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Relative Reactivities of Three Isomeric Aromatic Biradicals with a 1,4‐Biradical Topology Are Controlled by Polar Effects
Author(s) -
Ma Xin,
Jin Chunfen,
Wang Duanda,
Nash John J.,
Kenttämaa Hilkka I.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806106
Subject(s) - chemistry , dissociation (chemistry) , hydrogen atom abstraction , reactivity (psychology) , singlet state , photochemistry , protonation , iodide , radical ion , hydrogen atom , medicinal chemistry , ion , computational chemistry , radical , stereochemistry , inorganic chemistry , organic chemistry , group (periodic table) , medicine , physics , alternative medicine , pathology , nuclear physics , excited state
Unexpectedly, the 5‐dehydroquinoline radical cation was formed in the gas phase from the 5‐iodo‐8‐nitroquinolinium cation upon ion‐trap collision‐activated dissociation. This reaction involves the cleavage of a nitro group to generate an intermediate monoradical, namely, the 8‐dehydro‐5‐iodoquinolinium cation, followed by rearrangement through abstraction of a hydrogen atom from the protonated nitrogen atom by the radical site. Dissociation of the rearranged radical cation through elimination of an iodine atom generates the 5‐dehydroquinoline radical cation. The mechanism was probed by studying isomeric biradicals and performing quantum chemical calculations. The 5‐dehydroquinoline radical cation showed greater gas‐phase reactivity toward dimethyl disulfide, cyclohexane, and allyl iodide than the isomeric 5,8‐didehydroquinolinium cation, which is more reactive than the isomeric 5,8‐didehydroisoquinolinium cation studied previously. All three isomers have a 1,4‐biradical topology. The order of reactivity is rationalized by the vertical electron affinities of the radical sites of these biradicals instead of their widely differing singlet–triplet splittings.