Shortcomings of basing radical stabilization energies on bond dissociation energies of alkyl groups to hydrogen.
Stabilization energies (SE(H)) of carbon radicals (R(*)) are traditionally defined as the difference between the bond dissociation energy (BDE) of CH(3)-H, as a reference point, and of R-H. The term "stabilization energy" implies that it is an intrinsic property of the radical and a quantitative measure of stability. Applicable only to carbon-centered radicals, SE(H) stabilization energies are not transferable and cannot be used to estimate carbon-carbon BDE[R-R'], symmetrical BDE[R-R], or any other BDE[R-X]. SE(H) values by themselves are neither an intrinsic property nor a quantitative measure of stability. There is available an alternative that is not limited only to carbon-carbon and carbon-hydrogen bonds, does not depend on any one particular molecule or BDE as a reference point, and is accurate with several hundred different types of bonds.
Zavitsas
Andreas A
AA
Department of Chemistry and Biochemistry, Long Island University, University Plaza, Brooklyn, New York 11201, USA. zavitsas@liu.edu
Rogers
Donald W
DW
Matsunaga
Nikita
N
D000473:Alkanes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D013816:Thermodynamics
D000473:Alkanes; D000475:Alkenes; D005609:Free Radicals; D002244:Carbon; D006859:Hydrogen