Demonstration of tunable reactivity for meta-benzynes

John J Nash; Katrina E Nizzi; Anthony Adeuya; Michael J Yurkovich; Christopher J Cramer; Hilkka I Kenttämaa

doi:10.1021/ja0449473

Demonstration of tunable reactivity for meta-benzynes

J Am Chem Soc. 2005 Apr 27;127(16):5760-1. doi: 10.1021/ja0449473.

Authors

John J Nash¹, Katrina E Nizzi, Anthony Adeuya, Michael J Yurkovich, Christopher J Cramer, Hilkka I Kenttämaa

Affiliation

¹ Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA. jnash@purdue.edu

PMID: 15839653
DOI: 10.1021/ja0449473

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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Benzene Derivatives / chemistry*
Drug Design
Free Radicals / chemistry
Thermodynamics

Substances

Benzene Derivatives
Free Radicals