The subvalent aluminum compound [Cp*Al](4) (1) reacts with dioxygen, N2O, Or sulfur to yield the heterocubane complexes [Cp*AlX](4) [X = O (2) and S (3). Treatment of [Cp*AlO](4) (2) with (tBuO)(3)SiOH gave [(tBuO)(3)SiOAlO](4) (6) and Cp*H. The structures and spectroscopic data of the Al clusters are supported by density functional theory (DFT) calculations, which also dempnstratethe importance of noncovalent interactions (NCI) in oligomeric Al(I) cbinplexes as well as in [Cp*AlS](4) and the heavier homologues of Se and Te. The computed Al-27 NMR shifts indicate a deshielding at the Al centers with increasing electronegativity of the chalcogen atom as well as significant spin orbit shielding effects within the' eavierheterociibane [Al4E4] cores. Further 'hydrolysis of 6 with an additional amount of silanol in the presence of water resulted in the formation of [Al-4(OH)(6)(OH2)(2)(OSiOtBu(3))(6)] (7), which shows a structural motif found in boehmite and diaspore.