Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

3-2003

Journal or Book Title

Journal of the American Chemical Society

Volume

125

Issue

15

First Page

4643

Last Page

4651

DOI

10.1021/ja029571c

Abstract

We have regiospecifically generated the α,2-, α,3-, and α,4-dehydrophenoxide anions by collisional activation of o-, m-, and p-nitrobenzoate. The α,2 and α,4 isomers also were synthesized by reacting o-benzyne radical anion with carbon dioxide and electron ionization ofp-diazophenol. All three dehydrophenol radical anions were differentiated from each other and identified by probing their chemical reactivity with several reagents. Each isomer was converted to phenoxide and its corresponding quinone as well. Thermochemical measurements were carried out on all three radical anions and their hydrogen-atom affinities, proton affinities, and electron binding energies are reported. These measured quantities are combined in thermodynamic cycles to derive the heats of formation of each of the radical anions and their corresponding carbenes (i.e., α,2-, α,3-, and α,4-dehydrophenol). These results are compared to MCQDPT2, G3, G2+(MP2), and B3LYP calculations and experimental data for appropriate reference compounds.

Comments

Reprinted (adapted) with permission from Journal of the American Chemical Society 125 (2003): 4643, doi:10.1021/ja029571c. Copyright 2003 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

Share

COinS