Influence of connector groups on the interactions of substituents with carbon-centered radicals

Menon, Ambili S.; Bally, Thomas; Radom, Leo

doi:10.1021/jp3064245

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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
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

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