Kinetics and mechanism of the reactions of Ru(II)-arene complex with some biologically relevant ligands |
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Authors: | Ana RilakBiljana Petrovi? Sanja Grguri?-Šipka?ivoslav Teši? ?ivadin D Bugar?i? |
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Institution: | a University of Kragujevac, Faculty of Science, R. Domanovi?a 12, P.O. Box 60, 34000 Kragujevac, Serbia b University of Belgrade, Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia |
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Abstract: | The reactions of ruthenium(II)-arene complex RuII(η6-p-cym)(pydc)Cl] (where p-cym = p-isopropyl toluene, pydc = 2,3-pyridinedicarboxylato) with biologically nitrogen-donor nucleophiles, such as guanosine-5′-monophosphate (5′-GMP), guanosine (Guo) and l-histidine (l-His) were studied by UV-Vis spectrophotometry and 1H NMR spectroscopy. The reactions were studied at pH 2.5 and at 7.2. All reactions were followed under pseudo-first order conditions with large excess of the nucleophiles. The selected nucleophiles have a high affinity for Ru(II)-arene complex. The reactivity of the used ligands follow the same order at both pH values: Guo > 5′-GMP > l-His, while the reactions at pH 7.2 are always faster. The negative entropies of activation (ΔS≠) support an associative mode of activation. However, the rate constants obtained by 1H NMR at 295 K in D2O follow the same order of the ligand reactivity. The hydrolysis of the RuII(η6-p-cym)(pydc)Cl] complex was very fast and completed by the time the first spectrum was measured. Addition of excess of NaCl to equilibrium solutions reversed the hydrolysis. |
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Keywords: | [RuII(η6-p-cym)(pydc)Cl] chlorido(p-cymene)(2 3-pyridinedicarboxylato)ruthenium(II) p-cym p-isopropyl toluene pydc 2 3-pyridinedicarboxylato 5&prime -GMP guanosine-5&prime -monophosphate Guo guanosine l-His" target="_blank">l-His l-histidine" target="_blank">l-histidine Hepes buffer N-2-hydroxyethylpiperazine-N&prime -2-ethanesulfonic acid TSP trimethylsilylpropionic acid |
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