Articles producció científica> Química Física i Inorgànica

Reaction Pathway Discrimination in Alkene Oxidation Reactions by Designed Ti-Siloxy-Polyoxometalates

  • Datos identificativos

    Identificador: imarina:9156322
    Autores:
    Zhang, TengSole-Daura, AlbertFouilloux, HugoPoblet, Josep M.Proust, AnnaCarbo, Jorge J.Guillemot, Geoffroy
    Resumen:
    Titanium complexes of silanol functionalized polyoxometalates (THA)(3)[SbW9O33(RSiO)(3)Ti((OPr)-Pr-i)] (Ti-SiloxPOMs) catalyze alkene oxidation with tert-butyl hydrogen peroxide (TBHP). However catalytic activity and product distribution in the oxidation of allylic alcohols are shown to depend on the steric surrounding generated by the SiloxPOM (R=Bu-t, Pr-i, Pr-n). Combined experimental and computational studies clarify how steric repulsions between the oxidant (Bu-t group) and the surrounding SiloxPOM govern the reaction pathways leading either to oxidation of the alcohol function (R=Bu-t) or to alkene epoxidation (R=Pr-n). Moreover, another consequence of this steric repulsive interactions is that outer-sphere mechanisms become competitive with the inner-sphere ones (coordination of allylic alcohol), whether for the oxidative dehydrogenation reaction or for the epoxidation reaction. In the case of unfunctionalized olefins (linear and cyclic), we show that reducing the bulkiness surrounding the active site leads to higher conversion to epoxide, emphasizing that these Ti-SiloxPOMs may behave as structural and functional models for metal single-site in Ti-Silicates.
  • Otros:

    Autor según el artículo: Zhang, Teng; Sole-Daura, Albert; Fouilloux, Hugo; Poblet, Josep M.; Proust, Anna; Carbo, Jorge J.; Guillemot, Geoffroy;
    Departamento: Química Física i Inorgànica
    e-ISSN: 1867-3899
    Autor/es de la URV: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria / Solé Daura, Albert
    Palabras clave: Titanium compounds Titanium complexes Titanium Silicates Repulsive interactions Product distributions Polyoxotungstates Polyoxometalates Oxidative dehydrogenation reactions Oxidation reactions Oxidation Olefins Mechanistic study Epoxidation reactions Epoxidation Dft Dehydrogenation Coordination reactions Computational studies Catalytic oxidation Catalyst activity Alkene epoxidation Alkene
    Resumen: Titanium complexes of silanol functionalized polyoxometalates (THA)(3)[SbW9O33(RSiO)(3)Ti((OPr)-Pr-i)] (Ti-SiloxPOMs) catalyze alkene oxidation with tert-butyl hydrogen peroxide (TBHP). However catalytic activity and product distribution in the oxidation of allylic alcohols are shown to depend on the steric surrounding generated by the SiloxPOM (R=Bu-t, Pr-i, Pr-n). Combined experimental and computational studies clarify how steric repulsions between the oxidant (Bu-t group) and the surrounding SiloxPOM govern the reaction pathways leading either to oxidation of the alcohol function (R=Bu-t) or to alkene epoxidation (R=Pr-n). Moreover, another consequence of this steric repulsive interactions is that outer-sphere mechanisms become competitive with the inner-sphere ones (coordination of allylic alcohol), whether for the oxidative dehydrogenation reaction or for the epoxidation reaction. In the case of unfunctionalized olefins (linear and cyclic), we show that reducing the bulkiness surrounding the active site leads to higher conversion to epoxide, emphasizing that these Ti-SiloxPOMs may behave as structural and functional models for metal single-site in Ti-Silicates.
    Áreas temáticas: Química Physical and theoretical chemistry Organic chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Engenharias i Ciências biológicas ii Ciências ambientais Ciências agrárias i Ciência de alimentos Chemistry, physical Catalysis Biotecnología Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1867-3880
    Direcció de correo del autor: josepmaria.poblet@urv.cat j.carbo@urv.cat
    Identificador del autor: 0000-0002-4533-0623 0000-0002-3945-6721
    Fecha de alta del registro: 2024-07-27
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cctc.202001779
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Chemcatchem. 13 (4): 1220-1229
    Referencia de l'ítem segons les normes APA: Zhang, Teng; Sole-Daura, Albert; Fouilloux, Hugo; Poblet, Josep M.; Proust, Anna; Carbo, Jorge J.; Guillemot, Geoffroy; (2021). Reaction Pathway Discrimination in Alkene Oxidation Reactions by Designed Ti-Siloxy-Polyoxometalates. Chemcatchem, 13(4), 1220-1229. DOI: 10.1002/cctc.202001779
    DOI del artículo: 10.1002/cctc.202001779
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2021
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Catalysis,Chemistry, Physical,Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry
    Titanium compounds
    Titanium complexes
    Titanium
    Silicates
    Repulsive interactions
    Product distributions
    Polyoxotungstates
    Polyoxometalates
    Oxidative dehydrogenation reactions
    Oxidation reactions
    Oxidation
    Olefins
    Mechanistic study
    Epoxidation reactions
    Epoxidation
    Dft
    Dehydrogenation
    Coordination reactions
    Computational studies
    Catalytic oxidation
    Catalyst activity
    Alkene epoxidation
    Alkene
    Química
    Physical and theoretical chemistry
    Organic chemistry
    Medicina i
    Materiais
    Interdisciplinar
    Inorganic chemistry
    Farmacia
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas ii
    Ciências ambientais
    Ciências agrárias i
    Ciência de alimentos
    Chemistry, physical
    Catalysis
    Biotecnología
    Astronomia / física
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