Tuning the Molecular Structure and Reaction Mechanism of Olefin Metathesis by Model Bilayered Supported MoO_<i>x</i>/AlO_<i>x</i>/SiO₂ Catalysts

The molecular structure and activity of supported MoO _<i>x</i> olefin metathesis catalysts are heavily impacted by the choice of catalyst support. In this study, surface modification of the SiO₂ support with AlO _<i>x</i> and selective anchoring of the MoO _<i>x</i> on the surface AlO _<i>x</i> sites were used to tune the structure, activation, and reactivity of the resulting surface MoO _<i>x</i> sites. Extensive <i>in situ</i> molecular characterization, chemical probe studies, and density functional theory (DFT) calculations reveal that the enhanced activity of the supported MoO _<i>x</i> /AlO _<i>x</i> /SiO₂ catalyst over the MoO _<i>x</i> /SiO₂ catalyst is associated with more favorable activation and kinetics of surface MoO _<i>x</i> anchored at AlO _<i>x</i> sites.