Issue 36, 2009
From the journal:

Dalton Transactions

Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation†

Ümit İşci,ab   Pavel Afanasiev,a   Jean-Marc M. Millet,a   Evgeny V. Kudrik,a   Vefa Ahsenbc  and  Alexander B. Sorokin*a  

* Corresponding authors

a Institut de Recherches sur la Catalyse et l'Environnement de Lyon IRCELYON, UMR 5256, CNRS Université Lyon 1 2, av. A. Einstein, 69626 Villeurbanne Cedex, France
E-mail: alexander.sorokin@ircelyon.univ-lyon1.fr
Fax: +33 472445399
Tel: +33 472445337

b Department of Chemistry, Gebze Institute of Technology, Gebze 41400, Turkey

c Materials Institute, TUBITAK Marmara Research Center, Gebze 41470, Turkey

Abstract

μ-Nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and μ-nitrido-bis [tetra-(tert-butylsulfonyl) phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mössbauer techniques as well as by X-ray photoelectron and Fe K-edge X-ray absorption spectroscopies. Small changes at the periphery of the phthalocyanine ligand introduce a difference in the iron oxidation state. While 3b with tert-butyl substituents is a neutral complex with a mixed-valence Fe3.5–N–Fe3.5 structural unit, 3a having n-hexyl substituents is an oxidized cationic FeIV–N–FeIV complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe3.5–N–Fe3.5 unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 Å and the Fe–N bond distance of the linear Fe–N–Fe fragment is equal to 1.67 Å. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by tBuOOH. Toluene was oxidized to benzoic acid with 80% selectivity, and the total turnover number was as high as 197. p-Toluic acid was the principal product of p-xylene oxidation. In this case the turnover number achieved 587 substrate molecules per molecule of catalyst. The described catalytic system is complementary to the recently reported system based on μ-nitrido diiron tetrabutylphthalocyanine–H2O2 which effectively oxidizes the benzene ring.

Graphical abstract: Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

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Article information

DOI
https://doi.org/10.1039/B902592H
Article type
Paper
Submitted
09 Feb 2009
Accepted
10 Jun 2009
First published
21 Jul 2009

Dalton Trans., 2009, 7410-7420

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Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

Ü. İşci, P. Afanasiev, J. M. Millet, E. V. Kudrik, V. Ahsen and A. B. Sorokin, Dalton Trans., 2009, 7410 DOI: 10.1039/B902592H

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