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Regioselective Catalysis by the {Mo 132 } Nanocapsule: A Computational Inspection
Author(s) -
Bandeira Nuno A. G.,
Bo Carles
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800155
Subject(s) - regioselectivity , chemistry , selectivity , cycloaddition , catalysis , activation barrier , density functional theory , metal , combinatorial chemistry , reaction mechanism , computational chemistry , organic chemistry
By means of density functional calculations, we perform a mechanistic analysis of the Huisgen cycloaddition reaction taking place with the chemical involvement of the {Mo 132 } 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.