Redox‐active BIAN‐based Diimine Ligands in Metal‐Catalyzed Small Molecule Syntheses**

Abstract

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.

Cobalt-Catalyzed Alkylation of Nitriles with Alcohols

“…Due to our longstanding interest in the catalytic behavior of bis­(arylimino)­acenaphthene (BIAN)-ligand supported transition metals, ,,,− we began exploring the application of BIAN ligands in alkylation chemistry. BIAN ligands were first introduced to coordination chemistry by Elsevier and co-workers in 1994 and have gone on to be widely applied in catalysis − and in the support of reactive main-group species . They are a combination of an α,α′-diimine unit and the naphthalene system’s π-framework and provide robust support for metal complexes.…”

Zinc complexes bearing BIAN ligands as efficient catalysts for the formation of cyclic carbonates from CO2 and epoxides

“…The aryl and acenaphthene groups permit a wide variety of substituents that allow easy steric tunability and electronic versatility. [33][34][35] This flexibility coupled with a friendly environmental synthesis makes them attractive targets to build potential catalysts for the formation of carbonates from CO 2 and epoxides.…”

Diaza-1,3-butadienes as Useful Intermediate in Heterocycles Synthesis

“…On the other hand, because of the presence of nitrogen atoms in the structure of 1,4-diazadienes, they are known as ligands in coordination chemistry since the pioneering work of Dieck et al [ 21 ]. The 1,4-diazabutadienes are widely used as ligands in coordination chemistry and catalysis, and there are many up-to-date references on the subject [ 19 , 22 , 23 ]. The versatile ligands have been used to form coordination complexes with most of the metals in the periodic table, including heavy alkaline earth metals [ 24 ], lanthanides, and actinides [ 25 , 26 , 27 ].…”