Dynamic Reorganization and Confinement of TiIV Active Sites Controls Olefin Epoxidation Catalysis on Two-Dimensional Zeotypes

The effect of dynamic reorganization and confinement of isolated TiIV catalytic centers supported on silicates is investigated for olefin epoxidation. Active sites consist of grafted single-site calix[4]­arene–TiIV centers or their calcined counterparts. Their location is synthetically controlled to be either unconfined at terminal T-atom positions (denoted as type-(i)) or within confining 12-MR pockets (denoted as type-(ii); diameter ∼7 Å, volume ∼185 Å3) composed of hemispherical cavities on the external surface of zeotypes with *-SVY topology. Electronic structure calculations (density functional theory) indicate that active sites consist of cooperative assemblies of TiIV centers and silanols. When active sites are located at unconfined type-(i) environments, the rate constants for cyclohexene epoxidation (323 K, 0.05 mM TiIV, 160 mM cyclohexene, 24 mM tert-butyl hydroperoxide) are 9 ± 2 M–2 s–1; whereas within confining type-(ii) 12-MR pockets, there is a ∼5-fold enhancement to 48 ± 8 M–2 s–1. When a mixture of both environments is initially present in the catalyst resting state, the rate constants reflect confining environments exclusively (40 ± 11 M–2 s–1), indicating that dynamic reorganization processes lead to the preferential location of active sites within 12-MR pockets. While activation enthalpies are ΔH‡app = 43 ± 1 kJ mol–1 irrespective of active site location, confining environments exhibit diminished entropic barriers (ΔS‡app = −68 J mol–1 K–1 for unconfined type-(i) vs −56 J mol–1 K–1 for confining type-(ii)), indicating that confinement leads to more facile association of reactants at active sites to form transition state structures (volume ∼ 225 Å3). These results open new opportunities for controlling reactivity on surfaces through partial confinement on shallow external-surface pockets, which are accessible to molecules that are too bulky to benefit from traditional confinement within micropores.