Facilitating the Ferration of Aromatic Substrates through Intramolecular Sodium Mediation

Exploiting cooperative effects between Na and FeII centres present in tris(amide) ferrate complexes has led to the chemoselective ferration of pentafluorobenzene, benzene, toluene, anisole, pyridine being realised at room temperature. The importance this bimetallic partnership is demonstrated by neither relevant sodium amide (NaHMDS or NaTMP) nor Fe(HMDS)2 efficiently metallating these substrates under conditions study. By combining NMR studies with isolation key intermediates DFT calculations, we offer a possible mechanism for how reactions take place, uncovering surprising reaction pathway which metals cooperate synchronised manner. Although isolated products are formally result Fe-H exchange, theoretical calculations indicate that aromatic undergo Na-H exchange followed fast intramolecular transmetallation Fe, thus stabilizing newly generated aryl fragment.