title: Dioxygen Reactivity of an Iron Complex of 2-Aminophenol-Appended Ligand: Crystallographic Evidence of the Aromatic Ring Cleavage Product of the 2-Aminophenol Unit.
abstract: 2-Aminophenol appended pentadentate ligand H2GanAPwas 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)2·6H2O or Fe(ClO4)3·6H2O in the presence of tetrabutylammonium perchlorate, and Et3N under air and provided a μ2oxo-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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Guwahati , Guwahati 781 039, Assam India.
authors.forename: Ganesh Chandra
authors.initials: GC
authors.lastname: Paul
authors.affiliation: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science , 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700 032, India.
authors.forename: Sridhar
authors.initials: S
authors.lastname: Banerjee
authors.affiliation: Department of Chemistry, Indian Institute of Technology Guwahati , Guwahati 781 039, Assam India.
authors.forename: Chandan
authors.identifier: http://orcid.org/0000-0002-2771-2468
authors.initials: C
authors.lastname: Mukherjee