Metal-Ligand Synergies on YIII Heteroaryl-Containing Amidopyridinate Complexes

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 describe 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 the presence of selected protic reagents along with the investigation of their ability to undergo unexpected intramolecular reactivity paths, have allowed the isolation and full characterization of unique organolanthanides. A detailed discussion on the mechanistic paths underpinning the observed rearrangements will be tackled from an experimental and theoretical perspective.