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Rhodium(III) and iridium(III) complexes with 1,2-naphthoquinone-1-oximate as a bidentate ligand: synthesis, structure, and biological activity

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Abstract

The synthesis and characterization of three novel iridium(III) complexes and one rhodium(III) complex with 1-nitroso-2-naphthol (3) chelating as a 1,2-naphthoquinone-1-oximato ligand are described. The reaction of μ2-halogenido-bridged dimers [(η5-C5Me5)IrX2]2 [X is Cl (1a), Br (1b), I (1c)] and [(η5-C5Me5)RhCl2]2 (2a) with 3 in CH2Cl2 yields the mononuclear complexes (η5-C5Me5)IrX(η2-C10H6N2O) (4a, 4b, 4c) and (η5-C5Me5)RhCl(η2-C10H6N2O) (5a). All compounds were characterized by their 1H and 13C NMR, IR, and mass spectra, UV/vis spectra were recorded for 4a and 5a. The X-ray structure analyses revealed a pseudo-octahedral “piano-stool” configuration for the metals with bidentate coordination through oximato-N and naphthoquinone-O, forming a nearly planar five-membered metallacycle. The metal complexes 4a and 5a were evaluated in respect to their cytotoxicity and binding affinity toward double-stranded DNA. As determined in the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, both exerted a much stronger cytotoxic effect toward HeLa and HL60 cancer cell lines than did cisplatin. The remarkable cytotoxicity of the compounds tested may be attributed to necrosis, rather than to apoptosis, as it is evidenced by the caspase-3/7 activation assay. No clear evidence was found for interaction with double-stranded DNA. The melting experiments showed no significant differences between thermodynamic parameters of intact DNA and DNA incubated with 3, 4a, or 5a, although these derivatives altered DNA recognition by the BamHI restriction enzyme. Therefore, the screened iridium and rhodium complexes 4a and 5a may still be interesting as potential anticancer drugs owing to their high cytotoxicity toward cancer cell lines, whereas they do not modify DNA in a way similar to that of cisplatin.

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Acknowledgments

Financial support from the Center for Integrated Protein Science Munich (CIPS, LMU Excellent) is gratefully acknowledged. The biological part of this work was done in the Anticancer Screening Laboratory in the Department of Bioorganic Chemistry, Centre of Molecular and Macromolecular Studies of the Polish Academy of Sciences and was financially supported by the Ministry of Science and Higher Education through the Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, under Decision PBZ-MNiSW-07/I/2007 for the years 2008–2010.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Ludwig-Maximilian University Munich, Butenandtstr. 5-13 (House D), 81377, Munich, Germany

    Stefan Wirth, Christoph J. Rohbogner & Ingo-Peter Lorenz

  2. Department of Bioorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363, Lodz, Poland

    Marcin Cieslak, Julia Kazmierczak-Baranska, Stefan Donevski & Barbara Nawrot

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  1. Stefan Wirth
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Correspondence to Barbara Nawrot or Ingo-Peter Lorenz.

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Wirth, S., Rohbogner, C.J., Cieslak, M. et al. Rhodium(III) and iridium(III) complexes with 1,2-naphthoquinone-1-oximate as a bidentate ligand: synthesis, structure, and biological activity. J Biol Inorg Chem 15, 429–440 (2010). https://doi.org/10.1007/s00775-009-0615-4

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