Issue 33, 2010
From the journal:

Dalton Transactions

Reinvestigation of the formation of a mononuclear Fe(iii) hydroperoxido complex using high pressure kinetics†‡

Thomas Nebe,a   Alexander Beitat,a   Christian Würtele,a   Carlos Dücker-Benfer,b   Rudi van Eldik,b   Christine J. McKenziec  and  Siegfried Schindler*a  

* Corresponding authors

a Institute for Inorganic and Analytical Chemistry, University of Gießen, Heinrich-Buff-Ring 58, Gießen, Germany
E-mail: siegfried.schindler@chemie.uni-giessen.de
Fax: +49.641.9934149

b Inorganic Chemistry, Department of Chemistry and Pharmacy, University of Erlangen-Nürnberg, Egerlandstraße1, Erlangen, Germany
E-mail: rudi.vaneldik@chemie.uni-erlangen.de
Fax: +49.9131.8527387

c Department of Physics and Chemistry, University of Southern Denmark, Campusvej 55, 5230 Odense M
E-mail: chk@ifk.sdu.dk
Fax: +45.6615.8780

Abstract

Previous stopped flow kinetic experiments suggested an interchange associative mechanism for the ligand substitution reaction, [Fe(bztpen)(OMe)]2+ + H2O2→ {[Fe(bztpen)(OMe)(HOOH)]2+}‡→ [Fe(bztpen)(OOH)]2+ + MeOH (bztpen = N-benzyl-N, N',N'tris(2-methylpyridyl)-ethylenediamine). Thus a seven-coordinate transition state containing both the leaving methoxide and the incoming hydrogen peroxide ligands was proposed. On the basis of high pressure kinetic data we can now conclude that this is not the case since the rate of the reaction is independent of pressure for the formation of the purple low spin transient hydroperoxido complex, [Fe(bztpen)(OOH)]2+. [Fe(bztpen)(OOH)]2+ has so far proved to be too short-lived for solid state isolation. As part of our ongoing pursuit of this elusive species we have structurally characterised the nitrosyl and acetate iron(II) complexes, [Fe(bztpen)(NO)](OTf)2 and [Fe(bztpen)(OAc)](BPh4), as well as the air stable Co(II) complexes [Co(bztpen)Cl)]BF4, [Co(metpen)Cl]SbF6 and [Co(bztpen)(OAc)]BPh4. We did not realise our aim of accessing stable Co(III) hydroperoxido or peroxido complexes by reaction of the cobalt complexes with H2O2.

Graphical abstract: Reinvestigation of the formation of a mononuclear Fe(iii) hydroperoxido complex using high pressure kinetics

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Article information

DOI
https://doi.org/10.1039/C0DT00247J
Article type
Paper
Submitted
01 Apr 2010
Accepted
26 May 2010
First published
21 Jul 2010

Dalton Trans., 2010,39, 7768-7773

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Reinvestigation of the formation of a mononuclear Fe(III) hydroperoxido complex using high pressure kinetics

T. Nebe, A. Beitat, C. Würtele, C. Dücker-Benfer, R. van Eldik, C. J. McKenzie and S. Schindler, Dalton Trans., 2010, 39, 7768 DOI: 10.1039/C0DT00247J

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