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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Nebe, Thomas Würtele, Christian Mckenzie, Christine J. Beitat, Alexander Dücker-benfer, Carlos Schindler, Siegfried Van Eldik, Rudi
Description	Author Affiliation: Nebe T ( Institute for Inorganic and Analytical Chemistry, University of Giessen, Heinrich-Buff-Ring 58, 35392, Giessen, Germany.)
Abstract	Previous stopped flow kinetic experiments suggested an interchange associative mechanism for the ligand substitution reaction , [Fe(bztpen)(OMe)] $^{2+}$ + $H_{2}O_{2}→$ $\{[Fe(bztpen)(OMe)(HOOH)]^{2+}\}^{‡}→$ $[Fe(bztpen)(OOH)]^{2+}$ + 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)](BPh $_{4})$ , as well as the air stable Co( II) complexes $[Co(bztpen)Cl)]BF_{4},$ $[Co(metpen)Cl]SbF_{6}$ and [Co(bztpen)(OAc)]BPh $_{4}$ . We did not realise our aim of accessing stable Co( III) hydroperoxido or peroxido complexes by reaction of the cobalt complexes with $H_{2}O_{2}.$
ISSN	14779226
Issue Number	33
Volume Number	39
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2010-09-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Ferric Compounds Cobalt Crystallography, X-Ray Ferrous Compounds Hydrogen Peroxide Iron Kinetics Ligands Models, Molecular Molecular Structure Nitric Oxide Oxygen Pressure Journal Article Research Support, Non-U.S. Gov't Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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