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Therrien, Bruno

Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/382
_
0000-0002-0388-2745

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  • Publication
    Métadonnées seulement
    Biological Studies of Chalcogenolato-Bridged Dinuclear Half-Sandwich Complexes
    (2013)
    Johnpeter, Justin P.
    ;
    Gupta, Gajendra
    ;
    Kumar, Jerald Mahesh
    ;
    Srinivas, Gunda
    ;
    Nagesh, Narayana
    ;
    Therrien, Bruno 
    Cationic chalcogenolato-bridged diruthenium complexes [(?6-p-MeC6H4Pri)2Ru2(?-EC6H5)3]+ (E = S, 1; E = Se, 2; E = Te, 3) were obtained in EtOH from the reaction of (?6-p-MeC6H4Pri)2Ru2(?-Cl)2Cl2 with benzenethiol, benzeneselenol, and Na tellurophenolate, resp. The thiolato and selenolato derivs. are isolated in good yield as the chloride salts, while the tellurolato analog is isolated as the hexafluorophosphate salt. Similarly, the dinuclear pentamethylcyclopentadienyl (C5Me5) Rh and Ir complexes (?5-C5Me5)2M2(?-Cl)2Cl2 react with benzenethiol, benzeneselenol, and Na tellurophenolate in EtOH to give the corresponding cationic dinuclear complexes [(?5-C5Me5)2M2(?-EC6H5)3]+ (M = Rh, E = S, 4; E = Se, 5; E = Te, 6; M = Ir, E = S, 7; E = Se, 8; E = Te, 9). Cationic dinuclear complexes with mixed thiolato-selenolato and thiolato-tellurolato bridges were prepd., [(?6-p-MeC6H4Pri)2Ru2(?-EC6H5)(?-SCH2C6H4-p-But)2]+ (E = Se, 10; E = Te, 11) and [(?5-C5Me5)2M2(?-EC6H5)(?-SCH2C6H5)2]+ (M = Rh, E = Se, 12; E = Te, 13; M = Ir, E = Se, 14; E = Te, 15), starting from the neutral dinuclear complexes (?6-p-MeC6H4Pri)2Ru2Cl2(?-SCH2C6H4-p-But)2 and (?5-C5Me5)2M2Cl2(?-SCH2C6H5)2. All complexes are highly cytotoxic showing activity in the submicromolar range. The nature of the chalcogenolato bridges seems to have an impact on the activity, while the nature of the metal center plays a minor role. Among the complexes tested, the dinuclear complexes 1, 4, and 7 with the thiolato bridges show the highest activity on cancer cells and the best affinity for CT-DNA as demonstrated by cell biol. and biophys. expts. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Synthesis, molecular structure, computational study and in vitro anticancer activity of dinuclear thiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes
    (2013)
    Gupta, Gajendra
    ;
    Garci, Amine 
    ;
    Murray, Benjamin S.
    ;
    Dyson, Paul J.
    ;
    Fabre, Gabin
    ;
    Trouillas, Patrick
    ;
    Giannini, Federico
    ;
    Furrer, Julien
    ;
    Süss-Fink, Georg 
    ;
    Therrien, Bruno 
    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)]
  • Publication
    Accès libre
    Synthesis, molecular structure and cytotoxicity of molecular materials based on water soluble half-sandwich Rh(III) and Ir(III) tetranuclear metalla-cycles
    (2013)
    Gupta, Gajendra
    ;
    Murray, Benjamin S.
    ;
    Dyson, Paul J.
    ;
    Therrien, Bruno 
    The neutral dinuclear complexes [(?5-C5Me5)2Rh2(?-dhnq)Cl2] (1) and [(?5-C5Me5)2Ir2(?-dhnq)Cl2] (2) (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(?5-C5Me5)M(?-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 [(?5-C5Me5)4M4(?-dhnq)2(?-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 IR, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure anal. 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 mols. In addn., 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. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Syntheses and structural studies of mononuclear arene ruthenium complexes with nitrogen-based chelating ligands
    (2012)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Park, Sunhong
    ;
    Lee, Shim Sung
    ;
    Kim, Jinkwon
    Dinuclear arene Ru complexes [(?6-arene)Ru(?-Cl)Cl]2 (arene = C6H6; p-iPrC6H4Me; C6Me6) and monomeric cyclopentadienyl complex [(Cp)Ru(PPh3)2Cl] react with polypyridyl N ligands L1 (3-(pyridin-2-yl)-1H-1,2,4-triazole) and L2 (1,3-bis(di-2-pyridylaminomethyl)benzene) in MeOH to afford cationic mononuclear compds., [(?6-arene)Ru(L1)Cl]+ (arene = C6H6 (1); p-iPrC6H4Me (2); C6Me6 (3)), [(?6-arene)Ru(L2)Cl]+ (arene = C6H6 (4); p-iPrC6H4Me (5); C6Me6 (6)), [(Cp)Ru(L1)(PPh3)]+ (7) and [(Cp)Ru(L2)(PPh3)]+ (8). All cationic mononuclear compds. were isolated as their hexafluorophosphate salts and characterized by elemental analyses, NMR and IR spectroscopic methods and some representative complexes by UV-visible spectroscopy. The solid state structures of two derivs., [6]PF6 and [7]PF6, were detd. by x-ray structure anal. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    [Bis(2-pyridyl-?N)amine]chlorido(?6-hexamethylbenzene)ruthenium(II) hexafluoridophosphate dichloromethane solvate
    (2011)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Kim, Jinkwon
    In the title half-sandwich complex, [RuCl(?6-C12H18)(C10H9N3)]PF6·CH2Cl2, the Ru(II) ion is four-coordinated by a chloro, a hexamethylbenzene and a bidentate N,N'-chelating di(pyridin-2-yl)amine ligand. In the crystal, the amino N-H group forms a H bond with the chloro ligand of a neighboring complex, thus forming chains along the b axis. Weak intermol. C-H...F and C-H. Cl contacts are also obsd. Crystallog. data and at. coordinates are given. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Bis-(2-pyrid-yl-?N)amine]chlorido(?-hexa-methyl-benzene)-ruthenium(II) hexa-fluorido-phosphate dichloro-methane solvate
    (2011)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Kim, Jinkwon
    In the title half-sandwich complex, [RuCl(?(6)-C(12)H(18))(C(10)H(9)N(3))]PF(6)?CH(2)Cl(2), the ruthenium(II) ion is four-coordinated by a chloro, a hexa-methyl-benzene and a bidentate N,N'-chelating di(pyridin-2-yl)amine ligand. In the crystal, the amino N-H group forms a hydrogen bond with the chloro ligand of a neighbouring complex, thus forming chains along the b axis. Weak inter-molecular C-H(midline ellipsis)F and C-H(midline ellipsis) Cl contacts are also observed.[on SciFinder (R)]
  • Publication
    Accès libre
    Study of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands
    (2011)
    Gupta, Gajendra
    ;
    Gloria, Sairem
    ;
    Nongbri, Saphidabha. L.
