Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity

Handle URI:
http://hdl.handle.net/10754/566967
Title:
Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity
Authors:
Kuhn, Paul-Steffen; Cremer, Laura; Gavriluta, Anatolie; Jovanović, Katarina K.; Filipović, Lana; Hummer, Alfred A.; Büchel, Gabriel E. ( 0000-0002-5055-7099 ) ; Dojčinović, Biljana P.; Meier, Samuel M.; Rompel, Annette; Radulović, Siniša; Tommasino, Jean Bernard; Luneau, Dominique; Arion, Vladimir B.
Abstract:
A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by 13C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)]2− are coordinated to YIII and DyIII, respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4]5− (Ln=Y, Dy). While YIII is eight-coordinate in 2, DyIII is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N+ ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
Citation:
Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity 2015: Chemistry - A European Journal
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
10-Aug-2015
DOI:
10.1002/chem.201502026
Type:
Article
ISSN:
09476539
Is Supplemented By:
Kuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., … Arion, V. B. (2015). CCDC 1402056: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1j1ym4; DOI:10.5517/cc1j1ym4; HANDLE:http://hdl.handle.net/10754/624431; Kuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., … Arion, V. B. (2015). CCDC 1402057: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1j1yn5; DOI:10.5517/cc1j1yn5; HANDLE:http://hdl.handle.net/10754/624432; Kuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., … Arion, V. B. (2015). CCDC 951636: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10y7y4; DOI:10.5517/cc10y7y4; HANDLE:http://hdl.handle.net/10754/624243
Additional Links:
http://doi.wiley.com/10.1002/chem.201502026
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorKuhn, Paul-Steffenen
dc.contributor.authorCremer, Lauraen
dc.contributor.authorGavriluta, Anatolieen
dc.contributor.authorJovanović, Katarina K.en
dc.contributor.authorFilipović, Lanaen
dc.contributor.authorHummer, Alfred A.en
dc.contributor.authorBüchel, Gabriel E.en
dc.contributor.authorDojčinović, Biljana P.en
dc.contributor.authorMeier, Samuel M.en
dc.contributor.authorRompel, Annetteen
dc.contributor.authorRadulović, Sinišaen
dc.contributor.authorTommasino, Jean Bernarden
dc.contributor.authorLuneau, Dominiqueen
dc.contributor.authorArion, Vladimir B.en
dc.date.accessioned2015-08-13T11:30:13Zen
dc.date.available2015-08-13T11:30:13Zen
dc.date.issued2015-08-10en
dc.identifier.citationHeteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity 2015: Chemistry - A European Journalen
dc.identifier.issn09476539en
dc.identifier.doi10.1002/chem.201502026en
dc.identifier.urihttp://hdl.handle.net/10754/566967en
dc.description.abstractA series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by 13C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)]2− are coordinated to YIII and DyIII, respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4]5− (Ln=Y, Dy). While YIII is eight-coordinate in 2, DyIII is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N+ ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells.en
dc.language.isoenen
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://doi.wiley.com/10.1002/chem.201502026en
dc.rightsThis is the peer reviewed version of the following article: Kuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., Büchel, G. E., Dojčinović, B. P., Meier, S. M., Rompel, A., Radulović, S., Tommasino, J. B., Luneau, D. and Arion, V. B. (2015), Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity. Chem. Eur. J.. doi: 10.1002/chem.201502026, which has been published in final form at http://doi.wiley.com/10.1002/chem.201502026. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.en
dc.subjectantitumor agentsen
dc.subjectlanthanideen
dc.subjectnitrosylen
dc.subjectosmiumen
dc.subjectrutheniumen
dc.titleHeteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activityen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalChemistry - A European Journalen
dc.eprint.versionPost-printen
dc.contributor.institutionUniversity of Vienna, Faculty of Chemistry, Institute of Inorganic Chemistry, Währinger Strasse 42, 1090 Vienna (Austria)en
dc.contributor.institutionUniversité Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces (UMR 5615), Campus de la Doua, 69622 Villeurbanne cedex (France)en
dc.contributor.institutionInstitute for Oncology and Radiology of Serbia, Pasterova 14, 11000 Belgrade (Serbia)en
dc.contributor.institutionUniversität Wien, Fakultät für Chemie, Institut für Biophysikalische Chemie, Althanstraße 14, 1090 Wien (Austria)en
dc.contributor.institutionFaculty of Chemistry, Institute of Analytical Chemistry, University of Vienna, Währinger Strasse 38, 1090 Vienna (Austria)en
dc.contributor.institutionUniversity of Belgrade, Institute of Chemistry, Technology and Metallurgy, Center of Chemistry, Studentski trg 12-16, Belgrade (Serbia)en
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorBüchel, Gabriel E.en
dc.relation.isSupplementedByKuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., … Arion, V. B. (2015). CCDC 1402056: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1j1ym4en
dc.relation.isSupplementedByDOI:10.5517/cc1j1ym4en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624431en
dc.relation.isSupplementedByKuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., … Arion, V. B. (2015). CCDC 1402057: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1j1yn5en
dc.relation.isSupplementedByDOI:10.5517/cc1j1yn5en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624432en
dc.relation.isSupplementedByKuhn, P.-S., Cremer, L., Gavriluta, A., Jovanović, K. K., Filipović, L., Hummer, A. A., … Arion, V. B. (2015). CCDC 951636: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10y7y4en
dc.relation.isSupplementedByDOI:10.5517/cc10y7y4en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624243en
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