title: Intramolecular C-H and C-F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes.
abstract: Herein we report the intramolecular arene C-H and C-F bond oxygenation by tetranuclear iron complexes. Treatment of [LFe3(PhPz)3OFe][OTf]2 (1) or its fluorinated analog [LFe3(F2ArPz)3OFe][OTf]2 (5) with iodosobenzene results in the regioselective hydroxylation of a bridging pyrazolate ligand, converting a C-H or C-F bond into a C-O bond. The observed reactivity suggests the formation of terminal and reactive Fe-oxo intermediates. With the possibility of intramolecular electron transfer within clusters in 1 and 5, different reaction pathways (Fe(IV)-oxo vs Fe(III)-oxo) might be responsible for the observed arene hydroxylation.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Graham
authors.initials: G
authors.lastname: de Ruiter
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Niklas B
authors.initials: NB
authors.lastname: Thompson
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Michael K
authors.initials: MK
authors.lastname: Takase
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Theodor
authors.initials: T
authors.lastname: Agapie
mesh_terms: D002244:Carbon / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D046911:Macromolecular Substances / Q000737:chemistry*; D008958:Models, Molecular
chemical_list: D008024:Ligands; D046911:Macromolecular Substances; D005461:Fluorine; D002244:Carbon; D006859:Hydrogen; D007501:Iron