P-C Bond Cleavage Induced Ni(II) Complexes Bearing Rare-Earth-Metal-Based Metalloligand and Reactivities toward...

Protonolysis of β-diketiminato (nacnac) rare-earth metal bis-alkyl complexes L^nacnacLnR₂(THF) (Ln = Y and Lu) with 2 equiv of Ph₂PNHPh or Ph₂PCH₂NHPh afforded the bis-amido complexes L^nacnacY(Ph₂PNPh)₂ and L^nacnacLn(Ph₂PCH₂NPh)₂ (Ln = Y and Lu). Metalation of the latter complexes with 1 equiv of Ni(COD)₂ led to the isolation of unusual heterobimetallic Ni(II)-Ln(III) complexes formed via P-C bond cleavage of one [Ph₂PCH₂NPh]^- ligand. Notably, both the imine PhN═CH₂ and phosphide Ph₂P^- fragments from the P-C bond cleavage were trapped in the Ni(II)-Ln(III) core with a relatively weak interaction between the two metal centers. The Ni(II)-Y(III) complex have exhibited versatile reactivity, such as coordination of isonitrile to the Ni(II) center, insertion of nitrile with the coordinated imine, and ring-opening of the epoxide by nucleophilic attack from the phosphide group.