Demonstration of tunable reactivity for meta-benzynes.
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.
Nash
John J
JJ
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA. jnash@purdue.edu
Nizzi
Katrina E
KE
Adeuya
Anthony
A
Yurkovich
Michael J
MJ
Cramer
Christopher J
CJ
Kenttämaa
Hilkka I
HI
D001555:Benzene Derivatives / Q000737:chemistry*; D015195:Drug Design; D005609:Free Radicals / Q000737:chemistry; D013816:Thermodynamics
D001555:Benzene Derivatives; D005609:Free Radicals