Articles producció científica> Química Física i Inorgànica

Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented beta-Oxygen Transfer Mechanism

  • Identification data

    Identifier: imarina:3665547
    Handle: https://hdl.handle.net/20.500.11797/imarina3665547
    Authors:
    Jimenez-Lozano, PabloSkobelev, Igor Y.Kholdeeva, Oxana A.Poblet, Josep M.Carbo, Jorge J.
    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 ¿-oxygen transfer from the titanium hydroperoxo species becomes favored over the ¿-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.

  • Others:

    Author, as appears in the article.: Jimenez-Lozano, Pablo; Skobelev, Igor Y.; Kholdeeva, Oxana A.; Poblet, Josep M.; Carbo, Jorge J.;
    Department: Química Física i Inorgànica
    URV's Author/s: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria
    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 ¿-oxygen transfer from the titanium hydroperoxo species becomes favored over the ¿-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.
    Thematic Areas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: josepmaria.poblet@urv.cat j.carbo@urv.cat
    Author identifier: 0000-0002-4533-0623 0000-0002-3945-6721
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00621
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Inorganic Chemistry. 55 (12): 6080-6084
    APA: Jimenez-Lozano, Pablo; Skobelev, Igor Y.; Kholdeeva, Oxana A.; Poblet, Josep M.; Carbo, Jorge J.; (2016). Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented beta-Oxygen Transfer Mechanism. Inorganic Chemistry, 55(12), 6080-6084. DOI: 10.1021/acs.inorgchem.6b00621
    Article's DOI: 10.1021/acs.inorgchem.6b00621
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2016
    Publication Type: Journal Publications

  • Keywords:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Química
    Physical and theoretical chemistry
    Medicina i
    Materiais
    Interdisciplinar
    Inorganic chemistry
    General medicine
    Farmacia
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, inorganic & nuclear
    Chemistry (miscellaneous)
    Biotecnología
    Astronomia / física

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