Intermediates and mechanism in iron-catalyzed C–H methylation with trimethylaluminum

Abstract

A mechanistic study is performed on the reaction method for iron-catalyzed C–H methylation with AlMe₃ reagent, previously proposed to involve cyclometalated iron(III) intermediates and an iron(III)/(I) reaction cycle. Detailed spectroscopic studies (⁵⁷Fe Mössbauer, EPR) during catalysis and in stoichiometric reactions identify iron(II) complexes, including cyclometalated iron(II) intermediates, as the major iron species formed in situ under catalytic reaction conditions. Reaction studies identify a cyclometalated iron(II)-methyl species as the key intermediate leading to C–H methylated product upon reaction with oxidant, consistent with a previously proposed iron(II)/iron(III)/iron(I) reaction manifold for C–H arylation.