Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles

Materials

Gajendra Gupta²  Benjamin S. Murray¹  Paul J. Dyson¹ 

[1] Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne CH-1015, Switzerland; E-Mails:;Institute of Chemistry, University of Neuchatel, Avenue de Bellevaux 51, Neuchatel CH-2000, Switzerland; E-Mail:

关键词: metalla-cycles;    half-sandwich complexes;    bioorganometallic chemistry;    metal-based drugs;    metalla-rectangles;    anticancer activity;   

DOI  :  10.3390/ma6115352

来源: mdpi

【 摘 要 】

The neutral dinuclear complexes [(η⁵-C₅Me₅)₂Rh₂(μ-dhnq)Cl₂] (1) and [(η⁵-C₅Me₅)₂Ir₂(μ-dhnq)Cl₂] (2) (dhnqH₂ = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂ (M = Rh, Ir) with dhnqH₂ in the presence of CH₃COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF₃SO₃, affords the corresponding tetranuclear metalla-rectangles [(η⁵-C₅Me₅)₄M₄(μ-dhnq)₂(μ-L)₂]⁴⁺ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by infrared, ¹H and ¹³C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC₅₀ values in the low micromolar range.

【 授权许可】

CC BY   
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