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  • Publication
    Métadonnées seulement
    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, Michael
    ;
    ; ;
    Zava, Olivier
    ;
    Dyson, Paul J.
    Treatment of an arene-Ru dichloride dimer with thiols RSH to lead to cationic trithiolato complexes [(arene)2Ru2(SR)3]+ proceeds through the neutral thiolato complexes [(arene)2Ru2(SR)2Cl2], which were isolated and characterized for arene = p-MeC6H4CHMe2 and R = CH2Ph (1), CH2CH2Ph (2), CH2C6H4CMe3 (3), and C6H11 (4). The single-crystal x-ray structure anal. of the p-tert-butylbenzyl deriv. 3 reveals that the two Ru 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, deriv. 2 is highly cytotoxic against human ovarian cancer cells, with IC50 values of 0.20 ? for the A2780 cell line and 0.31 for the cisplatin-resistant cell line A2780cisR. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Ru2(CO)4(OOCR)2L2 sawhorse-type complexes containing axial 5-(4-pyridyl)-10,15,20-triphenylporphyrin ligands
    (2011)
    Gras, Michael
    ;
    Barry, Nicolas P. E.
    ;
    ;
    The thermal reaction of Ru3(CO)12 with various carboxylic acids (benzoic, 4-hydroxyphenylacetic, ferrocenic, stearic, oleic, 4-(octadecyloxy)benzoic) in refluxing THF, followed by addn. of 5-(4-pyridyl)-10,15,20-triphenylporphyrin (L), gives the dinuclear complexes Ru2(CO)4(OOCR)2L2 (1: R = -C6H5, 2: R = -CH2-p-C6H4OH, 3: R = -C5H4FeC5H5, 4: R = -(CH2)16CH3, 5: R = -(CH2)7CH=CH(CH2)7CH3, 6: R = -p-C6H4O(CH2)17CH3). Complexes 1-6 were characterized by IR, NMR, and ESI-MS as well as by elemental anal. The UV-visible spectra show the Soret band centered at 417 nm and the Q bands at 515, 550, 590 and 645 nm, resp. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Water-soluble arene ruthenium complexes containing pyridinethiolato ligands: Synthesis, molecular structure, redox properties and anticancer activity of the cations [(?6-arene)Ru(p-SC5H4NH)3]2+
    (2008)
    Gras, Michael
    ;
    ; ;
    Stepnicka, Petr
    ;
    Renfrew, Anna K.
    ;
    Dyson, Paul J.
    The cationic complexes [(?6-arene)Ru(SC5H4NH)3]2+, arene being C6H6 (1), MeC6H5 (2), p-iPrC6H4Me (3) or C6Me6 (4), have been synthesized from the reaction of 4-pyridinethiol with the corresponding precursor (?6-arene)2Ru2(?2-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 center through the sulfur atom, with the hydrogen atom transferred from the sulfur to the nitrogen atom. The electrochem. study of 1-4 shows a clear correlation between the Ru(II)/Ru(III) redox potentials and the no. 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 deriv. 4 being the most cytotoxic one. The corresponding reaction of the ortho-isomer, 2-pyridinethiol, with (?6-C6Me6)2Ru2(?2-Cl)2Cl2 does not lead to the expected 2-pyridinethiolato analog, but yields the neutral complex (?6-C6Me6)Ru(?2-SC5H4N)(?1-SC5H4N) (5). The analogous complex (?6-C6Me6)Ru(?2-SC9H6N)-(?1-SC9H6N) (6) is obtained from the similar reaction with 2-quinolinethiol. [on SciFinder(R)]