Campus Units

Chemistry

Document Type

Book Chapter

Publication Version

Published Version

Publication Date

7-23-2009

Journal or Book Title

Structure and Reactivity in Aqueous Solution

Volume

568

Issue

ACS Symposium Series

First Page

182

Last Page

195

DOI

10.1021/bk-1994-0568.ch013

Abstract

The nonradiative pathways of 7-azaindole are extremely sensitive to solvent. In alcohols, 7-azaindole executes an excited-state double-proton transfer. In water, this tautomerization is frustrated. Proton inventory experiments suggest a concerted double-proton transfer in the alcohols and point to another nonradiative process in water. We propose the following idealized picture. Whereas at room temperature 7-azaindole can form a cyclic hydrogen-bonded intermediate with a single alcohol molecule facilitating tautomerization, in water more than one solvent molecule coordinates to the solute and thus prohibits the concerted process. More detailed measurements, however, indicate that water and alcohols do not solvate 7-azaindole in fundamentally different ways, but rather that they represent two extremes of the same phenomenon.

Comments

Reprinted (adapted) with permission from Structure and Reactivity in Aqueous Solution, ACS Symposium Series, Vol. 568, Chapter 13 (1994): 182, doi: 10.1021/bk-1994-0568.ch013. Copyright 1994 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

Share

COinS