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  • Publication
    Métadonnées seulement
    Electron-Rich Arene-Ruthenium Metalla-architectures Incorporating Tetrapyridyl-Tetrathiafulvene Donor Moieties
    (2014)
    Vajpayee, Vaishali
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    Bivaud, Sebastien
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    Goeb, Sebastien
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    Croue, Vincent
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    Allain, Magali
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    Popp, Brian V.
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    ; ;
    Salle, Marc
    A series of arene ruthenium architectures have been prepd. from coordination-driven self-assembly using dinuclear p-cymene ruthenium acceptors and ?-donating tetratopic tetrapyridyl-tetrathiafulvalene donor ligands. The synthetic strategy, based on a geometric interaction approach, leads to four electroactive metalla-assemblies, 1-4 (one mol. cube and three metallaplates), that were characterized by NMR, ESI-MS, X-ray diffraction, and cyclic voltammetry. Rationalization of their formation discrepancy was completed by DFT calcns. supported by structural features of their constituting TTF and Ru-complex components. Metalla-architectures possessing electron-rich cores (3, cis-4, and trans-4) interact strongly with picric acid (PA) to yield cocrystd. products, PA + metalla-assemblies, confirmed by single-crystal X-ray structure analyses. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Insight into the dynamic ligand exchange process involved in bipyridyl linked arene ruthenium metalla-rectangles
    (2014) ;
    Marti, Simon
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    Schuerch, Stefan
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    The dynamic ligand exchange behavior of cationic arene ruthenium metalla-rectangles of the type [(p-cymene)4Ru4(OO?OO)2(N?N)2]4+ (OO?OO = oxalato, 2,5-dioxydo-1,4-benzoquinonato, 5,8-dioxydo-1,4-naphthoquinonato; N?N = 4,4'-bipyridine-H8, 4,4'-bipyridine-D8) has been studied in soln. The robustness of the rectangular architecture has been evidenced by NMR and ESI mass spectrometry. Thermodn. and kinetic aspects of the ligand exchange process have been explored using 1H/2D isotope labeling of the 4,4'-bipyridine connectors. This study shows that ligand exchange does not proceed spontaneously for these metalla-assemblies, even at high temp., unless an external stimulus is applied. [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
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    Murray, Benjamin S.
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    Dyson, Paul J.
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    Fabre, Gabin
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    Trouillas, Patrick
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    Giannini, Federico
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    Furrer, Julien
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    ;
    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
    Métadonnées seulement
    Synthesis, characterisation and in vitro anticancer activity of hexanuclear thiolato-bridged arene ruthenium metalla-prisms
    (2013)
    Furrer, Mona A.
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    ;
    Denoyelle-Di-Muro, Emmanuel
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    Trouillas, Patrick
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    Giannini, Federico
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    Furrer, Julien
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    Clavel, Catherine M.
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    Dyson, Paul J.
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    ;
    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
  • Publication
    Accès libre
    Dichlorido(furfurylamine-κN)(η6-hexamethylbenzene)ruthenium(II)
    The single-crystal X-ray structure analysis of [RuCl2(C12H18)(C5H7NO)] reveals a distorted piano-stool geometry around the RuII atom, with a hexamethylbenzene ligand, two chloride ligands and a furfurylamine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is observed as a result of N-H...Cl interactions between two symmetry-related molecules.
  • Publication
    Métadonnées seulement
    Dichlorido(furfuryl-amine-?N)(?-hexa-methyl-benzene)-ruthenium(II)
    The single-crystal X-ray structure analysis of [RuCl(2)(C(12)H(18))(C(5)H(7)NO)] reveals a distorted piano-stool geometry around the Ru(II) atom, with a hexa-methyl-benzene ligand, two chloride ligands and a furfuryl-amine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is observed as a result of N-H(midline ellipsis)Cl inter-actions between two symmetry-related mol-ecules.[on SciFinder (R)]
  • Publication
    Métadonnées seulement
    Dichlorido(furfurylmine-?N)(?6-hexamethylbenzene)ruthenium(II)
    The single-crystal x-ray structure anal. of [RuCl2(C12H18)(C5H7NO)] reveals a distorted piano-stool geometry around the RuII atom, with a hexamethylbenzene ligand, two chloride ligands and a furfurylamine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is obsd. as a result of N-H···Cl interactions between two symmetry-related mols. Crystallog. data and at. coordinates are given. [on SciFinder(R)]