title: Generation and reactivity toward oxygen of carbon-centered radicals containing indane, indene, and fluorenyl moieties.
abstract: Resonance-stabilized radicals containing indane, indene, and fluorenyl moieties exhibit attenuated reactivity toward oxygen. Rate constants of approximately 10(5) M(-1) s(-1) were observed for the most stabilized radicals. The dependence of k(OX) (rate constant for radical trapping by oxygen) on the corresponding bond dissociation energies revealed that stereoelectronic effects are more important than steric effects in determining the low radical reactivity with oxygen. Scavenging by the nitroxide TEMPO was also examined, and revealed that in this case steric effects are more important than in the case of oxygen. The rate constants for the hydrogen abstraction by cumyloxyl and tert-butoxyl radicals generated thermally and photochemically have been determined in benzene, and were in the range of ca. (1-13) x 10(6) M(-1) s(-1), showing that benzylic stabilization has a modest effect on substrate reactivity as a hydrogen donor toward alkoxyl radicals.
authors.affiliation: Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5.
authors.forename: Enrique
authors.initials: E
authors.lastname: Font-Sanchis
authors.forename: Carolina
authors.initials: C
authors.lastname: Aliaga
authors.forename: Elena V
authors.initials: EV
authors.lastname: Bejan
authors.forename: Raecca
authors.initials: R
authors.lastname: Cornejo
authors.forename: J C
authors.initials: JC
authors.lastname: Scaiano