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Demonstration of Tunable Reactivity for meta-Benzynes

Nash, J. J.; Nizzi, K. E.; Adeuya, A.; Yurkovich, M. J.; Cramer, C. J.; Kenttämaa; H. I.
J. Am. Chem. Soc. in press. 2005, 127, 5760.

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 changes in the potential energy surfaces for the dehydrocarbon separation.

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