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Therrien, Bruno
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Therrien, Bruno
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bruno.therrien@unine.ch
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Voici les éléments 1 - 10 sur 193
- PublicationMétadonnées seulementArene ruthenium and pentamethylcyclopentadienyl rhodium and iridium complexes containing N,O-chelating ligands derived from piroxicam: Synthesis, molecular structure and cytotoxicity(2014)
; ; ; - PublicationMétadonnées seulementHighly cytotoxic diruthenium trithiolato complexes of the type [(?6-p-MeC6H4Pri)2Ru2(?2-SR)3]+: synthesis, characterization, molecular structure and in vitro anticancer activity(2013)
; Cationic dinuclear p-cymene Ru complexes bridged by three thiophenolato ligands contg. various substituents mainly in meta and ortho positions, [(?6-p-MeC6H4Pri)2Ru2(?2-SR)3]+ (R = 3-C6H4Me: 1; R = 3-C6H4OMe: 2; R = 3-C6H4OEt: 3; R = 3-C6H4CF3: 4; R = 3-C6H4NH2: 5; R = 3-C6H4Cl: 6; R = 2-C6H4Me: 7; R = 2-C6H4OMe: 8; R = 2-C6H4Pri: 9; R = 2-C6H4CF3: 10; R = npt: 11 (npt = 2-naphthyl); R = mco: 12 (mco = 4-methylcoumarinyl); R = 3,5-C6H3Me2: 13; R = 3,5-C6H3(CF3)2: 14; R = 3,5-C6H3Cl2: 15; R = 3,4-C6H3(OMe)2: 16), were prepd. from the reaction of the neutral p-cymene diruthenium dichloride dimer, [(?6-p-MeC6H4Pri)2Ru2Cl4], with the corresponding thiophenol RSH. All cationic complexes were isolated as their chloride salts and fully characterized by spectroscopic and anal. methods. The mol. structures of 10 and 15 were solved by a single-crystal x-ray structure anal. of [10]Cl and [15]Cl, which show that the two Ru atoms adopt a pseudo-octahedral geometry without a metal-metal bond in accordance with the noble gas rule. All complexes are highly cytotoxic towards human ovarian cancer cells, the IC50 values being mostly in the nanomolar range. Complex 9 shows the highest cytotoxicity with an IC50 value of 0.03 ?M towards the A2780 cell line and the cisplatin-resistant mutant A2780cisR. The cytotoxicity of these complexes, which belong to the most active Ru anticancer compds. reported so far, can be correlated with the lipophilicity of the corresponding thiols. In comparison with the previous series, the positions of the substituents in the thiophenolato bridges are not as important as the nature of the substituents, alkyl substituents being the best ones in line with their lipophilic character. [on SciFinder(R)] - PublicationMétadonnées seulementSynthesis, characterisation and in vitro anticancer activity of hexanuclear thiolato-bridged arene ruthenium metalla-prisms(2013)
; ; Hexanuclear hexacationic thiolato-bridged arene ruthenium metalla-prisms of the general formula [[(?6-p-cymene)Ru]6(?-SR)6(?3-tpt)2][OTf]6 (R = CH2Ph, CH2C6H4-p-tBu, CH2CH2Ph; tpt = 2,4,6-tri-4-pyridyl-1,3,5-triazine), obtained from the self-assembly of dinuclear precursors [(p-cymene)2Ru2(?-SR)2Cl2] with tpt and AgCF3SO3, have been isolated and fully characterized as triflate salts. The metalla-prisms are highly cytotoxic against human ovarian cancer cells, esp. towards the cisplatin-resistant cell line A2780cisR (IC50 - PublicationMétadonnées seulementSynthesis, molecular structure, computational study and in vitro anticancer activity of dinuclear thiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes(2013)
