Issue 45, 2021

Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity

Abstract

Herein, we report the synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer, a structural analogue of a monocationic μ-nitrido-bridged iron phthalocyanine dimer, which is known to be one of the most potent molecule-based catalysts for methane oxidation. 1H-NMR and single-crystal X-ray structural analyses showed that the porphycene complex includes two Fe(IV) ions, and the structure around the Fe–N[double bond, length as m-dash]Fe core is quite similar to that of the monocationic μ-nitrido-bridged iron phthalocyanine dimer. Although methane was oxidized into MeOH, HCHO, and HCOOH in the presence of a silica-supported catalyst of this monocationic μ-nitrido-bridged iron porphycene dimer in an acidic aqueous solution containing excess H2O2, its reactive intermediate was not a high-valence iron-oxo species, as in the case of a monocationic μ-nitrido-bridged iron phthalocyanine dimer, but ˙OH. It is suggested that the high-valent iron-oxo species of the μ-nitrido-bridged iron porphycene dimer was gradually decomposed under these reaction conditions, and the decomposed compound catalyzed a Fenton-type reaction. This result indicates that the stability of the oxo-species is indispensable for achieving high catalytic methane oxidation activity using a μ-nitrido-bridged iron porphyrinoid dimer with an Fe–N[double bond, length as m-dash]Fe core as a catalyst.

Graphical abstract: Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity

Supplementary files

Article information

Article type
Paper
Submitted
31 Aug 2021
Accepted
09 Oct 2021
First published
12 Oct 2021

Dalton Trans., 2021,50, 16775-16781

Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity

Y. Yamada, Y. Miwa, Y. Toyoda, T. Yamaguchi, S. Akine and K. Tanaka, Dalton Trans., 2021, 50, 16775 DOI: 10.1039/D1DT02922C

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