Deprotonative metalation constitutes one of the most utilized and important chemical reactions, facilitating the functionalization of molecules and the generation of novel reactive species.^1,2 Traditionally these reactions are performed with monometallic organolithium or lithium amides, which are highly activated due to the large polarity of their Li-N or Li-C bonds.³ However, their high reactivity imposes challenges, which diminish the atom economy and synthetic processes that are far from sustainability.⁴ In particular, the metalation of most fundamental arenes such as benzene or other non-activated polyarenes challenging due to the lack of acidity based on the absence of functional groups. 

Herein, we report the deprotonative mono- and multi-metalation of highly challenging substrates mediated by bimetallic cooperativity. The combination of alkali metal sodium and the earth abundant iron in a bimetallic ate system allows a unique ability to promote direct Fe-H exchange on non-activated arenes at ambient conditions. With the isolation and characterization of the organometallic key intermediates, we were able to  study the metalation process, observing unusual regioselectivities, which cannot be obtained with conventional single metal bases. Further functionalization allows access to valuable precursors towards more complex  organic molecular scaffolds. 

[1] Mulvey, R. E.; Mongin, F.; Uchiyama, M.; Kondo, Y. D Angew. Chem. Int. Ed. 2007, 46 (21), 3802–3824.

[2] Schlosser, M. Angew. Chem. Int. Ed. 2005, 44 (3), 376–393.

[3] Anderson, D. E.; Tortajada, A.; Hevia, E.  Angew. Chem. Int. Ed. 2024, 63 (4), e202313556.

[4] Haag, B.; Mosrin, M.; Ila, H.; Malakhov, V.; Knochel, P.  Angew. Chem. Int. Ed. 2011, 50 (42), 9794–9824.