title: On the advantages of hydrocarbon radical stabilization energies based on R-H bond dissociation energies.
abstract: Hydrocarbon radical stabilization energy (RSE) estimates based on the differences in R-H vs CH(3)-H bond dissociation energies have inherent advantages over RSEs based on R-CH(3) vs CH(3)-CH(3), as well as R-R vs CH(3)-CH(3) comparisons, since the R-CH(3) and R-R reference systems are prone to unbalanced contaminating intramolecular interactions involving the R groups. When the effects of steric crowding, branching, protobranching, conjugation, and hyperconjugation are taken into account, R-CH(3) and R-R based RSE values are nearly identical to R-H RSEs. Corrections for electronegativity differences between H and R are not needed to achieve agreement.
authors.affiliation: School of Chemistry and Biochemistry, Université de Genève, 30 quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland.
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Wodrich
authors.forename: W Chad
authors.initials: WC
authors.lastname: McKee
authors.forename: Paul von Ragué
authors.initials: Pv
authors.lastname: Schleyer