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Issue 44, 2009
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Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties

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Abstract

Oxidation of N-bridged diiron tetra-tert-butylphthalocyanine (FePctBu)2N with tBuOOH in halogenated solvents afforded μ-nitrido diiron (IV) phthalocyanine cation radical complexes, (X)PcFeIV–N–FeIVPc+˙(X) (X = Cl, Br), as evidenced by UV-vis, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry (ESI-MS), Mössbauer, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data. Continuous introduction ESI-MS showed the initial formation of the t-butylperoxo diiron complex tBuOO-(FePctBu)2N followed by intermediate formation of a monohalogenated adduct which gave the dihalogenated complex as final stable product. Fe K-edge EXAFS analysis of (X)PcFeIV–N–FeIVPc+˙(X) showed bridging N atom at a distance of 1.69(1) Å. The distance between two equivalent hexacoordinated in-plane iron (IV) centers is 3.39(1) Å. Fe–X bond lengths are 2.33 and 2.54 Å for X = Cl and Br, respectively. The use of (Cl)PcFeIV–N–FeIVPc+˙(Cl) for the catalytic oxidation of organic substrates has been shown for the first time.

Graphical abstract: Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties

  • This article is part of the themed collection: FIGIPAS 2009
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Article information


Submitted
05 Aug 2009
Accepted
16 Sep 2009
First published
07 Oct 2009

Dalton Trans., 2009, 9828-9836
Article type
Paper

Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties

P. Afanasiev, D. Bouchu, E. V. Kudrik, J. M. Millet and A. B. Sorokin, Dalton Trans., 2009, 9828
DOI: 10.1039/B916047G

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