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Regioselective Catalysis by the {Mo-132} Nanocapsule: A Computational Inspection

  • Datos identificativos

    Identificador: imarina:5132233
    Autores:
    Bandeira N., Bo C.
    Resumen:
    By means of density functional calculations, we perform a mechanistic analysis of the Huisgen cycloaddition reaction taking place with the chemical involvement of the {Mo132} nanocapsule, initially reported by Besson and others [Dalton Trans. 2012, 41, 9852-9854], whereby a 2:1 regioselectivity is obtained by chemically grafting the reactants onto the cavity walls of this metal‐oxide catalyst. We explore the mechanistic pathways quantitatively and explore the basis of this regioselectivity. When propiolate is coordinated to the nanocapsule, the selectivity of the catalytic system is both kinetically and thermodynamically in favour of the formation of 1,4‐triazole, whereas in the alternative pathway, which begins with the triazidoacetate coordination, the selectivity is kinetic alone. The former and latter pathways have activation barrier differences between each isomer of 29.9 kJ/mol and 39.2 kJ/mol, respectively.
  • Otros:

    Autor según el artículo: Bandeira N., Bo C.
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Bo Jané, Carles
    Palabras clave: Polyoxometalates Nanoreactor Molybdenum Molibdè Keplerate Energy Density functional calculations Chemistry Approximation
    Resumen: By means of density functional calculations, we perform a mechanistic analysis of the Huisgen cycloaddition reaction taking place with the chemical involvement of the {Mo132} nanocapsule, initially reported by Besson and others [Dalton Trans. 2012, 41, 9852-9854], whereby a 2:1 regioselectivity is obtained by chemically grafting the reactants onto the cavity walls of this metal‐oxide catalyst. We explore the mechanistic pathways quantitatively and explore the basis of this regioselectivity. When propiolate is coordinated to the nanocapsule, the selectivity of the catalytic system is both kinetically and thermodynamically in favour of the formation of 1,4‐triazole, whereas in the alternative pathway, which begins with the triazidoacetate coordination, the selectivity is kinetic alone. The former and latter pathways have activation barrier differences between each isomer of 29.9 kJ/mol and 39.2 kJ/mol, respectively.
    Áreas temáticas: Química Medicina i Materiais Interdisciplinar Inorganic chemistry Farmacia Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Chemistry, inorganic & nuclear Astronomia / física
    ISSN: 14341948
    Direcció de correo del autor: carles.bo@urv.cat
    Identificador del autor: 0000-0001-9581-2922
    Página final: 2517
    Fecha de alta del registro: 2024-09-07
    Volumen de revista: 2018
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201800155
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: European Journal Of Inorganic Chemistry. 2018 (22): 2512-2517
    Referencia de l'ítem segons les normes APA: Bandeira N., Bo C. (2018). Regioselective Catalysis by the {Mo-132} Nanocapsule: A Computational Inspection. European Journal Of Inorganic Chemistry, 2018(22), 2512-2517. DOI: 10.1002/ejic.201800155
    DOI del artículo: 10.1002/ejic.201800155
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2018
    Página inicial: 2512
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry, Inorganic & Nuclear,Inorganic Chemistry
    Polyoxometalates
    Nanoreactor
    Molybdenum
    Molibdè
    Keplerate
    Energy
    Density functional calculations
    Chemistry
    Approximation
    Química
    Medicina i
    Materiais
    Interdisciplinar
    Inorganic chemistry
    Farmacia
    Engenharias iii
    Engenharias ii
    Ciências biológicas ii
    Ciências biológicas i
    Chemistry, inorganic & nuclear
    Astronomia / física
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