Naslov
Impact of the α-Ferrocenyl Group on the Solvolytic Reactivity - Electrofugality - of Ferrocenylphenylmethyl Cations

Autori
Marijan, Marijan ; Jurić, Sandra ; Mihalić, Zlatko ; Kronja, Olga

Izvornik
European journal of organic chemistry (1434-193X) 2019 (2019), 2-3; 537-546

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Cations ; Electrofugality ; Ferrocenyl groups ; Solvolysis ; Substituent effects

Sažetak
The electron-donating effect of the ferrocenyl group in α-position to the reaction center on SN1 solvolytic reactivity has been quantified by determining the electrofugalities (Ef) of a series of ferrocenyl-X-phenylmethyl cations according to the LFER equation: log k = sf(Ef + Nf). Due to highly stabilized transition state, the Ef values are about eight units higher than those of the corresponding benzhydryl cations. Impact of the phenyl group in ferrocenylphenylmethyl derivatives on stabilization of the positive charge is somewhat leveled by the ferrocenyl group, so the rate effect of the substituents on the phenyl ring is suppressed, causing narrow range of Ef parameters and small absolute values of the ρ+ constant. Calculations at B2PLYP-D3/may-cc-pVTZ level of theory showed that the positive charge in ferrocenylphenylmethyl cation is largely shifted from the phenyl to ferrocenyl moiety, and that the substituents on the phenyl ring have small impact on its stability.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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