The redox non-innocent bis-silylenyl ortho-carborane ligands [SiII(CCcage)SiII] (CCcage = o-C2B10H10, SiII = ArC(NtBu)2Si; Ar = C6H5, p–tBuC6H4), with their particular chelating and electronic properties, have been employed for the synthesis of new donor-stabilized SiII→AlIII complexes that could act as precursors to low oxidation state aluminium complexes. Due to the redox non-innocence of the carborane backbone, aluminium(III) iodide complexes with three ligand oxidation states were characterized: neutral and radical anionic closo– as well as dianionic nido-C2B10 cores. Reduction at the aluminium center could also be enacted with potassium/napthalene leading to naphthalene derivatives {K[SiII(CCcage)SiII]Al(C10H8)} from [1+4] cycloaddition reaction, pointing to transient low oxidation state aluminium species as likely intermediates.