000030568 001__ 30568
000030568 005__ 20131002114017.0
000030568 0248_ $$aoai:doc.rero.ch:20121109083820-MS$$punifr$$ppostprint$$prero_explore$$zcdu34$$zthesis_urn$$zreport$$zthesis$$zbook$$zcdu54$$zjournal$$zcdu16$$zpreprint$$zcdu1$$zdissertation
000030568 041__ $$aeng
000030568 080__ $$a54
000030568 100__ $$aMenon, Ambili S.$$uSchool of Chemistry and ARC Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Australia - Department of Chemistry, University of Fribourg, Switzerland
000030568 245__ $$9eng$$aInfluence of connector groups on the interactions of substituents with carbon-centered radicals
000030568 269__ $$c2012-10-05
000030568 520__ $$9eng$$aHigh-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 (<sup>•</sup>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).
000030568 700__ $$aBally, Thomas$$uDepartment of Chemistry, University of Fribourg, Switzerland
000030568 700__ $$aRadom, Leo$$uSchool of Chemistry and ARC Center of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Australia
000030568 773__ $$g2012/116/41/10203–10208$$tThe Journal of Physical Chemistry
000030568 775__ $$gPublished version$$ohttp://dx.doi.org/10.1021/jp3064245
000030568 8564_ $$fball_icg.pdf$$qapplication/pdf$$s277393$$uhttp://doc.rero.ch/record/30568/files/ball_icg.pdf$$yorder:1$$zpdf
000030568 8564_ $$fball_icg_sm.pdf$$qapplication/pdf$$s154193$$uhttp://doc.rero.ch/record/30568/files/ball_icg_sm.pdf$$yorder:2$$zSupplementary material
000030568 918__ $$aFaculté des sciences$$bDécanat, Ch. du Musée 6A, 1700 Fribourg$$cChimie
000030568 919__ $$aUniversité de Fribourg$$bFribourg$$ddoc.support@rero.ch
000030568 980__ $$aPOSTPRINT$$bUNIFR$$fART_JOURNAL
000030568 990__ $$a20121109083820-MS