Synthesis, Characterization, and Catalytic Properties of γ-Al2O3-Supported Zirconium Hydrides through a Combined Use of Surface Organometallic Chemistry and Periodic Calculations

The treatment of the alumina-supported [Zr(CH2tBu)4], [(AlsO)2Zr(CH2tBu)+(tBuCH2)Als-], where Als stands for surface aluminum atoms, by H2 yields a mixture of alumina-supported zirconium hydride species, [(AlsO)2Zr(H)(μ-H)AlVI] and [(AlsO)2Zr(H)(μ-R)AlVI], along with cationic [(AlsO)2Zr(H)]+ in the vicinity of anionic tetrahedral aluminum hydrides [AlIV-H-] according to mass balance analysis, reactivity studies, IR spectroscopy, and periodic calculations. Initial and final selectivities in the hydrogenolysis of alkanes as well as DFT calculations show that β-alkyl transfer is the key carbon−carbon cleavage step.