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  • Publication
    Accès libre
    Thiolato-Bridged Arene–Ruthenium Complexes: Synthesis, Molecular Structure, Reactivity, and Anticancer Activity of the Dinuclear Complexes [(arene)2Ru2 (SR)2Cl2]
    (2012)
    Ibao, Anne-Flore
    ;
    Gras, Michaël
    ;
    ; ;
    Zava, Olivier
    ;
    Dyson, Paul J.
    Treatment of an arene–ruthenium dichloride dimer with thiols RSH to lead to cationic trithiolato complexes of the type [(arene) 2Ru2(SR)3]+ was shown to proceed through the neutral thiolato complexes [(arene)2Ru2(SR)2Cl2], which have been isolated and characterized for arene = p-MeC6H4iPr and R = CH2Ph (1), CH2CH2Ph (2), CH2C6H4-p-tBu (3), and C6H11 (4). The single-crystal X-ray structure analysis of the p-tert-butylbenzyl derivative 3 reveals that the two ruthenium atoms are bridged by the two thiolato ligands without a metal–metal bond. The neutral dithiolato complexes[(arene)2Ru2(SR)2Cl2] (1–3) are intermediates in the formation of the cationic trithiolato complexes [(arene)2Ru2(SR)3]+ (5–7). Of the new [(arene)2Ru2(SR)2Cl2] complexes, derivative 2 is highly cytotoxic against human ovarian cancer cells, with IC50 values of 0.20 μM for the A2780 cell line and 0.31 for the cisplatin-resistant cell line A2780cisR.
  • Publication
    Accès libre
    Arene–ruthenium complexes with ferrocene-derived ligands: Synthesis and characterization of complexes of the type [Ru(η6-arene)(NC5H4CH2NHOC-C5H4FeC5H5)Cl2] and [Ru(η6-arene)(NC3H3N(CH2)2O2C–C5H4FeC5H5)Cl2]
    (2009)
    Auzias, Mathieu
    ;
    Gueniat, Joël
    ;
    ; ;
    Renfrew, Anna K.
    ;
    Dyson, Paul J.
    Arene–ruthenium complexes of general formula [Ru(η6-arene)(L)Cl2] where L = NC5H4CH2NHOC-C5H4FeC5H5, arene = p-iPrC6H4Me (1) or C6Me6 (2); L = NC3H3N(CH2) 2O2C–C5H4FeC5H5, arene = p-iPrC6H4Me (3) or C6Me6 (4), and diruthenium–arene complexes of general formula [Ru(η6-arene)Cl2] 2 (L) where L = 1,1′-(NC5H4CH2NHOC)2-C5H4FeC5H4, arene = p-iPrC6H4Me (5) or C6Me6 (6); L = 1,1′-(NC3H3N(CH2)2O2C)2–C5H4FeC5H4, arene = p-iPrC6H4Me (7) or C6Me6 (8) have been synthesized and characterized. The molecular structures of 1 and 3 were confirmed by single-crystal X-ray diffraction. The in vitro anticancer activities of complexes 1–8 have been studied comparatively to the uncoordinated ligands. The complexes exhibit fairly low cytotoxicities in comparison to related ferrocene-derived arene–ruthenium complexes.
  • Publication
    Accès libre
    Water-soluble arene ruthenium complexes containing pyridinethiolato ligands: Synthesis, molecular structure, redox properties and anticancer activity of the cations [(η6-arene)Ru(p-SC5H4NH)3]2+
    (2008)
    Gras, Michaël
    ;
    ; ;
    Štěpnička, Petr
    ;
    Renfrew, Anna K.
    ;
    Dyson, Paul J.
    The cationic complexes [(η6-arene)Ru(SC5H4NH)3]2+, arene being C6H6 (1), MeC6H5 (2), p-iPrC6H4Me (3) or C6Me6 (4), have been synthesised from the reaction of 4-pyridinethiol with the corresponding precursor (η6-arene)2Ru22-Cl)2Cl2 and isolated as the chloride salts. The single-crystal X-ray structure of [4](PF6)2 reveals three 4-pyridinethiol moieties coordinated to the ruthenium centre through the sulphur atom, with the hydrogen atom transferred from the sulphur to the nitrogen atom. The electrochemical study of 14 shows a clear correlation between the Ru(II)/Ru(III) redox potentials and the number of alkyl substituents at the arene ligand (E°′ (RuII/III): 1 > 2 > 3 > 4), whereas the cytotoxicity towards A2780 ovarian cancer cells follows the series 4 > 1 > 3 > 2, the hexamethylbenzene derivative 4 being the most cytotoxic one. The corresponding reaction of the ortho-isomer, 2-pyridinethiol, with (η6-C6Me6)2Ru22-Cl)2Cl2 does not lead to the expected 2-pyridinethiolato analogue, but yields the neutral complex (η6-C6Me6)Ru(η2-SC5H4N)(η1-SC5H4N) (5). The analogous complex (η6-C6Me6)Ru(η2-SC9H6N)-(η1-SC9H6N) (6) is obtained from the similar reaction with 2-quinolinethiol.