Vanadium(IV) Complexes with Methyl-Substituted 8-Hydroxyquinolines: Catalytic Potential in the Oxidation of Hydrocarbons and Alcohols with Peroxides and Biological Activity
Joanna Palion-Gazda,
André Luz,
Luis R. Raposo,
Katarzyna Choroba,
Jacek E. Nycz,
Alina Bieńko,
Agnieszka Lewińska,
Karol Erfurt,
Pedro V. Baptista,
Barbara Machura,
Alexandra R. Fernandes,
Lidia S. Shul’pina,
Nikolay S. Ikonnikov,
Georgiy B. Shul’pin
Affiliations
Joanna Palion-Gazda
Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland
André Luz
Associate Laboratory i4HB-Institute for Health and Bioeconomy, NOVA School of Science and Technology, NOVA University Lisbon, 2819-516 Caparica, Portugal
Luis R. Raposo
Associate Laboratory i4HB-Institute for Health and Bioeconomy, NOVA School of Science and Technology, NOVA University Lisbon, 2819-516 Caparica, Portugal
Katarzyna Choroba
Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland
Jacek E. Nycz
Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland
Alina Bieńko
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wroclaw, Poland
Agnieszka Lewińska
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wroclaw, Poland
Karol Erfurt
Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, 44-100 Gliwice, Poland
Pedro V. Baptista
Associate Laboratory i4HB-Institute for Health and Bioeconomy, NOVA School of Science and Technology, NOVA University Lisbon, 2819-516 Caparica, Portugal
Barbara Machura
Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland
Alexandra R. Fernandes
Associate Laboratory i4HB-Institute for Health and Bioeconomy, NOVA School of Science and Technology, NOVA University Lisbon, 2819-516 Caparica, Portugal
Lidia S. Shul’pina
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ulitsa Vavilova 28, 119991 Moscow, Russia
Nikolay S. Ikonnikov
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ulitsa Vavilova 28, 119991 Moscow, Russia
Georgiy B. Shul’pin
N.N Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina 4, 119991 Moscow, Russia
Methyl-substituted 8-hydroxyquinolines (Hquin) were successfully used to synthetize five-coordinated oxovanadium(IV) complexes: [VO(2,6-(Me)2-quin)2] (1), [VO(2,5-(Me)2-quin)2] (2) and [VO(2-Me-quin)2] (3). Complexes 1–3 demonstrated high catalytic activity in the oxidation of hydrocarbons with H2O2 in acetonitrile at 50 °C, in the presence of 2-pyrazinecarboxylic acid (PCA) as a cocatalyst. The maximum yield of cyclohexane oxidation products attained was 48%, which is high in the case of the oxidation of saturated hydrocarbons. The reaction leads to the formation of a mixture of cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone. When triphenylphosphine is added, cyclohexyl hydroperoxide is completely converted to cyclohexanol. Consideration of the regio- and bond-selectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicates that the oxidation proceeds with the participation of free hydroxyl radicals. The complexes show moderate activity in the oxidation of alcohols. Complexes 1 and 2 reduce the viability of colorectal (HCT116) and ovarian (A2780) carcinoma cell lines and of normal dermal fibroblasts without showing a specific selectivity for cancer cell lines. Complex 3 on the other hand, shows a higher cytotoxicity in a colorectal carcinoma cell line (HCT116), a lower cytotoxicity towards normal dermal fibroblasts and no effect in an ovarian carcinoma cell line (order of magnitude HCT116 > fibroblasts > A2780).
