Issue 1, 2011

Structure–reactivity relationships and substituent effect additivity in the aqueous oxidation of chlorophenols by cerium(iv)

Abstract

The oxidation of all 19 chlorophenols and unsubstituted phenol by cerium(IV) was studied in an acidic aqueous solution in order to carry out a systematic test of chlorine substituent effects on the reactivity. All reactions were found to show 2 ∶ 1 cerium(IV)  ∶ phenol stoichiometry and a simple second-order rate equation. Rate constants did not correlate well with characteristic parameters such as pK values, carbon-13 NMR chemical shifts or Hammett substituent constants. Nevertheless, a strict additivity of chlorine substituent effects was found in both characteristic and reactivity parameters. The data suggest that a proton-coupled electron transfer mechanism could be operative. 2,4,6-Trichlorophenol was found to show exceptionally high reactivity towards cerium(IV).

Graphical abstract: Structure–reactivity relationships and substituent effect additivity in the aqueous oxidation of chlorophenols by cerium(iv)

Supplementary files

Article information

Article type
Paper
Submitted
06 Jul 2010
Accepted
01 Oct 2010
First published
25 Oct 2010

New J. Chem., 2011,35, 235-241

Structure–reactivity relationships and substituent effect additivity in the aqueous oxidation of chlorophenols by cerium(IV)

A. Simon, C. Ballai, G. Lente and I. Fábián, New J. Chem., 2011, 35, 235 DOI: 10.1039/C0NJ00529K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements