The role of outer-sphere surface acidity in alkene epoxidation catalyzed by calixarene-Ti(IV) complexes

Cooperativity between Brønsted acidic defect sites on oxide surfaces and Lewis acid catalyst sites consisting of grafted calixarene-Ti(IV) complexes is investigated for controlling epoxidation catalysis. Materials are synthesized that, regardless of the surface or calixarene substituent, demonstrate nearly identical UV-visible ligand-to-metal charge-transfer bands and Ti K-edge X-ray absorption near edge spectral features consistent with site-isolated, coordinatively unsaturated Ti(IV) atoms. Despite similar Ti frontier orbital energies demonstrated by these spectra, replacing a homogeneous triphenylsilanol ligand with a silanol on a SiO₂ surface increases cyclohexene epoxidation rates with tert-butyl hydroperoxide 20-fold per Ti site. Supporting calixarene-Ti active sites on fully hydroxylated Al ₂O₃ or TiO₂, which possess lower average surface hydroxyl pK_a than that of SiO₂, reduces catalytic rates 50-fold relative to SiO₂. These effects are consistent with SiO₂ surfaces balancing two competing factors that control epoxidation rates-equilibrated hydroperoxide binding at Ti, disfavored by stronger surface Brønsted acidity, and rate-limiting oxygen transfer from this intermediate to alkenes, favored by strongly H-bonding intermediates. These observations also imply that Ti-OSi rather than Ti-OCalix bonds are broken upon hydroperoxide binding to Ti in kinetically relevant steps, which is verified by the lack of a calixarene upper-rim substituent effect on epoxidation rate. The pronounced sensitivity of observed epoxidation rates to the support oxide, in the absence of changes to the Ti coordination environment, provides experimental evidence for the importance of outer-sphere H-bonding interactions for the exceptional epoxidation reactivity of titanium silicalite and related catalysts.