Naslov
Nucleofugality of Carbonates

Autori
Matić, Mirela ; Denegri, Bernard ; Kronja, Olga

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
XXIV. Hrvatski skup kemičara i kemijskih inženjera - Knjiga sažetaka / Ukić, Šime ; Bolanča, Tomislav - Zagreb : Hrvatsko društvo kemijskih inženjera i tehnologa (HDKI), 2015, 140-140

ISBN
978-953-6894-54-3

Skup
XXIV. Hrvatski skup kemičara i kemijskih inženjera

Mjesto i datum
Zagreb, Hrvatska, 21.04.2015. - 24.04.2015

Vrsta sudjelovanja
Poster

Vrsta recenzije
Nije recenziran

Ključne riječi
nucleofugality; carbonates; kinetics; solvolysis; DFT

Sažetak
The leaving group abilities (nucleofugalities), defined by nucleofuge-specific parameters (Nf and sf), were determined for a series of aromatic and aliphatic carbonates from solvolysis rate constants of X, Y-substituted benzhydryl carbonates in a series of aqueous ethanol mixtures by applying the linear free energy relationship (LFER) equation: log k (25 °C) = sf (Ef + Nf). In this correlation equation k is the solvolysis first-order rate constant, sf (slope of the correlation line) and Nf (negative intercept on the abscissa) are the nucleofuge-specific parameters, whereas Ef represents the electrofugality parameter of variously substituted benzhydrylium electrofuges. Nf parameters can be employed for comparing heterolytic reactivities of diverse types of leaving groups in a wide range of reactivity. Furthermore, combining previously determined parameters, the duration of a particular solvolytic reaction can be estimated. The applicability of quantum-chemical model reaction (M06-2X method) has been examined for determination of Nf parameters of both aromatic and aliphatic carbonates (including HCO3−). A very good correlation between experimental and calculated reactivities makes possible to extend the nucleofugality scale significantly.

Izvorni jezik
Engleski

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