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Tauchman, Jiri

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Tauchman, Jiri
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https://libra.unine.ch/handle/123456789/634

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  • Publication
    Métadonnées seulement
    Arene ruthenium and pentamethylcyclopentadienyl rhodium and iridium complexes containing N,O-chelating ligands derived from piroxicam: Synthesis, molecular structure and cytotoxicity
    (2014)
    Raja, Mathiyazhagan Ulaganatha
    ;
    Tauchman, Jiri 
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Riedel, Tina
    ;
    Dyson, Paul J.
    The non-steroidal anti-inflammatory and anti-arthritic drug piroxicam (LH) reacts with arene ruthenium dichloride dimers in refluxing dichloromethane to give the complexes [(?6-arene)Ru(?2-N,O-L)Cl] (3: arene = C6H5Me, 4: arene = p-MeC6H4Pri, 5: arene = C6Me6). The reaction seems to proceed via the intermediates [(?6-arene)Ru(N-LH)Cl2], which can be obsd. for arene = C6H5Me (1) and isolated in the case of arene = p-MeC6H4Pri (2). The analogous reaction with pentamethylcyclopentadienyl rhodium and iridium gives the complexes [(?5-C5Me5)M(?2-N,O-L)Cl] (6: M = Rh, 7: M = Ir). The single-crystal x-ray structure analyses of the p-cymene ruthenium derivs. 4 and 2 show the metal atom in the archetypical piano stool geometry; in 4 the piroxicamato ligand is coordinated in a bidentate fashion through the pyridine nitrogen atom and the enolic oxygen atom, while in 2 the intact piroxicam ligand is coordinated in a monodentate fashion through the pyridine nitrogen atom. The piroxicamato complexes 3-5 are weakly cytotoxic towards human ovarian cancer cells. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Heterodinuclear Arene Ruthenium Complexes Containing a Glycine-Derived Phosphinoferrocene Carboxamide: Synthesis, Molecular Structure, Electrochemistry, and Catalytic Oxidation Activity in Aqueous Media
    (2012)
    Tauchman, Jiri 
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    ;
    Stepnicka, Petr
    Three 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)]