Structural evolution of iminopyridine support for nickel/palladium catalysts in ethylene (oligo)polymerization

The interest in the late transition metal catalyst based design of new architectures of polyethylene (PE) has continuously been increasing over the last few years. The structure of these catalysts is predominantly important in controlling the morphological and architectural properties of the resulting polyethylene. Particularly, iminopyridine is a versatile bidentate support for Ni and Pd catalysts in ethylene (oligo)polymerization providing a wide variety of products ranging from volatile oligomers to ultra-high molecular weight polyethylene. Extensive structural modifications have been induced in the iminopyridine ligand through steric and electronic substitution, tuning the catalyst behavior in terms of activity and properties of the resulting polymer. Carbocyclic-fused iminopyridine and N-oxide iminopyridine are the new state of the art iminopyridine ligand designs. In this review, we aim to summarize all the developments in mononuclear iminopyridine-nickel and -palladium catalysts for ethylene (oligo)polymerization since the first report published in 1999 to present, focusing on the correlation among the pre-catalyst, co-catalyst type, thermal stability and polymer/oligomer structure. For comparison, the structural variations in the binuclear iminopyridine-nickel catalysts are also described. The detailed comparison of the structural variations in these catalysts with respect to their polymerization performance will give deep understanding in the development of new efficient catalyst designs.