Metal-Ligand Synergies in Organolanthanides for the Catalytic Conversion of Unactivated Olefins into Materials and Commodities

Highly electrophilic 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 and hydroamination reactions. Recent studies from our group have unveiled the wealthy organometallic chemistry of these nitrogen-based systems, highlighting at the same time their unique structure-activity relationship. Herein, we present the synthesis and characterization of a series of YIII alkyl complexes stabilized by tridentate mono- or di-anionic heteroaryl-containing amidopyridinate ligands. A careful study of their reactivity in thepresence of selected protic reagents (silanes and anilines) along with the investigation of their ability to undergo unexpected intramolecular reactivity paths, has been carried out. During this study, unique organolanthanides have been isolated and completely characterized. A detailed discussion on the mechanistic paths underpinning the observed rearrangements will be tackled from a combined experimental and theoretical perspective.