Synthesis and Reactivity of Heterobimetallic Rare-Earth-Nickel Phosphido Complexes Supported by an Arene-Anchored Bis(phosphinomethylamido) Ligand

来源：ACS Publications

Heterobimetallic rare-earth-nickel alkyl complexes (RE-Ni-alkyl) supported by an arene-anchored bis(phosphinomethylamido) ligand were synthesized and further reacted with MesPH2 (Mes = 2,4,6-trimethylphenyl) to afford rare-earth-nickel phosphido complexes (RE-Ni-PHMes). The phosphido complexes have exhibited insertion reactivity toward a variety of unsaturated substrates, including alkyne, carbodiimide, ketone, organic azide, and diazomethane, leading to the formation of a series of heterobimetallic rare-earth-nickel complexes with various functional ligands. On the other hand, treatment of the phosphido complexes with bipyridine only allowed for the coordination on the rare-earth metal center. The observed short RE–Ni bond lengths (2.50–2.63 Å) and the formal shortness ratios (0.91–0.95) in these complexes are indicative of Ni(0)→RE(III) dative interactions.