Carbon–Carbon Bond Formation Reactivity of a Four-Coordinate NHC-Supported Iron(II) Phenyl Compound

Abstract

The preparation and characterization of a NHC-coordinated (NHC = N-heterocyclic carbene) ferrous phenyl complex [(IPr2Me2)2FePh2] (1; IPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) as well as its C–C bond formation reactivity have been studied. The four-coordinate iron(II) phenyl complex was prepared from the reaction of ferrous chloride with PhMgBr and IPr2Me2. It reacts with nonactivated primary and secondary alkyl bromides and chlorides to furnish cross-coupling products and the iron(II) monophenyl species (IPr2Me2)2FePhX (X = Br (2), Cl). When it is treated with cyclooctatetraene (cot) or [Cp2Fe][BArF4] in the presence of PMe3, it undergoes coordination or one-electron oxidation induced reductive elimination of biphenyl to form the corresponding iron(0) or iron(I) species [(IPr2Me2)2Fe(η4-cot)] (3) or [(IPr2Me2)2Fe(PMe3)2][BArF4] (4). All of these iron-containing products have been fully characterized by various spectroscopic methods. Complex 1 and (IPr2Me2)2FeCl2 catalyze the reaction of n...