Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents

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2019
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Angewandte Chemie International Edition. 2019, 58(49), pp. 17777-17781. ISSN 1433-7851. eISSN 1521-3773. Available under: doi: 10.1002/anie.201909843
Zusammenfassung

Functionalized aluminium alkyls enable an effective coordinative chain transfer polymerization with selective chain initiation by the functionalized alkyl. (ω-aminoalkyl)diisobutyl aluminum reagents (twelve examples studied) obtained by hydroalumination of α-amino-ω-enes with diisobutyl aluminum hydride promote the stereoselective catalytic chain growth of butadiene on aluminum in presence of Nd(versatate)3, Cp2Nd(allyl) or Cp2Gd(allyl) precatalysts and [PhNMe2H+]/[B(C6F5)4-]. Carbazolyl- and indolyl- aluminum reagents result in efficient molecular weight control and chain initiation by the aminoalkyl rather than isobutyl substitutent bound to aluminum. As evidenced for (3-(9H-carbazol-9-yl)propyl) initiated polybutadiene (PBD) inter alia by deuterium quenching studies, polymer chain transfer by β-hydride transfer is negligible in comparison to back-transfer to aluminum.

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Fachgebiet (DDC)
540 Chemie
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Coordinative Chain Transfer Polymerization, Functionalized Chain Transfer Reagents, Aluminum, Neodymium, Polybutadiene
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ISO 690GÖTTKER-SCHNETMANN, Inigo, Philip KENYON, Stefan MECKING, 2019. Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents. In: Angewandte Chemie International Edition. 2019, 58(49), pp. 17777-17781. ISSN 1433-7851. eISSN 1521-3773. Available under: doi: 10.1002/anie.201909843
BibTex
@article{GottkerSchnetmann2019-12-02Coord-47282,
  year={2019},
  doi={10.1002/anie.201909843},
  title={Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents},
  number={49},
  volume={58},
  issn={1433-7851},
  journal={Angewandte Chemie International Edition},
  pages={17777--17781},
  author={Göttker-Schnetmann, Inigo and Kenyon, Philip and Mecking, Stefan}
}
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