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Updated: Mar 20, 2026

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β-Oxygen Transfer Mechanism
Pablo Jiménez-Lozano1, Igor Y Skobelev2,3, Oxana A Kholdeeva2,3
1Department de Química Física i Inorgànica, Universitat Rovira i Vigili , Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
Abstract:
A DFT study revealed that the mechanism of alkene epoxidation with hydrogen peroxide catalyzed by Ti-containing polyoxometalates (POMs) depends on the Ti coordination environment: For rigid and hindered Ti centers, the unprecedented β-oxygen transfer from the titanium hydroperoxo species becomes favored over the α-oxygen one. Improving the model for catalyst description, the calculations were able to reproduce the Arrhenius activation energy values determined in kinetic studies. Unlike protonation, the possible ion-pairing between POMs and countercations has a minor effect on the electrophlicity of the catalyst and, consequently, on the activity of epoxidation.
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