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- Ruthenium metallodendrimers based on Nitrile-functionalized Poly(alkylidene imine)sPublication . Ornelas, Cátia; Vertlib, Viatcheslav; Rodrigues, João; Rissanen, KariThe preparation of the first- and second-generation of nitrilefunctionalized poly(alkylidene imine) dendrimers with the organometallic ruthenium complex [Ru(η5-C5H5)(PPh3)2Cl] peripherally attached is described. The reaction of N,N -bis(cyanomethyl)piperazine (1), N,N -bis[N ,N -bis(cyanoethyl)aminoethyl]piperazine (2), or N,N,N ,N -tetrakis(cyanoethyl)ethylenediamine (3) with [Ru(η5-C5H5)(PPh3)2Cl] (4) in the presence of TlPF6 gives the new air-stable ruthenium metallodendrimers 5, 6, and 7, respectively. These stable metallodendrimers are easily prepared and represent a novel quantitative method to solidify and chromatographically purify the otherwise semi-liquid nitrile-functionalized poly(alkylidene imine) dendrimers. The compounds were fully characterized by IR and 1H, 13C, and 31P NMR spectroscopy, and mass spectrometry. These dendrimers represent the first example of the utilization of nitrile-functionalized poly(alkylidene imine)s as cores in the preparation of metallodendrimers.
- 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 dendrimersPublication . Méry, Denise; Plault, Lauriane; Ornelas, Cátia; Ruiz, Jaime; Nlate, Sylvain; Astruc, Didier; Blais, Jean-Claude; Rodrigues, João; Cordier, Stéphane; Kirakci, Kaplan; Perrin, ChristianeHexasubstitution 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.