Low-Coordinate Mixed Ligand NacNac Complexes of Rare Earth Metals

We report the synthesis and characterization of two types of new mixed-ligand rare earth complexes: tetracoordinate (NacNac^Mes)Ln(BIAN^dipp) (Ln = Dy (1), Er (2) and Y (3)) and pentacoordinate (NacNac^Mes)Ln(AP^dipp)(THF) (Ln = Dy (4), Er (5) and Y (6)). The first three compounds were prepared by the reaction of [(BIAN^Dipp)LnI] with potassium β-diketiminate. The salt metathesis of β-diketiminato-supported rare earth dichlorides (NacNac^Mes)LnCl₂(THF)₂ with sodium o-amidophenolate results in compounds 4-6. The crystal structures of complexes 1-6 were determined by single-crystal analysis. The combination of bulky monoanionic N-mesityl-substituted β-diketiminates with sterically hindered redox-active ligands led to the very low coordination numbers of rare earths and strong distortion of the chelate ligands.