Transmetalation Reactions of Aromatic Dilithionickelole: Synthesis of Heterobimetallic Complexes Featuring Metalloles as Diene Ligands

The aromatic metallole dianions are important metallaaromatic compounds because of their various reactivities and extensive synthetic applications. Herein we report the reactions of dilithionickelole with MgCl2, EtAlCl2, Cp*ScCl2, Cp*LuCl2 and Pt(COD)Cl2 (COD=1,5‐cyclooctadiene) affording a series of Ni/M heterobimetallic complexes of the general formula (η4−C4R4M)Ni(COD), in which the metalloles act as diene ligands, as suggested by single‐crystal X‐ray, NMR and theoretical analyses. In these reactions, two electrons of the nickelole dianion transferred to Ni, representing different reactivity compared with main‐group metallole dianions. A general and efficient method to prepare Ni/M heterobimetallic complexes (M=Mg, Al, Sc, Lu, Pt) of the general formula (η4−C4R4M)Ni(COD) (COD=1,5‐cyclooctadiene) is realized through the transmetalation reactions of aromatic dilithionickelole. In these reactions, two electrons of the aromatic nickelole dianion transfer to the Ni atom, representing a novel reactivity compared with main‐group metallole dianions. The bonding mode of these heterobimetallic complexes is studied by manifold experimental and theoretical analyses.