Methyl Substitution Destabilizes Alkyl Radicals.

We have quantum chemically investigated how methyl substituents affect the stability of alkyl radicals Me m H 3-m C⋅ and the corresponding Me m H 3-m C-X bonds (X = H, CH 3 , 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<primary<secondary<tertiary, and that this is the underlying cause for the decrease in C-H bond strength along this series. Here, we provide evidence that falsifies this model and show that, on the contrary, the Me m H 3-m C⋅ radical is destabilized with increasing substitution. The reason that the corresponding C-H bond nevertheless becomes weaker is that substitution destabilizes the sterically more congested Me m H 3-m C-H molecule even more.