Cyclopolymerization reactions of diallyl monomers: Exploring electronic and steric effects using DFT reactivity indices

Ilke Uǧur, Freija De Vleeschouwer, Nurcan Tüzün, Viktorya Aviyente, Paul Geerlings, Shubin Liu, Paul W. Ayers, Frank De Proft*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

32 Citations (Scopus)

Abstract

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 spinpolarized 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.

Original languageEnglish
Pages (from-to)8704-8711
Number of pages8
JournalJournal of Physical Chemistry A
Volume113
Issue number30
DOIs
Publication statusPublished - 30 Jul 2009

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