Heteroleptic heterometallic N-bridged porphyrinoids: The effects of macrocycle and metal on oxidation reaction

Yüceel Ç., ŞAHİN Z., Yildiz D. B., DEDE Y., DUMOULIN F., İŞCİ Ü.

Journal of Catalysis, vol.450, 2025 (SCI-Expanded) identifier

  • Publication Type: Article / Article
  • Volume: 450
  • Publication Date: 2025
  • Doi Number: 10.1016/j.jcat.2025.116220
  • Journal Name: Journal of Catalysis
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, PASCAL, Applied Science & Technology Source, Chemical Abstracts Core, Chimica, Compendex, Computer & Applied Sciences, INSPEC
  • Keywords: Heteroleptic, Heterometallic, N-bridged, Oxidation, Phthalocyanine, Quantum calculation
  • Gazi University Affiliated: Yes

Abstract

Heteroleptic heterobimetallic µ-nitrido porphyrinoids MnPor-N-FePc and MnPc-N-FePor were prepared by using Mn-N3 porphyrinoid with corresponding iron porphyrinoid derivative and characterized by FT-IR, HRMS, MALDI-MS, UV–vis, EPR and Raman spectroscopic techniques. The characteristic Mn-N-Fe bands of both heteroleptic heterobimetallic µ-nitrido complexes were clearly confirmed by FT-IR and Raman spectroscopies. These two novel complexes were tested in oxidation of 2,3,5-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone. Interestingly, the heteroleptic heterobimetallic µ-nitrido porphyrinoid MnPor-N-FePc was more efficient catalyst than MnPc-N-FePor. Computational studies explain that the different catalytic efficiency between MnPor-N-FePc and MnPc-N-FePor depends on the thermodynamic stability of the intermediates of both complexes on oxidation reaction. The intermediates of MnPor-N-FePc have better thermodynamic stability than MnPc-N-FePor.