A new series of hypervalent radicals has been generated by neutralizing a fast beam of NH4(NH3)n+or CH3NH3(NH3)n+ ions in the electron transfer reactions NH4(NH3)n++ K (or Na) → NH4(NH3)n* + K+ (or Na+) (for n = 0–2) and CH3NH3(NH3)n++ K → CH3NH3(NH3)n* + K+ (for n = 0–1). Mass spectra of the reaction products have been obtained by the technique of charge stripping with NO2as collisional ionization gas. New results on the stabilities of CH3NH3, CH3N2H6, N3H10,and their deuterated forms are presented. The effects of internal excitation on the decomposition pathways of the radicals are discussed. These species constitute a novel class of radicals with ionization energies estimated to be in the range 3 to 4.5 eV.