Alkyne Coupling Enabled by Actinide-Transition Metal Cooperativity

Abstract

Alkyne coupling, pivotal for C-C bond formation, is dominated by transition-metal catalysis, while actinide-mediated variants remain underdeveloped and exclusively reliant on low-valent uranium (U(II/III)) intermediates. Here we report an unprecedented alkyne homocoupling and cross-coupling enabled by actinide-transition metal cooperativity within a heterometallic U-Pd cluster. This transformation bypasses low-valent uranium intermediates, changing a decades-old mechanistic paradigm. Both stepwise and one-pot protocols efficiently afford selective coupling products from identical or distinct alkynyl Grignard reagents. Structural and computational studies reveal unusual electron delocalization within the resulting products.