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

  • Stefan Wirth
  • Christoph J. Rohbogner
  • Marcin Cieslak
  • Julia Kazmierczak-Baranska
  • Stefan Donevski
  • Barbara Nawrot
  • Ingo-Peter Lorenz
Original Paper


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.


Rhodium Iridium N,O chelate Cytotoxicity DNA binding 



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.

Supplementary material

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Supplementary material (PDF 989 kb)


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Copyright information

© SBIC 2009

Authors and Affiliations

  • Stefan Wirth
    • 1
  • Christoph J. Rohbogner
    • 1
  • Marcin Cieslak
    • 2
  • Julia Kazmierczak-Baranska
    • 2
  • Stefan Donevski
    • 2
  • Barbara Nawrot
    • 2
  • Ingo-Peter Lorenz
    • 1
  1. 1.Department of Chemistry and BiochemistryLudwig-Maximilian University MunichMunichGermany
  2. 2.Department of Bioorganic Chemistry, Centre of Molecular and Macromolecular StudiesPolish Academy of SciencesLodzPoland

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