Methyl Substitution Destabilizes Alkyl Radicals.

We have quantum chemically investigated how methyl substituents affect the stability of alkyl radicals Me H C⋅ and the corresponding Me H C-X bonds (X = H, CH , OH; m = 0 - 3) using density functional theory at M06-2X/TZ2P. The state-of-the-art in physical organic chemistry is that alkyl radicals are stabilized upon an increase in their degree of substitution from methyl