Issue 6, 2005

Kinetics and mechanism of the Co(ii)-assisted oxidation of thioureas by dioxygen

Abstract

Catalytic oxidation of N,N′-dimethylthiourea and thiourea by dioxygen in water using a new cobalt(II) complex of octasulfophenyltetrapyrazinoporphyrazine was performed under mild conditions. The reaction is shown to include the formation of an intermediate anionic five-coordinate complex followed by an unusual two-electron oxidation to produce the corresponding urea and elemental sulfur (S8). Kinetic and thermodynamic parameters for the different reaction steps of the process were determined. Drastic differences in catalytic activity of cobalt and iron octasulfophenyltetrapyrazinoporphyrazines were observed.

Graphical abstract: Kinetics and mechanism of the Co(ii)-assisted oxidation of thioureas by dioxygen

Supplementary files

Article information

Article type
Paper
Submitted
24 Nov 2004
Accepted
27 Jan 2005
First published
14 Feb 2005

Dalton Trans., 2005, 1117-1122

Kinetics and mechanism of the Co(II)-assisted oxidation of thioureas by dioxygen

E. V. Kudrik, A. Theodoridis, R. van Eldik and S. V. Makarov, Dalton Trans., 2005, 1117 DOI: 10.1039/B417775D

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