Decomposition pathways leading to HONO for nitroalkenes

Abstract The reaction profiles for the dissociation of HONO from 1-nitro-2-methyl-1-propene have been examined for two distinct reaction pathways: a. The unimolecular dissociation of HONO from the intermediate CH2=C(CH3)CH=NOOH which in turn is formed by a unimolecular transfer of a hydrogen atom from the methyl group located cis to the nitro group in the parent molecule. b. The unimolecular dissociation of HONO from the intermediate formed by a bimolecular transfer of a hydrogen atom between two parent molecules. The overall activation enthalpies for the two processes are 62 and 50 kcal mol−1 respectively. The electronic nature of the transition states involved are discussed.