Abstract
Herein we explore the intrinsic organometallic reactivity of iron embedded in a tetradentate N(3)C macrocyclic ligand scaffold that allows the stabilization of aryl-Fe species, which are key intermediates in Fe-catalyzed cross-coupling and C-H functionalization processes. This study covers C-H activation reactions using (Me) L (H) and FeCl(2), biaryl C-C coupling product formation through reaction with Grignard reagents, and cross-coupling reactions using (Me) L (Br) or (H) L (Br) in combination with Fe(0)(CO)(5). Synthesis under light irradiation and moderate heating (50 °C) affords the aryl-Fe(II) complexes [Fe(II)(Br)( (Me) L)(CO)] (1 (Me) ) and [Fe(II)( (H) L)(CO)(2)]Br (1 (H) ). Exhaustive spectroscopic characterization of these rare low-spin diamagnetic species, including their crystal structures, allowed the investigation of their intrinsic reactivity.