Metal-Ligand Synergies in Early Organometallics and Organolanthanides for Polymerization and Hydroamination catalysis

Much of the current interest in organometallic chemistry is linked to the academic and industrial quest for novel types of efficient and selective homogeneous catalysts. For the target of improving the catalyst's performance, a precise control of the metal coordination sphere is desired; this is commonly accomplished by a fine tuning of the steric and electronic properties of the ancillary ligands. Highly electrophilic transition and lanthanide metal ions in combination with pyridylamido ligands are the basis of nonconventional, highly efficient and selective catalyst precursors of great promise for polyolefin production. Recent studies have unveiled the wealthy organometallic chemistry of these nitrogen-based systems highlighting at the same time their unique polymerization features and hydroamination performance especially in high temperature solution processes. An overview on the complex structureactivity relationship of these systems is provided along with their ability to promote the olefin polymerization and the intramolecular hydroamination of primary and secondary aminoalkenes. Finally, a tailored re-distribution of the ligand donor atoms set led to the obtainment of robust unsymmetrical "pincer-type" complexes featured by remarkable catalytic performance in the intramolecular hydroamination and olefin polymerization.