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 -C₄ R₄ M)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.