Electron-gain and electron-loss centres derived from chloro amines

Abstract

Exposure of dilute solutions of various dialkyl and cyclic N-chloro amines in trichlorofluoromethane to ⁶⁰Co γ-rays at 77K gave the corresponding cations, R₂ṄCl⁺, characterised by ¹⁴N, ³⁵Cl, and ¹H hyperfine coupling. The results suggest that these radicals are essentially planar at nitrogen, the SOMO being the N–Cl π* orbital. Similar treatment of dilute solutions in methanol or methyltetrahydrofuran gave the corresponding amino radicals, R₂N˙, also characterised by their e.s.r. spectra. There was no evidence for the formation of the parent radical anions. These results are contrasted with those for N-halogeno imides and with the formation of σ* radicals from the cations R₃N˙⁺ and halide ions.