Abstract
α-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.