New peripherally tetra-[trans-3,7-dimethyl-2,6-octadien-1-ol] substituted metallophthalocyanines: synthesis, characterization and catalytic activity studies on the oxidation of phenolic compounds


KANTEKİN H. , SAKA E. T. , ERTEM B. , MISIR M. N. , YALAZAN H., Sarkı G.

JOURNAL OF COORDINATION CHEMISTRY, cilt.71, ss.164-182, 2018 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 71 Konu: 1
  • Basım Tarihi: 2018
  • Doi Numarası: 10.1080/00958972.2018.1423560
  • Dergi Adı: JOURNAL OF COORDINATION CHEMISTRY
  • Sayfa Sayıları: ss.164-182

Özet

In this paper, we elucidated the synthesis, characterization, and investigation of catalytic activity studies of new metallophthalocyanines 4 and 5 as the catalyst for phenolic compounds oxidation by trying different types of oxygen sources. The structural characterization of the products was made by a combination of elemental analysis, FT-IR, LC-MS/MS (for phthalonitrile derivative3), MALDI-TOF mass spectral data (for metallophthalocyanines 4-7), UV-vis spectroscopy (for metallophthalocyanines 4-7), H-1 NMR and C-13 NMR spectroscopies (for compounds 3 and 6). The synthetic routes for the (trans-3,7-dimethyl-2,6-octadien-1-ol) substituted phthalonitrile derivative 3 and corresponding metallophthalocyanines 4-7 are outlined in Scheme 1. The MPc complexes 4-7 were synthesized via cyclotetramerization of compound 3 in the presence of the corresponding anhydrous metal salts (CoCl2 for 4, CuCl2 for 5, Zn(CH3COO)(2) for 6 and MnCl2 for 7) in dry n-pentanol as solvent and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as strong base at reflux temperature under nitrogen gas. Phthalocyanines and their metal complexes, in general, display poor solubility in most of the organic solvents, however, the synthesized metallophthalocyanine complexes 4-7 were highly soluble in common organic solvents because of the introduction of the methyl groups on alkyl chains of peripheral arms. The catalytic activity of compounds 4 and 5 was evaluated for the oxidation of phenolic compounds such as 4-nitrophenol, o-chlorophenol, 2,3-dichlorophenol, and p-methoxyphenol. CoPc 4 displayed good catalytic performance with a full oxidation of 4-nitrophenol into the corresponding benzoquinone and hydroquinone with the highest TON and TOF values within 3h.