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P–C Bond Cleavage Induced Ni(II) Complexes Bearing Rare-Earth-Metal-Based Metalloligand and Reactivities toward Isonitrile, Nitrile, and Epoxide

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journal contribution
posted 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 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.