Iminopyridine Ni(II) Catalysts Affording Oily Hyperbranched Ethylene Oligomers and/or Crystalline Polyethylenes Depending on the Reaction Conditions: Possible Role of In Situ Catalyst Structure Modifications

Nickel-based ethylene polymerization catalysts have unique features, being able to produce macromolecules with a variable content of branches, resulting in polymers ranging from semicrystalline plastics to elastomers to hyperbranched amorphous waxes and oils. In addition to Brookhart’s α-diimine catalysts, iminopyridine Ni(II) complexes are among the most investigated systems. We report that Ni(II) complexes bearing aryliminopyridine ligands with bulky substituents both at the imino moiety and in the 6-position of pyridine afford either hyperbranched low molecular weight polyethylene oils or prevailingly linear crystalline polyethylenes or both, depending on the ligand structure and the reaction conditions. The formation of multiple active species in situ is suggested by analysis of the post-polymerization catalyst residues, showing the partial reduction of the imino function. Some related arylaminopyridine Ni(II) complexes were also synthesized and tested, showing a peculiar behavior, i.e., the number of branches of the produced polyethylenes increases while ethylene pressure increases.

Efficient incorporation of a polar comonomer for direct synthesis of hyperbranched polar functional ethylene oligomers

Hyperbranched polar functional ethylene oligomers with very high incorporation can be accessible via ethylene–MA co-oligomerization with iminopyridyl Pd(ii) catalysts.

Preparation and in situ chain-end-functionalization of branched ethylene oligomers by monosubstituted α-diimine nickel catalysts

Chain-end-functionalization of (highly) branched ethylene oligomers was achieved in situ with the most/least bulky α-diimine nickel catalysts for the first time.

(Phenoxyimidazolyl-salicylaldimine)iron complexes: synthesis, properties and iron catalysed ethylene reactions

(Salicyladimine)iron(iii) pre-catalysts, from iron(ii) precursors, form catalysts for ethylene oligomerisation, polymerisation and alkylation of aromatic solvents by the ethylene oligomers.