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    A series of mono-cationic dinuclear half sandwich ruthenium, rhodium and iridium metal complexes have been synthesized using ((pyridin-2-yl)methylimino)nicotinamide (L1) and ((picolinamido)phenyl)picolinamide (L2) ligands: [(η6-arene)2Ru2 (μ-L1)Cl3]+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(μ-L1)Cl3] + (M = Rh, 4; Ir, 5), and [(η6-arene)2Ru2(μ-L2)(μ-Cl)]+ (arene = C6H6, 6; p-iPrC6H4Me, 7; C6Me6, 8), [(η5-C5Me5)2M2(μ-L2)Cl2]+ (M = Rh, 9; Ir, 10). All the complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR and IR spectroscopy. The solid state structure of three representatives 4, 6 and 9 has been determined by X-ray crystallographic studies. Interestingly, in the molecular structure of 4, the first metal is bonded to two nitrogen atoms whereas the second metal center is coordinated to only one nitrogen atom with two terminal chloride ligands. Fascinatingly in the case of the complexes with the symmetrical ligand L2, both ruthenium centers having η6-arene groups are bonded to nitrogen atoms with a bridging chloride atom between the two metal centers, whereas the metals with η5-Cp∗ groups are bonded to the ligand N,O and N,N fashion.
  • Publication
    Accès libre
    Study of half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two di-pyridylamine units linked by an aromatic spacer
    (2011)
    Gupta, Gajendra
    ;
    Sairem, Gloria
    ;
    Therrien, Bruno 
    ;
    Babulal, Das
    ;
    Rao, Kollipara Mohan
    A general approach for the preparation of dinuclear η5- and η6-cyclic hydrocarbon platinum group metal complexes, viz. [(η6-arene)2Ru2 (NN∩NN)Cl2]2+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(NN∩NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(η5-C5H5)2M2(NN∩NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(η5-C5Me5)2Ru2(NN∩NN)(PPh3)2]2+ (8) and [(η5-C9H7)2Ru2(NN∩NN)(PPh3)2]2+ (9), bearing the bis-bidentate ligand 1,2-bis(di-2-pyridylaminomethyl)benzene (NN∩NN), which contains two chelating di-pyridylamine units connected by an aromatic spacer, is reported. The cationic dinuclear complexes have been isolated as their hexafluorophosphate or hexafluoroantimonate salts and characterized by use of a combination of NMR, IR and UV–vis spectroscopic methods and by mass spectrometry. The solid state structure of three derivatives, [2][SbF6]2, [3][PF6]2 and [4][PF6]2, has been determined by X-ray structure analysis.
  • Publication
    Accès libre
    [Bis(2-pyridyl-κN)amine]chlorido(η6-hexamethylbenzene)ruthenium(II) hexafluoridophosphate dichloromethane solvate
    (2011)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Kim, Jinkwom
    In the title half-sandwich complex, [RuCl(η6-C12H18)(C10H9N3)]PF6•CH2Cl2, the ruthenium(II) ion is four-coordinated by a chloro, a hexamethylbenzene and a bidentate N, N'-chelating di(pyridin-2-yl)amine ligand. In the crystal, the amino N-H group forms a hydrogen bond with the chloro ligand of a neighbouring complex, thus forming chains along the b axis. Weak intermolecular C-H...F and C-H... Cl contacts are also observed.
  • Publication
    Accès libre
    Half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two pyrazolyl-pyridine units linked by an aromatic spacer
    (2010)
    Gupta, Gajendra
    ;
    Therrien, Bruno 
    ;
    Rao, Kollipara Mohan
    Reaction of the bis-bidentate ligand, 1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene (NN∩NN), containing two chelating pyrazolyl-pyridine units connected by an aromatic spacer with platinum group metal complexes results in a series of cationic binuclear complexes, [(η6-arene)2Ru2(NN∩NN)Cl2]2+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(NN∩NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(η5-C5H5)2M2(NN∩NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(η5-C5Me5)2Ru2(NN∩NN)(PPh3)2]2+ (8) and [(η5-C9H7)2Ru2(NN∩NN)(PPh3)2]2+ (9). All these complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR spectroscopy, IR spectroscopy and mass spectrometry. The solid state structures of three complexes, [2][PF6]2, [4][PF6]2 and [6][PF6]2, has been determined by X-ray crystallographic studies.