Menon, Ambili S. Bally, Thomas Radom, Leo 2012-10-05 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–, −<i>p-</i>C₆H₄–, −<i>m-</i>C₆H₄–, and −<i>o-</i>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). application/pdf https://folia.unifr.ch/global/documents/302590 https://folia.unifr.ch/documents/302590/files/ball_icg.pdf https://folia.unifr.ch/documents/302590/files/ball_icg_sm.pdf eng info:eu-repo/semantics/altIdentifier/doi/10.1021/jp3064245 info:eu-repo/semantics/openAccess License undefined The Journal of Physical Chemistry. - 2012, vol. 116, no. 41, p. 10203–10208 info:eu-repo/classification/udc/54 Influence of connector groups on the interactions of substituents with carbon-centered radicals http://purl.org/coar/resource_type/c_6501