Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of CuI-thiolate and other CuI complexes

Bruce C. Gilbert; Stephen Silvester; Paul H. Walton

Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of Cu^I-thiolate and other Cu^I complexes

Bruce C. Gilbert^*, Stephen Silvester, Paul H. Walton

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Both free-radical and non-radical routes for peroxide oxidation of Cu^I can be identified for copper complexes obtained by the reduction of Cu^II by thiols, including glutathione. Copper(I)-thiolate complexes are obtained, except in the presence of e.g. 1,10-phenanthroline, and these undergo ready reaction with H₂O₂ and ^tBuOOH. EPR spin-trapping studies establish a free-radical reaction mechanism (to give ^tBuO^•) with the latter, and the formation of HO^• from the former occurs only at low concentrations of copper. Kinetic studies (using UV-vis and EPR spectroscopies), together with NMR analysis, lead to the proposal that Cu^I aggregates react via non-radical pathways in contrast to monomeric Cu^I.

Original language	English
Pages (from-to)	1115-1121
Number of pages	7
Journal	Journal of the Chemical Society. Perkin Transactions 2
Issue number	6
Publication status	Published - 1 Jun 1999

Cite this

@article{9f833817771a4de5ba709af8e45fbc18,

title = "Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of CuI-thiolate and other CuI complexes",

abstract = "Both free-radical and non-radical routes for peroxide oxidation of CuI can be identified for copper complexes obtained by the reduction of CuII by thiols, including glutathione. Copper(I)-thiolate complexes are obtained, except in the presence of e.g. 1,10-phenanthroline, and these undergo ready reaction with H2O2 and tBuOOH. EPR spin-trapping studies establish a free-radical reaction mechanism (to give tBuO•) with the latter, and the formation of HO• from the former occurs only at low concentrations of copper. Kinetic studies (using UV-vis and EPR spectroscopies), together with NMR analysis, lead to the proposal that CuI aggregates react via non-radical pathways in contrast to monomeric CuI.",

author = "Gilbert, {Bruce C.} and Stephen Silvester and Walton, {Paul H.}",

year = "1999",

month = jun,

day = "1",

language = "English",

pages = "1115--1121",

journal = "Journal of the Chemical Society. Perkin Transactions 2",

issn = "0300-9580",

publisher = "Chemical Society",

number = "6",

}

Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of Cu^I-thiolate and other Cu^I complexes. / Gilbert, Bruce C.; Silvester, Stephen; Walton, Paul H.
In: Journal of the Chemical Society. Perkin Transactions 2, No. 6, 01.06.1999, p. 1115-1121.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of CuI-thiolate and other CuI complexes

AU - Gilbert, Bruce C.

AU - Silvester, Stephen

AU - Walton, Paul H.

PY - 1999/6/1

Y1 - 1999/6/1

N2 - Both free-radical and non-radical routes for peroxide oxidation of CuI can be identified for copper complexes obtained by the reduction of CuII by thiols, including glutathione. Copper(I)-thiolate complexes are obtained, except in the presence of e.g. 1,10-phenanthroline, and these undergo ready reaction with H2O2 and tBuOOH. EPR spin-trapping studies establish a free-radical reaction mechanism (to give tBuO•) with the latter, and the formation of HO• from the former occurs only at low concentrations of copper. Kinetic studies (using UV-vis and EPR spectroscopies), together with NMR analysis, lead to the proposal that CuI aggregates react via non-radical pathways in contrast to monomeric CuI.

AB - Both free-radical and non-radical routes for peroxide oxidation of CuI can be identified for copper complexes obtained by the reduction of CuII by thiols, including glutathione. Copper(I)-thiolate complexes are obtained, except in the presence of e.g. 1,10-phenanthroline, and these undergo ready reaction with H2O2 and tBuOOH. EPR spin-trapping studies establish a free-radical reaction mechanism (to give tBuO•) with the latter, and the formation of HO• from the former occurs only at low concentrations of copper. Kinetic studies (using UV-vis and EPR spectroscopies), together with NMR analysis, lead to the proposal that CuI aggregates react via non-radical pathways in contrast to monomeric CuI.

UR - http://www.scopus.com/inward/record.url?scp=0000554394&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000554394

SN - 0300-9580

SP - 1115

EP - 1121

JO - Journal of the Chemical Society. Perkin Transactions 2

JF - Journal of the Chemical Society. Perkin Transactions 2

IS - 6

ER -

Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of CuI-thiolate and other CuI complexes

Abstract

Other files and links

Cite this

Spectroscopic, kinetic and mechanistic studies of the influence of ligand and substrate concentration on the activation by peroxides of Cu^I-thiolate and other Cu^I complexes