EPR Studies of Amine Radical Cations, Part 1: Thermal and Photoinduced Rearrangements of n-Alkylamine Radical Cations to their Distonic Forms in Low-Temperature Freon Matrices

The thermal and photochemical transformations of primary amine radical cations (n‐propyl 1.+, n‐butyl 5.+) generated radiolytically in freon matrices have been investigated by using low‐temperature EPR spectroscopy. Assignment of the spectra was facilitated by parallel studies on the corresponding N,N‐dideuterioamines. The identifications were supported by quantum chemical calculations on the geometry, electronic structure, hyperfine splitting constants and energy levels of the observed transient radical species. The rapid generation of the primary species by a short exposure (1–2 min) to electron‐beam irradiation at 77 K allowed the thermal rearrangement of 1.+ to be monitored kinetically as a first‐order reaction at 125–140 K by the growth in the well‐resolved EPR signal of the distonic radical cation .CH2CH2CH2NH3+. By comparison, the formation of the corresponding .CH2CH2CH2CH2NH3+ species from 5.+ is considerably more facile and already occurs within the short irradiation time. These results directly verify the intramolecular hydrogen‐atom migration from carbon to nitrogen in these ionised amines, a reaction previously proposed to account for the fragmentation patterns observed in the mass spectrometry of these amines. The greater ease of the thermal rearrangement of 5.+ is in accordance with calculations on the barrier heights for these intramolecular 1,5‐ and 1,4‐hydrogen shifts, the lower barrier for the former being associated with minimisation of the ring strain in a six‐membered transition state. For 1.+, the 1,4‐hydrogen shift is also brought about directly at 77 K by exposure to ∼350 nm light, although there is also evidence for the 1,3‐hydrogen shift requiring a higher energy. A more surprising result is the photochemical formation of the H2CN. radical as a minor product under hard‐matrix conditions in which diffusion is minimal. It is suggested that this occurs as a consequence of the β‐fragmentation of 1.+ to the ethyl radical and the CH2NH2+ ion, followed by consecutive cage reactions of deprotonation and hydrogen transfer from the iminonium group. Additionally, secondary ion–molecule reactions were studied in CFCl2CF2Cl under matrix conditions that allow diffusion. The propane‐1‐iminyl radical CH3CH2CHN. was detected at high concentrations of the n‐propylamine substrate. Its formation is attributed to a modified reaction sequence in which 1.+ first undergoes a proton transfer within a cluster of amine molecules to yield the aminyl radi