METAL-LIGAND SYNERGIES IN GROUP-IV ORGANOMETALLICS AND ORGANOLANTHANIDES FOR POLYMERIZATION AND HYDROAMINATION CATALYSIS

Contemporary organometallic chemistry research is focused on the academic and industrial quest for novel types of efficient and selective homogeneous catalysts. To date, huge efforts have been paid to the improvement of the catalysts performance through a fine tuning of the stereoelectronic properties of their ancillary ligands. On this regard, the design of novel ligand scaffolds suitable for coordination to early transition or rare-earth metal ions, the isolation of the corresponding complexes along with the investigation of their structure-reactivity relationship, represent a challenging area of modern organometallic chemistry applied to homogeneous catalysis. 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.1,2 Recent studies have unveiled the wealthy organometallic chemistry of these nitrogen-based systems,3 highlighting at the same time their unique polymerization features3b,4 and hydroamination performance,3d,5 especially in solution processes at high temperature. An overview of the latest examples of this category prepared in our group is given, along with their catalytic performance in polymerization and intramolecular hydroamination of primary and secondary aminoalkenes.