Premium
Effects of a Hydroxyl Substituent on the Reactivity of the 2,4,6‐Tridehydropyridinium Cation, an Aromatic σ,σ,σ‐Triradical
Author(s) -
Jankiewicz Bartłomiej J.,
Vinueza Nelson R.,
Reece Jennifer N.,
Lee Young C.,
Williams Peggy,
Nash John J.,
Kenttämaa Hilkka I.
Publication year - 2012
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.201102641
Subject(s) - reactivity (psychology) , chemistry , iodide , substituent , tetrahydrofuran , medicinal chemistry , dimethyl disulfide , photochemistry , stereochemistry , organic chemistry , sulfur , medicine , alternative medicine , pathology , solvent
The reactivity of 3‐hydroxy‐2,4,6‐tridehydropyridinium cation was found to be drastically different from the reactivity of 2,4,6‐tridehydropyridinium cation. While the latter triradical reacts with tetrahydrofuran, dimethyl disulfide and ally iodide via three consecutive atom or group abstractions, the former triradical exhibits this behavior only with tetrahydrofuran. Only a single atom or group abstraction was observed for the 3‐hydroxy‐2,4,6‐tridehydropyridinium cation upon interaction with dimethyl disulfide and allyl iodide. This change in reactivity is caused by the hydroxyl group that strengthens the interactions between the two radical sites adjacent to it, thus reducing their reactivity. This explanation is supported by the observation of similar behavior for related biradicals.