Abstract
The fine-tuning of the local environment around a metal center beyond the primary coordination sphere is of major import in the pursuit of more efficient and selective catalytic systems. Herein, we present a new synthetic pathway to prepare a class of tripodal ligands based on the triamidoamine (tren) scaffold. These ligands are bulky, multidentate and electron rich, enabling the stabilization of metals in unusual environments and oxidation states. Our ligands are prepared through the condensation of nitrilotracetyl chloride with different anilines in the presence of a sacrificial base, followed by reduction. They can be deprotonated to form stable trilithium salts and subsequently transmetalated to produce metal complexes with interesting coordination geometries. Also, direct ligand transamination was carried out successfully, resulting in an intramolecular carbon-nitrogen coupling reaction..