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https://doi.org/10.5562/cca3040

Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates

Mirela Matić ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, HR-10000 Zagreb, Croatia
Nives Bebek ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, HR-10000 Zagreb, Croatia
Bernard Denegri   ORCID icon orcid.org/0000-0001-6335-6723 ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, HR-10000 Zagreb, Croatia
Olga Kronja ; University of Zagreb, Faculty of Pharmacy and Biochemistry, Ante Kovačića 1, HR-10000 Zagreb, Croatia

Puni tekst: engleski, pdf (2 MB) str. 355-362 preuzimanja: 706* citiraj
APA 6th Edition
Matić, M., Bebek, N., Denegri, B. i Kronja, O. (2016). Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates. Croatica Chemica Acta, 89 (3), 355-362. https://doi.org/10.5562/cca3040
MLA 8th Edition
Matić, Mirela, et al. "Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates." Croatica Chemica Acta, vol. 89, br. 3, 2016, str. 355-362. https://doi.org/10.5562/cca3040. Citirano 19.01.2021.
Chicago 17th Edition
Matić, Mirela, Nives Bebek, Bernard Denegri i Olga Kronja. "Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates." Croatica Chemica Acta 89, br. 3 (2016): 355-362. https://doi.org/10.5562/cca3040
Harvard
Matić, M., et al. (2016). 'Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates', Croatica Chemica Acta, 89(3), str. 355-362. https://doi.org/10.5562/cca3040
Vancouver
Matić M, Bebek N, Denegri B, Kronja O. Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates. Croatica Chemica Acta [Internet]. 2016 [pristupljeno 19.01.2021.];89(3):355-362. https://doi.org/10.5562/cca3040
IEEE
M. Matić, N. Bebek, B. Denegri i O. Kronja, "Nucleofugality of Pentafluorophenolate in Various Solvents: Solvolytic Behavior of Phenolates", Croatica Chemica Acta, vol.89, br. 3, str. 355-362, 2016. [Online]. https://doi.org/10.5562/cca3040

Sažetak
The leaving group ability (nucleofugality) of the pentafluorophenolate anion has been determined from first order solvolytic rate constants (k) of X,Y-substituted benzhydryl pentafluorophenolates measured in a series of solvents, by using the three parameter LFER equation: log k = sf (Ef + Nf). Comparison with other leaving groups reveals that pentafluorophenolate is a moderate leaving group, whose nucleofugality (Nf value) is between the nucleofugalities of phenyl carbonate and 3,5-dinitrobenzoate leaving groups. However, due to its high reaction constant (sf = 1.29 in 80 % aq. ethanol), relative reactivities of benzhydryl pentafluorophenolates and corresponding benzhydryl carboxylates vary with the electrofugality of a carbocation formed in the heterolytic step, i.e., inversion of the reactivity of benzhydryl series with different leaving groups occurs. The plots of ΔG° vs. ΔrG° for solvolysis of benzhydryl phenolates and carboxylates reveal that phenolates solvolyze over the lower Marcus intrinsic barrier than corresponding carboxylates.

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Ključne riječi
nucleofugality; leaving group; LFER; phenolate; intrinsic barrier; solvolysis

Hrčak ID: 172243

URI
https://hrcak.srce.hr/172243

Posjeta: 958 *