P–C Bond Cleavage Induced Ni(II) Complexes Bearing Rare-Earth-Metal-Based Metalloligand and Reactivities toward Isonitrile, Nitrile, and Epoxide
journal contributionposted on 15.02.2021, 06:12 by Peng Cui, Xia Huang, Jun Du, Zeming Huang
Protonolysis of β-diketiminato (nacnac) rare-earth metal bis-alkyl complexes LnacnacLnR2(THF) (Ln = Y and Lu) with 2 equiv of Ph2PNHPh or Ph2PCH2NHPh afforded the bis-amido complexes LnacnacY(Ph2PNPh)2 and LnacnacLn(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 PhNCH2 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.