Room‐Temperature Direct Spectroscopic Observation of High‐Valent Terminal Iron‐Oxo Species of a µ‐Nitrido‐Bridged Iron Phthalocyanine Dimer Deposited on a Highly Oriented Pyrolytic Graphite Surface

High‐valent metal‐oxo species, such as iron(IV)‐oxo porphyrin π‐cation radical, are known to be involved in a variety of oxidative CH bond activation by metal complexes in the presence of oxidants. Although spectroscopic observations of these high‐valent metal‐oxo species are important for understanding reaction mechanisms, their high reactivities sometimes hamper direct observations, especially at ambient temperature. Herein, a high‐valent iron‐oxo species, involved in catalytic CH 4 oxidation by a µ‐nitrido‐bridged iron phthalocyanine dimer in an aqueous solution in the presence of excess H 2 O 2 , was successfully investigated by X‐ray photoelectron spectroscopy (XPS), X‐ray absorption spectroscopy (XAS), Raman, and matrix‐assisted laser desorption and ionization‐time‐of‐flight mass spectroscopy (MALDI‐TOF MS) studies after deposition on a highly oriented pyrolytic graphite (HOPG) surface at room temperature. XPS study indicated the formation of a species with high oxidation states after treatment of the µ‐nitrido‐bridged iron phthalocyanine dimer attached on a HOPG with H 2 O 2 . Raman and O K‐edge XAS studies, in combination with MALDI‐TOF MS results, indicated the evidence for the formation of a species containing an oxygen atom with a double‐bond character.