Solvent effects in catalytic reactions have received widespread attention as they can promote reaction rates and product selectivities by orders of magnitude. It is well accepted that the stable five-membered cyclic intermediates formed between the solvent molecules and Ti species are crucial to the alkene epoxidation in a heterogeneous Ti(IV)-HO system. However, the direct spectroscopic evidence of these intermediates is still missing and the corresponding reaction pathway for the alkene epoxidation remains unclear. By combining in situ C MAS NMR, two-dimensional (2D) H-C heteronuclear correlation (HETCOR) NMR spectroscopy and theoretical calculations, the five-membered ring structures, where the protic solvents (ROH), and aprotic solvent (acetone), coordinate and stabilize the active Ti species, are identified for the first time over Ti-Beta/HO system. Moreover, the role of these cyclic intermediates in the alkene epoxidation/hydration conversion is clarified. These results provide new insights into the solvent effect in liquid-phase epoxidation/hydration reactions over Ti(IV)-HO system.
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