Prev. Article Next Article Table of Contents

Article

Copper(III) Pyrophosphate Complexes in Aqueous Solution. A Pulse Radiolysis Study at Ambient and High Pressure

Figures
Citing Articles

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

Purchase the full-text

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

Diane E. Cabelli,*^† James F. Wishart,^† Jerzy Holcman,^‡ Martin Meier,^§ and Rudi van Eldik*^§

Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973, Chemistry Department, Risø National Laboratory, DK 4000 Roskilde, Denmark, and Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany

J. Phys. Chem. A, 1997, 101 (28), pp 5131–5136

DOI: 10.1021/jp970002e

Publication Date (Web): July 10, 1997

Abstract

The reaction between OH radicals and [Cu^II(P₂O₇)₂(H₂O)₂]^6- results in the formation of a Cu(III) complex. No reaction is observed with N₃^• or Br₂^•-, whereas SO₄^•- initiates the same steps as seen with ^•OH. This suggests that the mechanism probably involves a ligand interchange or H^• atom abstraction process. The Cu(III) complex undergoes a rapid first-order reaction, probably loss of a P₂O₇^4- chelate, followed by addition of OH^- (pK_OH ≈ 10) to yield a Cu(III) complex that is predominantly hydroxylated and has a relatively long half life. The effect of pressure (up to 150 MPa) on the formation and subsequent reactions of the Cu(III) complex is used to help elucidate the mechanism of the different steps.

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

Citing Articles

View all 4 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).

High-Pressure Pulse Radiolysis as a Tool in the Study of Transition Metal Reaction Mechanisms
Rudi van Eldik and Dan Meyerstein
Accounts of Chemical Research2000 33 (4), 207-214
- High-Pressure Pulse Radiolysis as a Tool in the Study of Transition Metal Reaction Mechanisms
  Rudi van Eldik and Dan Meyerstein
  Accounts of Chemical Research2000 33 (4), 207-214
  The unique combination of high-pressure and pulse radiolysis kinetic techniques enables detailed mechanistic insight for a large variety of chemical processes to be gained. Typical examples for transition metal reactions are presented. These include ...
  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 July 10, 1997
Received December 17, 1996
Revised April 29, 1997

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

Article

Copper(III) Pyrophosphate Complexes in Aqueous Solution. A Pulse Radiolysis Study at Ambient and High Pressure

Abstract

Citing Articles

High-Pressure Pulse Radiolysis as a Tool in the Study of Transition Metal Reaction Mechanisms