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Browsing by Author "Blais, Jean-Claude"

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  • From simple monopyridine clusters [Mo6Br13(Py-R)][n-Bu4N] and hexapyridine clusters [Mo6X8(Py-R)6][OSO2CF3]4 (X = Br or I) to cluster-cored organometallic stars, dendrons, and dendrimers
    Publication . Méry, Denise; Plault, Lauriane; Ornelas, Cátia; Ruiz, Jaime; Nlate, Sylvain; Astruc, Didier; Blais, Jean-Claude; Rodrigues, João; Cordier, Stéphane; Kirakci, Kaplan; Perrin, Christiane
    Hexasubstitution of apical triflate ligands in the octahedral clusters [M]2[Mo6X8(CF3SO3)6] (M = n-Bu4N or Cs, X = Br or I) and monosubstitution in [n-Bu4N]2[Mo6Br13(CF3SO3)] was carried out in tetrahydrofuran at 60 degrees C with simple pyridines and then extended to organometallic pyridines, yielding cluster-cored stars, and to dendronic polyallyl- and polyferrocenylpyridines, yielding cluster-cored polyallyl and polyferrocenyl dendrimers and dendrons. The orange pyridine-substituted clusters, whose pyridine protons are deshielded in 1H NMR (a practical tool for characterization), are air-stable and thermally stable with simple pyridines, light- and air-sensitive with organometallic pyridines, and air-fragile and thermally fragile with large dendronized pyridines.
    2006-02-06Journal article Restricted access Show more
  • Organometallic syntheses of hexa and nonanitrile ligands and their ruthenium complexes
    Publication . Ornelas, Cátia; Ruiz, Jaime; Blais, Jean-Claude; Rodrigues, João; Astruc, Didier
    Hexa- and nonanitrile ligands were synthesized by the known CpFe+-induced hexaallylation of hexamethylbenzene in [FeCp(η6-C6Me6)][PF6] and nonaallylation of mesitylene in [FeCp(η6-1,3,5-C6H3Me3)][PF6], respectively, followed by Pt-catalyzed regioselective hydrosilylation of the iron-free polyolefins using (chloromethyl)dimethylsilane and sodium iodide catalyzed Williamson coupling with p-hydroxybenzonitrile. The hexanitrile star was coordinated to the piano-stool ruthenium complex [RuCp(PPh3)2Cl] by substitution of the six ruthenium-bound chlorides with nitriles using TlPF6 to give the hexacationic hexaruthenium star complex, whereas the analogous metalation reaction partly failed, due to bulk constraint with the nonanitrile ligand. The strategy that involved lengthening of the tethers of the latter, however, successfully provided a nonacationic nonaruthenium complex.
    2004Journal article Restricted access Show more