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Communication

Demonstration of Tunable Reactivity for meta-Benzynes

John J. Nash,*^† Katrina E. Nizzi,^† Anthony Adeuya,^† Michael J. Yurkovich,^† Christopher J. Cramer,*^‡ and Hilkka I. Kenttämaa*^†; ;

Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, and the Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455

J. Am. Chem. Soc., 2005, 127 (16), pp 5760–5761

DOI: 10.1021/ja0449473

Publication Date (Web): March 29, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

Purdue University.

‡

University of Minnesota.

, jnash@purdue.edu, ; , hilkka@purdue.edu, ; , cramer@chem.umn.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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