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Paper
Dalton Trans., 2009, 9828 - 9836, DOI: 10.1039/b916047g
Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties
Pavel Afanasiev, Denis Bouchu, Evgeny V. Kudrik, Jean-Marc M. Millet and Alexander B. Sorokin
Oxidation of N-bridged diiron tetra-tert-butylphthalocyanine (FePctBu)2N with tBuOOH in halogenated solvents afforded
-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) 
. The distance between two equivalent hexacoordinated in-plane iron (IV) centers is 3.39(1) . Fe–X bond lengths are 2.33 and 2.54 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.
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