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Therrien, Bruno
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Therrien, Bruno
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bruno.therrien@unine.ch
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- PublicationMétadonnées seulementBiological Studies of Chalcogenolato-Bridged Dinuclear Half-Sandwich Complexes(2013)
;Johnpeter, Justin P. ;Gupta, Gajendra ;Kumar, Jerald Mahesh ;Srinivas, Gunda ;Nagesh, NarayanaCationic 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)] - PublicationMétadonnées seulementSynthesis, molecular structure, computational study and in vitro anticancer activity of dinuclear thiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes(2013)
;Gupta, Gajendra; ;Murray, Benjamin S. ;Dyson, Paul J. ;Fabre, Gabin ;Trouillas, Patrick ;Giannini, Federico ;Furrer, Julien; 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 seulementSyntheses and structural studies of mononuclear arene ruthenium complexes with nitrogen-based chelating ligands(2012)
;Gupta, Gajendra; ;Park, Sunhong ;Lee, Shim SungKim, JinkwonDinuclear 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)] - PublicationMétadonnées seulement[Bis(2-pyridyl-?N)amine]chlorido(?6-hexamethylbenzene)ruthenium(II) hexafluoridophosphate dichloromethane solvate(2011)
;Gupta, Gajendra; Kim, JinkwonIn 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)] - PublicationMétadonnées seulementBis-(2-pyrid-yl-?N)amine]chlorido(?-hexa-methyl-benzene)-ruthenium(II) hexa-fluorido-phosphate dichloro-methane solvate(2011)
;Gupta, Gajendra; Kim, JinkwonIn 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)] - PublicationMétadonnées seulementStudy of novel ?5-cyclopentadienyl and ?6-arene platinum group metal complexes containing a N4-type ligand and their structural characterization(2009)
;Gupta, Gajendra ;Yap, Glenn P. A.; Rao, Kollipara MohanThe mononuclear ?5-cyclopentadienyl complexes [(?5-C5H5)Ru(PPh3)2Cl], [(?5-C5H5)Os(PPh3)2Br] and pentamethylcyclopentadienyl complex [(?5-C5Me5)Ru(PPh3)2Cl] react in the presence of 1 equiv. of the tetradentate N,N'-chelating ligand 3,5-bis(2-pyridyl)pyrazole (bpp-H) and 1 equiv. of NH4PF6 in methanol to afford the mononuclear complexes [(?5-C5H5)Ru(PPh3)(bpp-H)]PF6 ([1]PF6), [(?5-C5H5)Os(PPh3)(bpp-H)]PF6 ([2]PF6) and [(?5-C5Me5)Ru(PPh3)(bpp-H)]PF6 ([3]PF6), resp. The dinuclear ?5-pentamethylcyclopentadienyl complexes [(?5-C5Me5)Rh(?-Cl)Cl]2 and [(?5-C5Me5)Ir(?-Cl)Cl]2 as well as the dinuclear ?6-arene ruthenium complexes [(?6-C6H6)Ru(?-Cl)Cl]2 and [(?6-p-iPrC6H4Me)Ru(?-Cl)Cl]2 react with 2 equiv. of bpp-H in the presence of NH4PF6 or NH4BF4 to afford the corresponding mononuclear complexes [(?5-C5Me5)Rh(bpp-H)Cl]PF6 ([4]PF6), [(?5-C5Me5)Ir(bpp-H)Cl]PF6 ([5]PF6), [(?6-C6H6)Ru(bpp-H)Cl]BF4 ([6]BF4) and [(?6-p-iPrC6H4Me)Ru(bpp-H)Cl]BF4 ([7]BF4). However, in the presence of 1 equiv. of bpp-H and NH4BF4 the reaction with the same ?6-arene ruthenium complexes affords the dinuclear salts [(?6-C6H6)2Ru2(bpp)Cl2]BF4 ([8]BF4) and [(?6-p-iPrC6H4Me)2Ru2(bpp)Cl2]BF4 ([9]BF4), resp. These compds. have been characterized by IR, NMR and mass spectrometry, as well as by elemental anal. The mol. structures of [1]PF6, [5]PF6 and [8]BF4 have been established by single crystal x-ray diffraction studies and some representative complexes have been studied by UV-vis spectroscopy. [on SciFinder(R)]