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Demonstration of tunable reactivity for meta-benzynes
John J Nash1, Katrina E Nizzi, Anthony Adeuya
1Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA. jnash@purdue.edu
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.
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