A Hexametallic Copper Aluminylene Aluminyl

Heterobimetallic compounds with aluminyl ligands have hitherto gained a significant interest due to promising small molecule activation pathways including challenging substrates. While recently some trimetallic derivatives have been introduced, the steric demands required by these known systems has precluded the access of higher nuclearity systems. We herein report on a first hexametallic copper aluminylene aluminyl namely [(AlCp*)Cu{Al(HMDS)2}]2 ([5]2). The synthesis and characterization are enabled via designed Al(I) transfer using (AlCp*)4 and precursor complex [(PtBu3)Cu(HMDS)] (1). The associated pathway for aluminum transfer via different intermediates is discussed. This includes single crystal X-ray crystallography (SC-XRD), multinuclear NMR spectroscopy, control experiments and state-of-the art quantum chemical calculations. Preliminary reactivity studies showed that [5]2 can not only be constructed stepwise but also deconstructed to a bimetallic species with an N-heterocyclic carbene