; ; Neutral dinuclear dithiolato-bridged pentamethylcyclopentadienyl Rh(III) complexes (C5Me5)2Rh2(?-SR)2Cl2 (R = CH2Ph, 1; R = CH2CH2Ph, 2) and cationic dinuclear trithiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes [(C5Me5)2M2(?-SR)3]+ (M = Rh, R = CH2Ph, 3; M = Rh, R = CH2CH2Ph, 5; M = Rh, R = CH2C6H4-p-tBu, 7: M = Ir, R = CH2Ph, 4; M = Ir, R = CH2CH2Ph, 6; M = Ir, R = CH2C6H4-p-tBu, 8) were synthesized from the chloro-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) dimers (C5Me5)2M2(?-Cl)2Cl2 by reaction with the corresponding thiol deriv. (RSH). Complexes 3-8 were isolated as chloride salts. All complexes were obtained in good yield and were fully characterized by spectroscopic methods. The mol. structures of the neutral complexes (1 and 2) show interesting features: the two Rh atoms are bridged by two thiolato ligands with no metal-metal bonds and the pentamethylcyclopentadienyl and chlorido ligands are oriented syn to each other, an uncommon conformation for such dinuclear complexes. These structural features were rationalized using DFT calcns. Addnl., the antiproliferative activity of the complexes was evaluated against the cancerous A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) human ovarian cell lines and on the noncancerous HEK293 human embryonic kidney cells. All complexes are active and the cationic Ir complexes 4, 6 and 8 are particularly cytotoxic, with IC50 values in the nanomolar range (IC50 < 0.1 ?M). The catalytic activity of the complexes for the oxidn. of glutathione (GSH) to GSSG was evaluated by NMR spectroscopy. [on SciFinder(R)] - PublicationMétadonnées seulementArene ruthenium dichloro complexes containing isonicotinic ester ligands: Synthesis, molecular structure and cytotoxicity(2013)
; ; - PublicationMétadonnées seulementDifferent coordination modes of dipyridyl ketimine ligands in cationic arene ruthenium complexes(2013)
; 2,2'-Dipyridyl-N-arylimines L (L1 = 2,4,6-trimethyl(di-2-pyridylmethylene)aniline, L2 = 2,6-diisopropyl(di-2-pyridylmethylene)aniline) react with arene ruthenium dichloride dimer in methanol to give cationic arene ruthenium complexes of the general type [(arene)Ru(?2-N,N-L)Cl]+ (arene = C6H6, p-MeC6H4Pri). Two coordination modes of the chelating ligands N,N-L are obsd. In the major isomer, the ketimine nitrogen atom and one of the two pyridine nitrogen atoms are coordinated to ruthenium, while in the minor isomer the two pyridine nitrogen atoms coordinate to the metal center. In the case of L1, the minor isomer of the p-cymene ruthenium chloro complex could be isolated as the tetrafluoroborate salt and characterized by single crystal X-ray anal. The mol. structure of the major isomer was detd. by X-ray crystallog. in the case of the tetraphenylborate salt of the benzene ruthenium chloro deriv. In both structures, the ruthenium atom shows the expected pseudo-tetrahedral coordination geometry. [on SciFinder(R)] - PublicationAccès libreEncapsulation of Photosensitizers in Hexa- and Octanuclear Organometallic Cages: Synthesis and Characterization of Carceplex and Host-Guest Systems in SolutionCationic arene ruthenium assemblies of the general formulas [Ru6(p-cymene)6(tris-pvb)2(?2-Cl)6]6+, [Ru6(p-cymene)6(tris-pvb)2(OO?OO)3]6+ (tris-pvb = 1,3,5-tris{2-(pyridin-4-yl)vinyl}benzene), and [Ru8(p-cymene)8(NN?NN)2(OO?OO)4]8+ (NN?NN = 1,2,4,5-tetrakis{2-(pyridin-4-yl)vinyl}benzene, 1,2,4,5-tetrakis{2-(pyridin-4-yl)ethynyl}benzene) have been obtained from the corresponding dinuclear arene ruthenium complexes [Ru2(p-cymene)2(?-Cl)2Cl2] and [Ru2(p-cymene)2(OO?OO)Cl2] (OO?OO = oxalato, 2,5-dioxido-1,4-benzoquinonato, 2,5-dichloro-1,4-benzoquinonato, 5,8-dioxido-1,4-naphthoquinonato, 5,8-dioxido-1,4-anthraquinonato, 6,11-dioxido-5,12-naphthacenedionato) by reaction with the multidentate ligands and silver trifluoromethanesulfonate. These cationic hexa- and octanuclear cages have been isolated and characterized as their triflate salts. Addn. of coronene during the synthesis of the large hexanuclear assemblies leads to the direct encapsulation of coronene in the cavity of the trigonal-prismatic