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Tetranuclear coordination assemblies based on half-sandwich ruthenium(II) complexes: Noncovalent binding to DNA and cytotoxicity

Lookup NU author(s): Dr Miguel Galindo-Cuesta


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The reaction of [(cymene)RuCI2]2 with K 2Hoxonate (H3oxonic=4,6-dihydroxy-2-carboxy-1,3,5-triazine acid) in methanol leads to the formation of the dinuclear half-sandwich ruthenium(II) complex [(cymene)2Ru2(μ-Hoxonato)Cl 2] (1a). Removal of the chloride ligands of 1a by treatment with AgCF3SO3 yields [(cymene)2Ru 2(μ-Hoxonato)(CF3SO3)2] (1b), which, upon posterior reaction with N,N-linkers (L=4,4′-bipyridine (4,4′-bpy), 4,7-phenantroline (4,7-phen)), gives rise to the formation of the tetranuclear open boxes [(cymene)4Ru4(μ-Hoxonato) 2(μ-N, N-L)2](CF3SO3)4 (2a, L=4,4′-bpy; 2b, L= 4,7-phen). These systems have been characterized by1H NMR, UV - vis, and ESI-MS. The single-crystal structures of the dinuclear precursor 1a and of the clathrate 2b⊂4,7-phen have been determined. The interaction of these systems with cysteine, mononucleotides, and calf-thymus DNA has been studied by means of 1H NMR, UV - vis, circular dicroism, competitive binding assays, and atomic force microscopy imaging. The results show that the robust tetracationic ruthenium(II) cyclic systems 2a and 2b do not give ligand exchange reactions toward biorelevant ligands. Nevertheless, these systems are able to noncovalently bind to DNA, probably at the surface of the major groove, inducing significant conformational changes in this biomolecule. It is also interesting to note that compounds 2a and 2b, in spite of only giving supramolecular interactions with biomolecules, exhibit antitumor activity, particularly toward the human ovarian cancer cell line A2780cisR, showing acquired resistance to cisplatin, with respective 4.6 and 8.3 microM IC50 values. © 2009 American Chemical Society.

Publication metadata

Author(s): Linares F, Galindo M, Galli S, Romero M, Navarro J, Barea E

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2009

Volume: 48

Issue: 15

Pages: 7413-7420

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society


DOI: 10.1021/ic900980y


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