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: 2023-02-18

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: http://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