Abstract
Compared to the inert and highly cytotoxic dinuclearp-cymene ruthenium trithiolato complexes, the less cytotoxic mono- and dithiolato complexes readily hydrolyse in aqueous solution and form adducts with cysteine, but do not interact with DNA.
Highlights
The hydrolysis and the reactivity of two dinuclear p-cymene ruthenium monothiolato complexes, [(h6-pMeC6H4Pri)2Ru2Cl2(m-Cl)(m-S-m-9-B10C2H11)] (1) and [(h6-p-MeC6H4Pri)2Ru2Cl2(m-Cl)(m-SCH2-p-C6H4– NO2)] (2), and of two dinuclear p-cymene ruthenium dithiolato complexes, [(h6-p-MeC6H4Pri)2Ru2(mSCH2CH2Ph)2Cl2] (3) and [(h6-p-MeC6H4Pri)2Ru2(SCH2C6H4-p-OMe)2Cl2] (4) towards amino acids, nucleotides, and a single-stranded DNA dodecamer were studied using NMR and mass spectrometry
By varying the synthetic procedure, we succeeded in isolating neutral dithiolato complexes of the type [(h6-p-MeC6H4Pri)2Ru2(m-SR)2Cl2]41 and subsequently monothiolato complexes of the general formula [(h6-p-MeC6H4Pri)2Ru2Cl2(m-Cl)(m-SR)],42 intermediates in the formation of the cationic trithiolato complexes, opening new avenues for the ne-tuning the properties of dinuclear thiolato-bridged arene ruthenium complexes (Scheme 1).[43]
Unlike other arene ruthenium complexes, these results suggest that DNA is not a target of thiolato-bridged arene ruthenium complexes and that they exert their cytotoxicity through other mechanisms
Summary
The hydrolysis and the reactivity of two dinuclear p-cymene ruthenium monothiolato complexes, [(h6-pMeC6H4Pri)2Ru2Cl2(m-Cl)(m-S-m-9-B10C2H11)] (1) and [(h6-p-MeC6H4Pri)2Ru2Cl2(m-Cl)(m-SCH2-p-C6H4– NO2)] (2), and of two dinuclear p-cymene ruthenium dithiolato complexes, [(h6-p-MeC6H4Pri)2Ru2(mSCH2CH2Ph)2Cl2] (3) and [(h6-p-MeC6H4Pri)2Ru2(SCH2C6H4-p-OMe)2Cl2] (4) towards amino acids, nucleotides, and a single-stranded DNA dodecamer were studied using NMR and mass spectrometry. The dithiolato complexes 3 and 4 are stable in water under acidic conditions, but undergo slow hydrolysis under neutral and basic conditions In both cases, the cationic hydroxo complexes [(h6-p-MeC6H4Pri)2Ru2(OD)(CD3CN)(m-SR)2]+ are the only species observed in D2O/CD3CN at equilibrium. By varying the synthetic procedure, we succeeded in isolating neutral dithiolato complexes of the type [(h6-p-MeC6H4Pri)2Ru2(m-SR)2Cl2]41 and subsequently monothiolato complexes of the general formula [(h6-p-MeC6H4Pri)2Ru2Cl2(m-Cl)(m-SR)],42 intermediates in the formation of the cationic trithiolato complexes, opening new avenues for the ne-tuning the properties of dinuclear thiolato-bridged arene ruthenium complexes (Scheme 1).[43]. No adducts were identi ed, but Cys and GSH undergo a catalytic oxidation in the presence of the trithiolato complexes, forming cystine and GSSG.[35] Such a mode of action has already been proposed for arene ruthenium azopyridine iodo complexes, which are surprisingly cytotoxic despite their inertness
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