Influence of connector groups on the interactions of substituents with carbon-centered radicals
- Menon, Ambili S. School of Chemistry and ARC Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Australia - Department of Chemistry, University of Fribourg, Switzerland
- Bally, Thomas Department of Chemistry, University of Fribourg, Switzerland
- Radom, Leo School of Chemistry and ARC Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Australia
-
05.10.2012
Published in:
- The Journal of Physical Chemistry. - 2012, vol. 116, no. 41, p. 10203–10208
English
High-level G3X(MP2)-RAD calculations have been carried out to examine the effect of interposing a “connector” group (W) on the interaction between a substituent (X) and the radical center in carbon-centered radicals (•CH₂–W–X). The connector groups include −CH₂–, −CH═CH–, −C≡C–, −p-C₆H₄–, −m-C₆H₄–, and −o-C₆H₄–, and the substituents include H, CF₃, CH₃, CH═O, NH₂, and CH═CH₂. Analysis of the results is facilitated by introducing two new quantities termed radical connector energies and molecule connector energies. We find that the −CH₂– connector effectively turns off π-electron effects but allows the transmission of σ-electron effects, albeit at a reduced level. The effect of a substituent X attached to the −CH═CH– and −C≡C– connector groups is to represent a perturbation of the effect of the connector groups themselves (i.e., CH═CH₂ and C≡CH).
- Faculty
- Faculté des sciences et de médecine
- Department
- Département de Chimie
- Language
-
- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
-
- RERO DOC 30568
- DOI 10.1021/jp3064245
- Persistent URL
- https://folia.unifr.ch/unifr/documents/302590
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