Inorganic Chemistry, Vol.60, No.5, 3249-3258, 2021
P-C Bond Cleavage Induced Ni(II) Complexes Bearing Rare-Earth-Metal-Based Metalloligand and Reactivities toward Isonitrile, Nitrile, and Epoxide
Protonolysis of beta-diketiminato (nacnac) rare-earth metal bis-alkyl complexes L(nacnac)LnR,(THF) (Ln = Y and Lu) with 2 equiv of Ph2PNHPh or Ph2PCH2NHPh afforded the bis-amido complexes (LY)-Y-nacnac(Ph2PNPh)(2) and L(nacnac)Ln-(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.