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

Isci, Uemit; Afanasiev, Pavel; Millet, Jean-Marc M.; Kudrik, Evgeny V.; Ahsen, Vefa; Sorokin, Alexander B.


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  "@context": "https://schema.org/", 
  "@id": 93697, 
  "@type": "ScholarlyArticle", 
  "creator": [
    {
      "@type": "Person", 
      "name": "Isci, Uemit"
    }, 
    {
      "@type": "Person", 
      "affiliation": "Univ Lyon 1, IRCELYON, CNRS, UMR 5256, F-69626 Villeurbanne, France", 
      "name": "Afanasiev, Pavel"
    }, 
    {
      "@type": "Person", 
      "affiliation": "Univ Lyon 1, IRCELYON, CNRS, UMR 5256, F-69626 Villeurbanne, France", 
      "name": "Millet, Jean-Marc M."
    }, 
    {
      "@type": "Person", 
      "affiliation": "Univ Lyon 1, IRCELYON, CNRS, UMR 5256, F-69626 Villeurbanne, France", 
      "name": "Kudrik, Evgeny V."
    }, 
    {
      "@type": "Person", 
      "name": "Ahsen, Vefa"
    }, 
    {
      "@type": "Person", 
      "affiliation": "Univ Lyon 1, IRCELYON, CNRS, UMR 5256, F-69626 Villeurbanne, France", 
      "name": "Sorokin, Alexander B."
    }
  ], 
  "datePublished": "2009-01-01", 
  "description": "mu-Nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and mu-nitrido-bis [tetra-(tert-butylsulfonyl)phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mossbauer 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 Fe-3.5-N-Fe-3.5 structural unit, 3a having n-hexyl substituents is an oxidized cationic Fe-IV-N-Fe-IV complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe-3.5-N-Fe-3.5 unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 angstrom and the Fe-N bond distance of the linear Fe-N-Fe fragment is equal to 1.67 angstrom. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by (BuOOH)-Bu-t. 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 mu-nitrido diiron tetrabutylphthalocyanine-H2O2 which effectively oxidizes the benzene ring.", 
  "headline": "Preparation and characterization of mu-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation", 
  "identifier": 93697, 
  "image": "https://aperta.ulakbim.gov.tr/static/img/logo/aperta_logo_with_icon.svg", 
  "license": "http://www.opendefinition.org/licenses/cc-by", 
  "name": "Preparation and characterization of mu-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation", 
  "url": "https://aperta.ulakbim.gov.tr/record/93697"
}
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