Iron-catalyzed C―C cross-coupling in the absence of additional ligands: active species and off-cycle pathways

Guillaume Lefèvre (1, 2) , Lidie Rousseau (2, 1) , P. Dorlet (3) , Christian Herrero (4) , Martin Clémancey (5) , J.-M Latour (5)

1 CSB2D - Catalysis, Synthesis of Biomolecules and Sustainable Development
2 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
3 I2BC - Institut de Biologie Intégrative de la Cellule
4 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
5 LCBM - UMR 5249 - Laboratoire de Chimie et Biologie des Métaux

Iron-catalyzed cross-coupling between a Grignard reagent RMgX and an electrophile R'─X was discovered by Kochi in the 1970s and witnessed recent improvements. This transformation can be carried out using simple iron salts such as FeCl$_2$ , FeCl$_3$ or Fe(acac)$_3$ in the absence of additional ligand. However, these systems lead to short-lived reactive species, making in-situ mechanistic analysis challenging. By means of Mössbauer, cw-and pulse-EPR spectroscopies, we demonstrated that two arene-stabilized Fe$^0$ and Fe$^I$ resting states were obtained by reduction of the precursor in toluene (Fig. 1a). Analysis of the bulk revealed that the ($\eta^4$-C$_6$H$_5$Me)$_2$Fe$^0$ complex catalyzes efficiently aryl-heteroaryl coupling, via a Fe$^0$ /Fe$^{II}$ cycle (Fig. 1b). Preliminary results moreover show that transient tris(aryl) species such as [Ph$_3$ Fe$^{II}$ ]-are key intermediates in the formation of the lower oxidation states. Fe$^0$ and Fe$^I$ are respectively afforded by 2-electron reductive elimination and by redox disproportionation of the +II ox. state.

Domains: Chemical Sciences; Material chemistry

Guillaume Lefèvre, Lidie Rousseau, P. Dorlet, Christian Herrero, Martin Clémancey, et al.. Iron-catalyzed C―C cross-coupling in the absence of additional ligands: active species and off-cycle pathways. International Conference on Coordination Chemistry, Jul 2018, Sendai, Japan. ⟨cea-02340033⟩