complexes. Photosensitizers such as porphin, phthalocyanine, and Zn-phthalocyanine present during the synthesis of these metalla-cages are encapsulated in five of these arene ruthenium complexes to give photosensitizer-encapsulated systems. The host-guest properties of these systems were studied in soln. by DOSY, 2D NOESY and 2D ROESY NMR spectroscopy. The H···H distances between guests and selected metalla-cages were estd. by 2D ROESY NMR spectroscopy and modelization. NMR analyzes indicate that the guest photosensitizers are completely encapsulated in two of these metalla-cages, while in the three other ruthenium cages NMR spectra reveal an equil. between empty and filled cages. [on SciFinder(R)]
- PublicationMétadonnées seulementHeterodinuclear Arene Ruthenium Complexes Containing a Glycine-Derived Phosphinoferrocene Carboxamide: Synthesis, Molecular Structure, Electrochemistry, and Catalytic Oxidation Activity in Aqueous Media(2012)
; ; ; Stepnicka, PetrThree series of heterodinuclear Ru-Fe complexes were synthesized from (?6-arene)ruthenium dichloride dimers and phosphinoferrocene ligands contg. glycine-based carboxamido substituents. The neutral complexes [(?6-arene)RuCl2(Ph2PfcCONHCH2CO2Me-?P)] (4, arene = benzene (a), p-cymene (b), hexamethylbenzene (c); fc = ferrocene-1,1'-diyl) were obtained by the bridge cleavage reaction of [(?6-arene)RuCl2]2 with Ph2PfcCONHCH2CO2Me (1) in CHCl3 soln. [(?6-P-cymene)RuCl2(Ph2PfcCONHCH2CONH2-?P)] (6b) was synthesized in the same way from Ph2PfcCONHCH2CONH2 (3); the prepn. of [(?6-p-cymene)RuCl2(Ph2PfcCONHCH2CO2H-?P)] (5b), featuring the ferrocene ligand in the free acid form (2), failed due to side reactions and isolation problems. [(?6-Arene)RuCl(MeCN)(1-?P)][PF6] (7a-c) and [(?6-arene)Ru(MeCN)2(1-?P)][PF6]2 (8a-c) were prepd. from 1 and the MeCN precursors [(?6-arene)RuCl(MeCN)2][PF6] and from 4a-c via halide removal with Ag[PF6] in MeCN soln., resp. Alternative synthetic routes to 7b and 8b were also studied. The compds. were fully characterized by elemental anal., multinuclear NMR, IR, and electrospray ionization mass spectra, and their electrochem. properties were studied by cyclic voltammetry at a Pt-disk electrode. The single-crystal x-ray analyses of two representatives (4b and 8b) revealed a pseudotetrahedral coordination geometry at the Ru centers and eclipsed conformations of the ferrocene moieties, with the substituents at the two cyclopentadienyl rings being anti with respect to each other. All complexes showed high activity for the catalytic oxidn. of secondary alcs. with tert-Bu hydroperoxide to give ketones in aq. media. The most active catalyst was obtained from the neutral p-cymene complex 4b, showing a catalytic turnover frequency of 13,200 h-1 at room temp. for the oxidn. of 1-phenylethanol at a substrate/catalyst ratio of 100,000. [on SciFinder(R)] - PublicationMétadonnées seulementHighly cytotoxic trithiophenolatodiruthenium complexes of the type [(?6-p-MeC6H4Pri)2Ru2(SC6H4-p-X)3]+: synthesis, molecular structure, electrochemistry, cytotoxicity, and glutathione oxidation potential(2012)
; ; - PublicationMétadonnées seulementHeteronuclear complexes containing the N,N'-di(2-pyridyl)amidocarboxylferrocene ligand(2012)
; The ferrocene-derived ligand (NC5H4)2NOC-C5H4FeC5H5 reacts with arene ruthenium complexes [(?6-arene)RuCl2]2 to give the cationic complexes [(?6-p-iPrC6H4Me)RuCl{(NC5H4)2NOC-C5H4FeC5H5}]+ (1) and [(?6-C6Me6)RuCl{(NC5H4)2NOC-C5H4FeC5H5}]+ (2), isolated as the hexafluorophosphate and tetrafluoroborate salts, resp., while the reaction with K2PtCl4 yields the neutral complex PtCl2{(NC5H4)2NOC-C5H4FeC5H5} (3). The mol. structures of 2 and 3 were confirmed by single-crystal x-ray diffraction. [on SciFinder(R)]