title: Demonstration of tunable reactivity for meta-benzynes.
abstract: A combined computational and experimental study on the gas-phase structures and reactivities of charged 1,3-didehydroarenes (meta-benzynes) demonstrates that the reactivity of such biradicals can be "tuned" by using appropriate substituents. Substituents that destabilize a specific zwitterionic resonance structure can change the reactivity of the biradical from mildly carbocationic to radical-like. These substituent effects are not the result of changes in the singlet-triplet gaps of the biradicals, but rather reflect changes in the potential energy surfaces for the dehydrocarbon separation.
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA. jnash@purdue.edu
authors.forename: John J
authors.initials: JJ
authors.lastname: Nash
authors.forename: Katrina E
authors.initials: KE
authors.lastname: Nizzi
authors.forename: Anthony
authors.initials: A
authors.lastname: Adeuya
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Yurkovich
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
authors.forename: Hilkka I
authors.initials: HI
authors.lastname: Kenttämaa
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D015195:Drug Design; D005609:Free Radicals / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D001555:Benzene Derivatives; D005609:Free Radicals