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Kinetics and Mechanism of Oxidation of Hydroxyurea Derivatives with Hexacyanoferrate(III) in Aqueous Solution


Budimir, Ana; Weitner, Tin; Kos, Ivan; Šakić, Davor; Gabričević, Mario; Bešić, Erim; Biruš, Mladen
Kinetics and Mechanism of Oxidation of Hydroxyurea Derivatives with Hexacyanoferrate(III) in Aqueous Solution // Croatica chemica acta, 84 (2011), 2; 133-147 doi:10.5562/cca1799 (međunarodna recenzija, članak, znanstveni)


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Naslov
Kinetics and Mechanism of Oxidation of Hydroxyurea Derivatives with Hexacyanoferrate(III) in Aqueous Solution

Autori
Budimir, Ana ; Weitner, Tin ; Kos, Ivan ; Šakić, Davor ; Gabričević, Mario ; Bešić, Erim ; Biruš, Mladen

Izvornik
Croatica chemica acta (0011-1643) 84 (2011), 2; 133-147

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

Ključne riječi
methoxyurea; N-methylhydroxyurea; hexacyanoferrate; oxidation; kinetics; NBO; quantum chemical study

Sažetak
Kinetics and mechanisms of the oxidation of methoxyurea and N-methylhydroxyurea were studied in neutral and basic aqueous solutions. The obtained pH dependences of the oxidation rates indicate that for both hydroxyureas the reactive species are the deprotonated ones. The second order rate constants, the activation enthalpies and the activation entropies for the reactions of methoxyurea (O- methylhydroxyurea) and N- methylhydroxyurea anions with Fe(CN)6 3− at 25 oC, I = 2 mol dm−3 (NaClO4) were determined as (5.06 ± 0.01) x 102 mol−1 dm3 s−1, (1.92 ± 0.02) x 104 mol −1 dm3 s−1, 27 ± 1 kJ mol −1, 16 ± 1 kJ mol−1, −101 ± 2 J mol−1 K−1, and −107 ± 4 J mol−1 K−1, respectively. The pKa value of methoxyurea at 25 oC and 2 mol dm−3 ionic strength was determined kinetically as 12.7 ± 0.1 and the thermodynamic parameters for the deprotonation reaction were determined as ΔaH = 43 ± 1 kJ mol−1, and ΔaS = −96 ± 4 J mol−1 K−1. When the kinetic results are compared with the data reported for hydroxyurea, an inverse dependence of the rate constants on the pKa of the hydroxyurea derivatives at 25 oC is observed. Such unexpected behaviour has been explained by the ab initio calculations and NBO analysis of HOMOs for all three hydroxyureates.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Farmacija



POVEZANOST RADA


Projekt / tema
006-0061247-0009 - Kinetika i mehanizam katalitičkog antioksidacijskog djelovanja Mn-porfirina (Ana Budimir, )
006-0061247-0978 - Gastrin kao kofaktor unosa željeza u organizam. (Mario Gabričević, )

Ustanove
Farmaceutsko-biokemijski fakultet, Zagreb

Profili:

Avatar Url Ivan Kos (autor)

Avatar Url Mario Gabričević (autor)

Avatar Url Erim Bešić (autor)

Avatar Url Ana Budimir (autor)

Avatar Url Mladen Biruš (autor)

Avatar Url Tin Weitner (autor)

Avatar Url Davor Šakić (autor)

Citiraj ovu publikaciju

Budimir, Ana; Weitner, Tin; Kos, Ivan; Šakić, Davor; Gabričević, Mario; Bešić, Erim; Biruš, Mladen
Kinetics and Mechanism of Oxidation of Hydroxyurea Derivatives with Hexacyanoferrate(III) in Aqueous Solution // Croatica chemica acta, 84 (2011), 2; 133-147 doi:10.5562/cca1799 (međunarodna recenzija, članak, znanstveni)
Budimir, A., Weitner, T., Kos, I., Šakić, D., Gabričević, M., Bešić, E. & Biruš, M. (2011) Kinetics and Mechanism of Oxidation of Hydroxyurea Derivatives with Hexacyanoferrate(III) in Aqueous Solution. Croatica chemica acta, 84 (2), 133-147 doi:10.5562/cca1799.
@article{article, year = {2011}, pages = {133-147}, DOI = {10.5562/cca1799}, keywords = {methoxyurea, N-methylhydroxyurea, hexacyanoferrate, oxidation, kinetics, NBO, quantum chemical study}, journal = {Croatica chemica acta}, doi = {10.5562/cca1799}, volume = {84}, number = {2}, issn = {0011-1643}, title = {Kinetics and Mechanism of Oxidation of Hydroxyurea Derivatives with Hexacyanoferrate(III) in Aqueous Solution}, keyword = {methoxyurea, N-methylhydroxyurea, hexacyanoferrate, oxidation, kinetics, NBO, quantum chemical study} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus


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