Articles producció científica> Química Física i Inorgànica

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

  • Identification data

    Identifier: imarina:5132233
    Authors:
    Bandeira N., Bo C.
    Abstract:
    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.
  • Others:

    Author, as appears in the article.: Bandeira N., Bo C.
    Department: Química Física i Inorgànica
    URV's Author/s: Bo Jané, Carles
    Keywords: Polyoxometalates Nanoreactor Molybdenum Molibdè Keplerate Energy Density functional calculations Chemistry Approximation
    Abstract: 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.
    Thematic Areas: 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
    Author's mail: carles.bo@urv.cat
    Author identifier: 0000-0001-9581-2922
    Last page: 2517
    Record's date: 2024-09-07
    Journal volume: 2018
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejic.201800155
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: European Journal Of Inorganic Chemistry. 2018 (22): 2512-2517
    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
    Article's DOI: 10.1002/ejic.201800155
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2018
    First page: 2512
    Publication Type: Journal Publications
  • Keywords:

    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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