Allyl type radical formation in X-irradiated glutarimide crystals studied by ENDOR and ENDOR-induced EPR

Glutarimide single crystals X-irradiated at room temperature were reinvestigated at 150 K with the purpose to obtain information about possible ring opening and other fragmentation processes involving free radicals in this compound, previously only observed to take place in aqueous solutions. In previous work, using EPR,ENDOR and EIE spectroscopy, two H-abstraction radicals present in a 3∶1 relative ratio in the irradiated crystals were identified. In the present work the detection of a third radical species, III, is reported. The g- and hyperfine coupling tensors for all three radicals at 150 K were obtained. Based on simulations of the EPR spectra the relative abundance of the three radicals was estimated to be 60, 25 and 15% for radicals I, II and III, respectively. Radical III is proposed to be of the allyl radical type –CHCH–˙CH– formed formally by a concerted H2 elimination from C2 and C3 of radical I and/or from C3 and C4 of radical II. This proposal and structure is at variance with observations from aqueous solution studies of succinimide, where the CO–CH2 bond was susceptible for rupture. However, the assignment is consistent with density functional theory (DFT) calculations, predicting equivalent hyperfine interactions to the two α-type protons at C2 and C4 in excellent agreement with the experimentally determined hyperfine coupling tensors. EIE results confirmed that both couplings originate from the same radical species. Possible mechanisms for the formation of radical III are discussed.