Organolanthanide Complexes Supported by Thiazole-Containing Amidopyridinate Ligands: Synthesis, Characterization and Catalytic Activity in the Isoprene Polymerization (Articolo in rivista)

Type
Label
  • Organolanthanide Complexes Supported by Thiazole-Containing Amidopyridinate Ligands: Synthesis, Characterization and Catalytic Activity in the Isoprene Polymerization (Articolo in rivista) (literal)
Anno
  • 2014-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/om500918y (literal)
Alternative label
  • Luconi, L.; Lyubov, D. M.; Rossin, A.; Glukhova, T. A.; Cherkasov, A. V.; Tuci, G.; Fukin, G. K.; Trifonov, A. A.; Giambastiani, G. (2014)
    Organolanthanide Complexes Supported by Thiazole-Containing Amidopyridinate Ligands: Synthesis, Characterization and Catalytic Activity in the Isoprene Polymerization
    in Organometallics (Online); ACS, American chemical society, Washington, DC (Stati Uniti d'America)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Luconi, L.; Lyubov, D. M.; Rossin, A.; Glukhova, T. A.; Cherkasov, A. V.; Tuci, G.; Fukin, G. K.; Trifonov, A. A.; Giambastiani, G. (literal)
Pagina inizio
  • 7125 (literal)
Pagina fine
  • 7134 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 33 (literal)
Rivista
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  • 10 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Institute of Chemistry of OrganoMetallic Compounds, ICCOM-CNR, Via Madonna del Piano, 10, 50019 Sesto Fiorentino, (Florence), Italy G. A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, Tropinina 49, GSP-445, 603950 Nizhny Novgorod, Russia (literal)
Titolo
  • Organolanthanide Complexes Supported by Thiazole-Containing Amidopyridinate Ligands: Synthesis, Characterization and Catalytic Activity in the Isoprene Polymerization (literal)
Abstract
  • Neutral bis(alkyl)-organolanthanide complexes supported by tridentate (N-,N,N) monoanionic 5-methylthiazole- or benzothiazole-amidopyridinate ligands have been prepared and completely characterized: (LThiaMe2)Ln(CH2SiMe3)2 [Ln = Lu3+ (3), Er3+ (7), Yb3+ (8)] and (LBnThMe2)Lu(CH2SiMe3)2 (5). Similarly to related Y3+ systems, the nature of the thiazole unit controls the ultimate catalyst stability in solution. In the diamagnetic Lu3+ complex 5, a progressive and complete rearrangement of its metal coordination sphere takes place through a metal-to-ligand alkyl migration with subsequent benzothiazole ring-opening and generation of the Lu3+ mono(alkyl)-arylthiolate species stabilized by a tetradentate (N-,N,N,S)- dianionic ligand. On the other hand, the 5-methylthiazole containing complexes 3, 7 and 8 showed no evidence of any ligand rearrangement. Complexes 3-8 have been tested as homogeneous catalysts in the isoprene (IP) polymerization, after activation with selected organoborates. Binary systems 3/TB and 7/TB [TB = tritylium tetrakis(pentafluorophenyl)borate] show the highest activity and living character toward the IP polymerization affording polymers with relatively high trans-1,4-selectivity (up to 76.4 %), moderate molecular weights (Mn up to 146 000 g/mol) and narrow polydispersities (Mw/Mn). Depending on the rare-earth ion of choice, a prevalent trans-1,4 (Lu3+, Er3+, Yb3+; up to 76.4 %) or a dominant 3,4 (Y3+; 92.7 %) polymer structure is observed. The influence of the ligand type, metal ion and activator(s) on the ultimate catalyst activity and selectivity are discussed. (literal)
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