Dynamic Reorganization and Confinement of Ti^IV Active Sites Controls Olefin Epoxidation Catalysis on Two-Dimensional...

The effect of dynamic reorganization and confinement of isolated Ti^IV catalytic centers supported on silicates is investigated for olefin epoxidation. Active sites consist of grafted single-site calix[4]arene-Ti^IV 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 ų) 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 Ti^IV centers and silanols. When active sites are located at unconfined type-(i) environments, the rate constants for cyclohexene epoxidation (323 K, 0.05 mM Ti^IV, 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 Δ H^‡_app = 43 ± 1 kJ mol^-1 irrespective of active site location, confining environments exhibit diminished entropic barriers (Δ S^‡_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 ų). 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.