Reactive metallocarbenes will be discussed in the context of gold and polymer chemistry, with a particular focus on the migratory insertion mechanistic manifold for such species. A combination of experimental and theoretical studies revealed that migratory insertion at gold(III) is not only viable but rapid even at -40 °C; subsequent reductive elimination out-competes further migratory insertion at the same gold(III), a process that, if viable, would amount to propagation in carbene polymerization. Ligand modification toward manipulation of the reaction manifold will be explored. On the other hand, palladium(II) catalysts that are less prone to reductive elimination offer an opportunity for carbene polymerization—indeed, as demonstrated by Inoue and Ihara. However, to date, the mechanistic understanding of palladium-catalyzed carbene polymerization remains somewhat superficial, and living carbene polymerization remains an unmet challenge. Progress toward this goal will be described.

Advances in carbene migratory insertion directed toward transition-metal catalyzed polymer synthesis

256th National Meeting (2018)

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