Combinatorial Synthesis of Acacen-Type Ligands and Their Coordination Compounds

A highly modular synthetic method for the preparation of acacen-type ligands and their coordination compounds was developed. A series of 46 acacen-type ligands were synthesized by a combinatorial acid-catalyzed transamination between six primary diamines and eight enaminones. The bis-enaminone products were used as tetradentate ligands for coordination of copper­(II), nickel­(II), cobalt­(II), and palladium­(II). Dependence of the preferred E- or Z-configuration of the enaminone ligand on the α-substituent of the enaminone moiety in solution was determined by NMR and confirmed by X-ray diffraction. The copper­(II) complexes were tested for their suitability as catalysts in 3 + 2 cycloaddition of azomethine imine to methyl propiolate.