title: Homolytic cleavages in pyridinium ions, an excited state process.
abstract: The favored fragmentation pathway for protonated and alkylated pyridinium cations of the general formula p-XC(6)H(4)CH(2)CH(2)CH=CH Py(+)R (R=H, Me; Py=pyridine) is a C-C homolytic cleavage. The tendency to form radicals is higher for alkylated pyridinium cations than for the protonated ones that can also afford closed-shell products. Theoretical calculations show that the singlet-triplet gap for transient structures with an elongated benzylic C-C bond is very low and the formation of radicals may result from mixing of these states. In addition to the notable substituent effect on the fragmentation efficiency of the cations under study, calculated results show a clear substituent effect on the singlet-triplet transitions. We also observe that triphenylphosphonium cations behave notably different. Thus, the pyridinium system that contains a p-chloro benzyl moiety loses a benzyl radical readily while the analogous triphenylphosphonium cation is very stable under the same conditions.
authors.affiliation: Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Haifa, Israel. chchagit@tx.technion.ac.il
authors.forename: Chagit
authors.initials: C
authors.lastname: Denekamp
authors.forename: Elena
authors.initials: E
authors.lastname: Tenetov
authors.forename: Yonit
authors.initials: Y
authors.lastname: Horev