title: Completing the Heterocubane Family [Cp*AlE]4 (E = O, S, Se, and Te) by Selective Oxygenation and Sulfuration of [Cp*Al]4: Density Functional Theory Calculations of [Cp*AlE]4 and Reactivity of [Cp*AlO]4 toward Hydrolysis.
abstract: 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)3SiOH gave [(tBuO)3SiOAlO]4 (6) and Cp*H. The structures and spectroscopic data of the Al clusters are supported by density functional theory (DFT) calculations, which also demonstrate the importance of noncovalent interactions (NCI) in oligomeric Al(I) complexes as well as in [Cp*AlS]4 and the heavier homologues of Se and Te. The computed (27)Al 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 heavier heterocubane [Al4E4] cores. Further hydrolysis of 6 with an additional amount of silanol in the presence of water resulted in the formation of [Al4(OH)6(OH2)2(OSiOtBu3)6] (7), which shows a structural motif found in boehmite and diaspore.
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Straße 2, 12489 Berlin, Germany.
authors.forename: Adrian C
authors.initials: AC
authors.lastname: Stelzer
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Hrobárik
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Straße 2, 12489 Berlin, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Braun
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Kaupp
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin , Brook-Taylor-Straße 2, 12489 Berlin, Germany.
authors.forename: Beatrice
authors.initials: B
authors.lastname: Braun-Cula