Selenolated Copper Hydride Clusters for Visible-Light Photocatalytic Iodofluoroalkylation of Alkynes

The photocatalytic iodofluoroalkylation of unsaturated systems is of great interest, with significant potential in the synthesis of fluorinated compounds. Herein, we introduce a selenate-protected <b>Cu</b>_<b>18</b> hydride cluster, [Cu₁₈H₉(dppy)₆(PhCH₂Se)₆](PF₆)₃ (dppy = diphenyl-2-pyridylphosphine, PhCH₂Se = benzylselenate), that enables visible light-mediated iodofluoroalkylative difunctionalization of alkynes. Single crystal X-ray structural analysis reveals that the cluster comprises a hydride-embedded hexagonal close-packed Cu₁₈ kernel of the <i>D</i>_3<i>d</i> symmetry, coprotected by benzylselenate and dppy ligands. Mechanistic studies suggest the reaction proceeds through a single-electron-transfer process from the photoexcited state [<b>Cu</b>_<b>18</b>are similar to those reported in The [<b>Cu</b>_<b>18</b>]⁺ complexes then further oxidize the vinyl radicals to form vinyl cations, completing the redox-neutral catalytic cycle. This work presents an efficient method for synthesizing fluoroalkylated iodoalkenes and offers valuable insights into the design of catalytically active metal clusters for the advancement of organic synthesis.