While research on earth abundant transition metal-mediated transformations continues to move forward apace, finding widespread applications in synthesis and catalysis, one area where these metals have shown little promise so far is in metallation chemistry.<br/>Breaking new ground in this field, this talk will present new bimetallic strategies whereby pairing a divalent transition metal such as Fe or Co with an alkali-metal selective ferration (or cobaltation) of a wide range of aromatic molecules is observed. Isolation of key organometallic intermediates demonstrates that these products are formally the result of Fe-H (or Co-H) exchange processes. Demonstrating its synergistic origin, this bimetallic approach induces chemo- and regioselectivities that neither sodium or iron amides are capable of facilitating on their own. Combining DFT calculations with spectroscopic and reactivity studies we shed light on the origins of this bimetallic cooperation which operates in a unique, unexpected way, with each metal playing a distinct key role. Extension of these studies to Li/Mn(II) bimetallic species will also be discussed, revealing the ability of these systems to promote direct Mn-halogen exchange processes, a type of reactivity traditionally considered exclusive of s-block polar organometallics.

Advancing earth abundant transition metal 'Ates for chemical cooperativity

ACS Fall 2021

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