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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
Department of Chemistry, University of Fribourg, Switzerland
School of Chemistry and ARC Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Australia
- The Journal of Physical Chemistry. - 2012, vol. 116, no. 41, p. 10203–10208
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).
- Faculté des sciences et de médecine
- Département de Chimie
- ball_icg.pdf: 24
- ball_icg_sm.pdf: 11