Trans-metal-trapping : concealed crossover complexes en route to transmetallation?

Uzelac, Marina and Mulvey, Robert E. (2018) Trans-metal-trapping : concealed crossover complexes en route to transmetallation? Chemistry - A European Journal, 24 (31). pp. 7786-7793. ISSN 0947-6539

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    Abstract

    Defined as the transfer of ligands from one metal to another, transmetallation is a common reaction in organometallic chemistry. Its chemical celebrity stems from its role in important catalytic cycles of cross-coupling reactions such as those of Negishi, Sonogashira, Stille, or Suzuki. This article focuses on trans-metal-trapping (TMT), which could be construed as partially complete transmetallations. On mixing two distinct organometallic compounds, of for example lithium with aluminium or gallium, the two metals meet in a crossover co-complex, but the reaction ceases at that point and full transmetallation is not reached. Though in its infancy, trans-metal-trapping shows promise in transforming failed lithiations into successful lithiations and in stabilising sensitive carbanions through cooperative bimetallic effects making them more amenable to onward reactivity.