Metal-Ligand Interactions on Group-III and Group-IV Organometallics for polymerization and Hydroamination Catalysis

The control of single-site catalysts efficiency by tailoring ligand frameworks is an ultimate goal as well as one of the most challenging issue for many inorganic and organometallic chemists. Early transition-metal and rare-earth metal complexes stabilized by nitrogen-containing ligands have been identified as valuable candidates for a number of highly efficient and selective catalytic transformations. This contribution will focus on the use of highly electrophilic metals in combination with amido-pyridinate ligands for the preparation of polymerization and hydroamination catalysts, unveiling original and catalytically non-innocent metal-ligand interactions. A re-drawing of the amido-pyridinate frameworks, while maintaining the original donor atoms set unchanged, will also be discussed. In accordance to that, more robust pincer-type complexes capable of matching the requirements of more efficient and selective catalytic transformations, have been prepared.