versatility of BIAN ligands resides within their ability to undergo facile electronic manipulations. This review highlights key aspects of BIAN ligands in metal complexes and summarizes recent contributions of metal-BIAN catalysts to syntheses of small and functionalized organic molecules.

On the occasion of the 60 th birthday of Matthias BellerHydrogenations have been dominated by transition metal catalysis, while the use of more abundant and inexpensive main group metal catalysts has remained a great challenge. Here, a bimetallic Li/Al dihydride was successfully applied to catalytic hydrogenations of imines. The catalyst [( Dipp BIAN)Al(μ-H) 2 Li-(OEt 2 ) 2 ] was easily prepared from the 2e-reduced BIAN derivative and LiAlH 4 .