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

The neutral dinuclear complexes [(η(5)-C(5)Me(5))(2)Rh(2)(μ-dhnq)Cl(2)] (1) and [(η(5)-C(5)Me(5))(2)Ir(2)(μ-dhnq)Cl(2)] (2) (dhnqH(2) = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η(5)-C(5)Me(5))M(μ-Cl)Cl](2) (M = Rh, Ir) with dhnqH(2) in the presence of CH(3)COONa. Treatm...

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Autores principales: Gupta, Gajendra, Murray, Benjamin S., Dyson, Paul J., Therrien, Bruno
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2013
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5452765/
https://www.ncbi.nlm.nih.gov/pubmed/28788394
http://dx.doi.org/10.3390/ma6115352
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author Gupta, Gajendra
Murray, Benjamin S.
Dyson, Paul J.
Therrien, Bruno
author_facet Gupta, Gajendra
Murray, Benjamin S.
Dyson, Paul J.
Therrien, Bruno
author_sort Gupta, Gajendra
collection PubMed
description The neutral dinuclear complexes [(η(5)-C(5)Me(5))(2)Rh(2)(μ-dhnq)Cl(2)] (1) and [(η(5)-C(5)Me(5))(2)Ir(2)(μ-dhnq)Cl(2)] (2) (dhnqH(2) = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η(5)-C(5)Me(5))M(μ-Cl)Cl](2) (M = Rh, Ir) with dhnqH(2) in the presence of CH(3)COONa. 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 AgCF(3)SO(3), affords the corresponding tetranuclear metalla-rectangles [(η(5)-C(5)Me(5))(4)M(4)(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, (1)H and (13)C 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 IC(50) values in the low micromolar range.
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spelling pubmed-54527652017-07-28 Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles Gupta, Gajendra Murray, Benjamin S. Dyson, Paul J. Therrien, Bruno Materials (Basel) Article The neutral dinuclear complexes [(η(5)-C(5)Me(5))(2)Rh(2)(μ-dhnq)Cl(2)] (1) and [(η(5)-C(5)Me(5))(2)Ir(2)(μ-dhnq)Cl(2)] (2) (dhnqH(2) = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η(5)-C(5)Me(5))M(μ-Cl)Cl](2) (M = Rh, Ir) with dhnqH(2) in the presence of CH(3)COONa. 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 AgCF(3)SO(3), affords the corresponding tetranuclear metalla-rectangles [(η(5)-C(5)Me(5))(4)M(4)(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, (1)H and (13)C 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 IC(50) values in the low micromolar range. MDPI 2013-11-20 /pmc/articles/PMC5452765/ /pubmed/28788394 http://dx.doi.org/10.3390/ma6115352 Text en © 2013 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).
spellingShingle Article
Gupta, Gajendra
Murray, Benjamin S.
Dyson, Paul J.
Therrien, Bruno
Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles
title Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles
title_full Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles
title_fullStr Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles
title_full_unstemmed Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles
title_short Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles
title_sort synthesis, molecular structure and cytotoxicity of molecular materials based on water soluble half-sandwich rh(iii) and ir(iii) tetranuclear metalla-cycles
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5452765/
https://www.ncbi.nlm.nih.gov/pubmed/28788394
http://dx.doi.org/10.3390/ma6115352
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