title: Isolation and characterization of a tetramethyliron(III) ferrate: an intermediate in the reduction pathway of ferric salts with MeMgBr.
abstract: While iron-catalyzed Kumada cross-coupling reactions with simple iron salts have been known since the early 1970s, the nature of the in situ-formed iron species remains elusive. Herein, we report the synthesis of the homoleptic tetralkyliron(III) ferrate complex [MgCl(THF)5][FeMe4] from the reaction of FeCl3 with MeMgBr in THF. Upon warming, this distorted square-planar S = (3)/2 species converts to the S = (1)/2 species originally observed by Kochi and co-workers with concomitant formation of ethane, consistent with its intermediacy in the reduction pathway of FeCl3 to generate the reduced iron species involved in catalysis.
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Malik H
authors.initials: MH
authors.lastname: Al-Afyouni
authors.forename: Kathlyn L
authors.initials: KL
authors.lastname: Fillman
authors.forename: William W
authors.initials: WW
authors.lastname: Brennessel
authors.forename: Michael L
authors.initials: ML
authors.lastname: Neidig
mesh_terms: D001965:Bromides / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D005290:Ferric Compounds / Q000737:chemistry*; D017616:Magnesium Compounds / Q000737:chemistry*; D008745:Methylation; D015394:Molecular Structure; D012492:Salts / Q000737:chemistry*
chemical_list: D001965:Bromides; D005290:Ferric Compounds; D017616:Magnesium Compounds; D012492:Salts; C586611:magnesium bromide