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Selective 3,4-polymerization mechanism of isoprene catalyzed by rare earth alkyl complexes

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Abstract

The mechanism of selective 3,4-polymerization reaction of isoprene catalyzed by the rare earth lutecium( III) alkyl complexes [2,6-Me2Ph-N-CH2-C(CH2SiMe3)=N-PhMe2-2,6]Lu(CH2SiMe3)2(THF) was investigated by means of the M06/sdd method with solvation effects taken into account. The results show that the structure of the catalyst core remained almost unchanged as the isoprene molecules were alternatively inserted into the complex at two opposite sides. The Gibbs free energies of the coordination complexes, transition state and intermediates indicate that all the isoprene molecules prefer to insert into the complex with the 3,4-polymerization selectivity as catalyzed by the catalyst, which is consistent with the experimental observations. It is found that the insertion reaction of each isoprene is exothermic, which comes mainly from the coordination of the isoprene molecule to the lutecium( III) atom. The solvation effects were confirmed important in predicting the Gibbs free energies of the present reaction system.

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Authors and Affiliations

  1. School of Chemistry, Beijing Institute of Technology, Beijing, 100081, P. R. China

    Ying Liu, Cuihong Sun, Xiaofang Li & Shaowen Zhang

  2. College of Chemical Engineering, Shijiazhuang University, Shijiazhuang, 050035, P. R. China

    Cuihong Sun

Authors
  1. Ying Liu
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  2. Cuihong Sun
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  3. Xiaofang Li
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  4. Shaowen Zhang
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Corresponding authors

Correspondence to Xiaofang Li or Shaowen Zhang.

Additional information

Supported by the National Natural Science Foundation of China(Nos.21173022, 20974014, 21274012).

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Liu, Y., Sun, C., Li, X. et al. Selective 3,4-polymerization mechanism of isoprene catalyzed by rare earth alkyl complexes. Chem. Res. Chin. Univ. 30, 114–118 (2014). https://doi.org/10.1007/s40242-014-3483-6

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  • DOI: https://doi.org/10.1007/s40242-014-3483-6

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