Open AccessWell-Defined Aryl-FeII Complexes in Cross-Coupling and C–H Activation Processes
Author(s) -
Carla Magallón,
Oriol Planas,
Steven Roldán-Gómez,
Josep M. Luis,
Anna Company,
Xavi Ribas
Publication year - 2021
Publication title -
organometallics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.231
H-Index - 172
eISSN - 1520-6041
pISSN - 0276-7333
DOI - 10.1021/acs.organomet.1c00100
Subject(s) - chemistry , reactivity (psychology) , aryl , ligand (biochemistry) , reagent , coupling reaction , catalysis , stereochemistry , crystal structure , crystallography , medicinal chemistry , photochemistry , organic chemistry , receptor , pathology , medicine , biochemistry , alkyl , alternative medicine
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 B r 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.