Theoretical Chemistry Accounts

, Volume 97, Issue 1–4, pp 277–282

Formation of 2-hexene by cationic dimerization of propene: an ab initio and density functional theory study

  • N. Salhi-Benachenhou
  • J. R. Alvarez-Idaboy
  • S. Lunell
  • L. A. Eriksson
Article
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Abstract.

The formation of a 2-hexene radical cation from a propene radical cation and a neutral propene molecule is investigated by means of ab initio UHF and spin projected MP2 calculations, as well as the SVWN and B3LYP levels of density functional theory. A stable addition complex, with loose CC bonds, is found. To proceed from the addition complex to the product, a locally planar transition state must be passed, with a migrating hydrogen located half-way between the donating and the accepting carbon atoms. At the highest computational levels considered, PMP2/6-31G(d,p)//MP2/3-21G and B3LYP/6-31G(d,p), this transition state lies approximately 11 and 13 kcal/mol, respectively, above the addition complex. The high barrier is believed to be one reason why radical cation oligomerization of propene has not been detected experimentally, in contrast to the case of ethene, where the corresponding barrier is only a few kcal/mol.

Key words: Propene cation Cationic dimerization 2-Hexene 

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Copyright information

© Springer-Verlag Berlin Heidelberg 1997

Authors and Affiliations

  • N. Salhi-Benachenhou
    • 1
  • J. R. Alvarez-Idaboy
    • 1
  • S. Lunell
    • 1
  • L. A. Eriksson
    • 2
  1. 1.Department of Quantum Chemistry, Uppsala University, P.O. Box 518, S-751 20 Uppsala, SwedenSE
  2. 2.Department of Physics, Stockholm University, P.O. Box 6730, S-113 85 Stockholm, SwedenSE

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