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