Prev. Article Next Article Table of Contents

Article

Rate and Driving Force for Protonation of Aryl Radical Anions in Ethanol^†

Your current credentials do not allow retrieval of the full text.

Purchase the full-text

PDF/HTML,
figures/images,
references and tables,
(where available)

Alison M. Funston, Sergei V. Lymar, Barbara Saunders-Price, Gidon Czapski, and John R. Miller*

Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973

J. Phys. Chem. B, 2007, 111 (24), pp 6895–6902

DOI: 10.1021/jp071450h

Publication Date (Web): May 25, 2007

Section:

Physical Organic Chemistry

Abstract

Aryl radical anions created in liquid alcohols decay on the microsecond time scale by transfer of protons from the solvent.^1,2 This paper reports a 4.5 decade range of rate constants for proton transfer from a single weak acid, ethanol, to a series of unsubstituted aryl radical anions, Ar^-•. The rate constants correlate with free energy change, ΔG°, despite wide variations in the two factors that contribute to ΔG°: (a) the reduction potentials of the aryls and (b) the Ar−H^• bond strengths in the product radicals. For aryl radical anions containing CH₂OH substituents, such as 2,2‘-biphenyldimethanol^•- which is protonated with a rate constant of 3 × 10⁹ s^-1, the faster rates do not fit well in the free energy correlation, suggesting a change in mechanism.

View: Full Text HTML | Hi-Res PDF | PDF w/ Links

Citing Articles

View all 3 citing articles

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

This article has been cited by 1 ACS Journal articles (1 most recent appear below).

Electrochemical and Chemical Reduction of Disulfur Dinitride: Formation of [S₄N₄]^−•, EPR Spectroscopic Characterization of the [S₂N₂H]^• Radical, and X-ray Structure of [Na(15-crown-5)][S₃N₃]
Tracey L. Roemmele, Jari Konu, René T. Boeré and Tristram Chivers
Inorganic Chemistry2009 48 (19), 9454-9462
- Electrochemical and Chemical Reduction of Disulfur Dinitride: Formation of [S₄N₄]^−•, EPR Spectroscopic Characterization of the [S₂N₂H]^• Radical, and X-ray Structure of [Na(15-crown-5)][S₃N₃]
  Tracey L. Roemmele, Jari Konu, René T. Boeré and Tristram Chivers
  Inorganic Chemistry2009 48 (19), 9454-9462
  Voltammetric studies of S2N2 employing both cyclic voltammetry (CV) and rotating disk electrode (RDE) methods on GC electrodes at room temperature (RT) revealed two irreversible reduction processes at about −1.4 V and −2.2 V in CH3CN, CH2Cl2, and ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

Tools

SciFinder Links

Explore by:

Author of this Article Any Author Research Topic

History

Published In Issue June 21, 2007
Received February 20, 2007
Revised March 30, 2007

Select a CAS section from the 5 main topical divisions below:

Article

Rate and Driving Force for Protonation of Aryl Radical Anions in Ethanol^†

Abstract

Citing Articles

Electrochemical and Chemical Reduction of Disulfur Dinitride: Formation of [S₄N₄]^−•, EPR Spectroscopic Characterization of the [S₂N₂H]^• Radical, and X-ray Structure of [Na(15-crown-5)][S₃N₃]