Abstract
The thermal unimolecular decomposition of 2‐phenylethylamine (PhCH2CH2NH2) into benzyl and aminomethyl radicals has been studied under very‐low‐pressure conditions, and the enthalpy of formation of the aminomethyl radicals, ΔH°f, 298K (H2NCH2·) = 37.0 ± 2.0 kcal/mol, has been derived from the kinetic data. This result leads to a value for the C—H bond dissociation energy in methylamine, BDE(H2NCH2—H) = 94.6 ± 2.0 kcal/mol, which is about 3.4 kcal/mol lower than in C2H6 (98 kcal/mol), indicating a sizable stabilization in α‐aminoalkyl radicals.