Cu(III)–bis-thiolato complex forms an unusual mono-thiolato Cu(III)–peroxido adduct

Jane M. Donnelly; Frederik Lermyte; Juliusz A. Wolny; Marc Walker; Ben G. Breeze; Russell J. Needham; Christina S. Müller; Peter B. O’Connor; Volker Schünemann; Joanna F. Collingwood; Peter J. Sadler

doi:10.1039/D0CC06921C

Cu(iii)–bis-thiolato complex forms an unusual mono-thiolato Cu(iii)–peroxido adduct†

Jane M. Donnelly,

^a Frederik Lermyte,

^b Juliusz A. Wolny,

^c Marc Walker,

^d Ben G. Breeze,

^d Russell J. Needham,

^e Christina S. Müller,

^c Peter B. O’Connor,

^e Volker Schünemann,

^c Joanna F. Collingwood

^a and Peter J. Sadler

*^e

Author affiliations

* Corresponding authors

^a School of Engineering, University of Warwick, Gibbet Hill Road, Coventry CV4 7Al, UK

^b Department of Chemistry, Technical University of Darmstadt, Alarich-Weiss-Strasse 4, 64287 Darmstadt, Germany

^c Department of Physics, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße 46, 67663 Kaiserslautern, Germany

^d Department of Physics, University of Warwick, Gibbet Hill Road, Coventry CV4 7Al, UK

^e Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK
E-mail: P.J.Sadler@warwick.ac.uk

Abstract

The stable complex [bis(toluene-3,4-dithiolato)copper(III)][NEt₃H] has been synthesised and characterised as a square-planar Cu(III) complex by X-ray photoelectron spectroscopy, cyclic voltammetry and DFT calculations. Intriguingly, when fragmented in FTICR-MS, an unusual [(toluene-3,4-dithiolate)Cu(III)(peroxide)]⁻ complex is formed by reaction with oxygen. Natural 1,2-dithiolenes known to bind molybdenum might stabilise Cu(III) in vivo.

Chemical Communications

Cu(iii)–bis-thiolato complex forms an unusual mono-thiolato Cu(iii)–peroxido adduct†

Abstract

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Cu(III)–bis-thiolato complex forms an unusual mono-thiolato Cu(III)–peroxido adduct

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