Cyclopolymerization Reactions of Diallyl Monomers: Exploring Electronic and Steric Effects Using DFT Reactivity Indices

Ugur I., De Vleeschouwer F., Tüzün N., Aviyente V., Geerlings P., Liu S., ...Daha Fazla

JOURNAL OF PHYSICAL CHEMISTRY A, cilt.113, sa.30, ss.8704-8711, 2009 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 113 Sayı: 30
  • Basım Tarihi: 2009
  • Doi Numarası: 10.1021/jp903371b
  • Dergi Adı: JOURNAL OF PHYSICAL CHEMISTRY A
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.8704-8711
  • İstanbul Teknik Üniversitesi Adresli: Evet

Özet

The regioselectivity in the cyclopolymerization of diallyl monomers is investigated using DFT-based reactivity indices. In the first part, the experimentally observed mode of cyclization (exo versus endo) of 11 selected radicals involved in this process is reproduced by the computation of activation energies, entropies, enthalpies, and Gibb's free energies for the 5- and 6-membered cyclization reactions. The application of a recently proposed energy partitioning of the activation barriers shows that the regioselectivity cannot be explained by the steric effect alone. Next, a number of relevant DFT-based reactivity indices, such as non-spin-polarized and spin-polarized Fukui functions, spin densities, and dual descriptors, were applied to probe the role of the polar and stereoelectronic effects in this reaction. The dual descriptor has been found to reproduce best the experimental trends, confirming the important role of the stereoelectronic effects.