2-Aminophenol appended pentadentate ligand H(2)Gan(AP) was synthesized by mixing equimolar amounts of 2-[bis(2-pyridylmethyl)aminomethyl]aniline (A) and 3,5-di-tert-butyl catechol in hexane in the presence of Et3N under air. The ligand reacted with Fe(ClO4)(2).6H(2)O or Fe(ClO4)(3).6H(2)O in the presence of tetrabutylammonium perchlorate, and Et3N under air and provided a mu(2) oxo-bridged dinuclear iron complex (1). X-ray single-crystal analysis of complex 1 revealed the presence of a furan derivative, resulting from the oxidative aromatic C-C bond cleavage product of 2-aminophenol derivative, in the coordination sphere of each iron center. Mechanistic investigation for the formation of complex 1 established that in the absence of molecular oxygen no oxidation of the appended 2-amidophenolate unit took place. An iron(III)-amidophenolate complex, formed initially, further reacted with molecular oxygen and caused oxidative aromatic C-C bond cleavage via a putative alkylperoxo species.