μ-nitrido diiron phthalocyanines: Electron-withdrawing vs electron-donating substituent effect on oxidation reaction catalysis

Eren O., ŞAHİN Z., DUMOULIN F., İŞCİ Ü.

Journal of Porphyrins and Phthalocyanines, cilt.28, sa.11-12, ss.806-813, 2024 (SCI-Expanded) identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 28 Sayı: 11-12
  • Basım Tarihi: 2024
  • Doi Numarası: 10.1142/s1088424624500639
  • Dergi Adı: Journal of Porphyrins and Phthalocyanines
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica
  • Sayfa Sayıları: ss.806-813
  • Anahtar Kelimeler: benzoic acids, benzyl alcohols, iron phthalocyanine, N-bridged dimer, nitrido, oxidation catalysis
  • Marmara Üniversitesi Adresli: Evet

Özet

Two μ-nitrido phthalocyanine complexes tetra non-peripherally substituted with either electron-withdrawing hexylsulfonyl chains ([FePc(SO2Hex)4]2N) or electron-donating hexyloxy chains ([FePc(OHex)4]2N) were prepared and fully characterized by FT-IR, MALDI-MS and UV-vis spectroscopic techniques, to investigate the effect of the substitution pattern on their catalytic properties. Iron atoms in both μ-nitrido complexes are in the FeIV-N=FeIV oxidation state, hence under their cationic form, as evidenced by the N3 peak in FT-IR and the fact that they are EPR silent. Both [FePc(SO2Hex)4]2N and [FePc(OHex)4]2N complexes were tested as catalysts for the oxidation of different benzyl alcohols by tBuOOH and gave the corresponding benzoic acids with excellent selectivity and complete conversion. The electron-withdrawing hexylsulfonyl-substituted μ-nitrido complex [FePc(SO2Hex)4]2N exhibited slightly better catalytic activities and selectivity towards the benzoic acid products than the electron-donating hexyloxy substituted μ-nitrido complex [FePc(OHex)4]2N.