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Water-soluble arene ruthenium complexes containing pyridinethiolato ligands: Synthesis, molecular structure, redox properties and anticancer activity of the cations [(η<sup>6</sup>-arene)Ru(<i>p</i>-SC<sub>5</sub>H<sub>4</sub>NH)<sub>3</sub>]<sup>2+</sup>
Auteur(s)
Gras, Michaël
Štěpnička, Petr
Renfrew, Anna K.
Dyson, Paul J.
Date de parution
2008
In
Journal of Organometallic Chemistry, Elsevier, 2008/693/21-22/3419-3424
Résumé
The cationic complexes [(η<sup>6</sup>-arene)Ru(SC<sub>5</sub>H<sub>4</sub>NH)<sub>3</sub>]<sup>2+</sup>, arene being C<sub>6</sub>H<sub>6</sub> (<b>1</b>), MeC<sub>6</sub>H<sub>5</sub> (<b>2</b>), <i>p-<sup>i</sup></i>PrC<sub>6</sub>H<sub>4</sub>Me (<b>3</b>) or C<sub>6</sub>Me<sub>6</sub> (<b>4</b>), have been synthesised from the reaction of 4-pyridinethiol with the corresponding precursor (η<sup>6</sup>-arene)<sub>2</sub>Ru<sub>2</sub> (μ<sup>2</sup>-Cl)<sub>2</sub>Cl<sub>2</sub> and isolated as the chloride salts. The single-crystal X-ray structure of [<b>4</b>](PF<sub>6</sub>)<sub>2</sub> 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 <b>1</b>–<b>4</b> shows a clear correlation between the Ru(II)/Ru(III) redox potentials and the number of alkyl substituents at the arene ligand (<i>E</i>°′ (RuII/III): <b>1</b> > <b>2</b> > <b>3</b> > <b>4</b>), whereas the cytotoxicity towards A2780 ovarian cancer cells follows the series <b>4</b> > <b>1</b> > <b>3</b> > <b>2</b>, the hexamethylbenzene derivative <b>4</b> being the most cytotoxic one. The corresponding reaction of the <i>ortho</i>-isomer, 2-pyridinethiol, with (η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (μ<sup>2</sup>-Cl)<sub>2</sub>Cl<sub>2</sub> does not lead to the expected 2-pyridinethiolato analogue, but yields the neutral complex (η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)Ru(η<sup>2</sup>-SC<sub>5</sub>H<sub>4</sub>N)(η<sup>1</sup>-SC<sub>5</sub>H<sub>4</sub>N) (<b>5</b>). The analogous complex (η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)Ru(η<sup>2</sup>-SC<sub>9</sub>H<sub>6</sub>N)-(η<sup>1</sup>-SC<sub>9</sub>H<sub>6</sub>N) (<b>6</b>) is obtained from the similar reaction with 2-quinolinethiol.
Identifiants
Type de publication
journal article
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