Selective Oligomerization and [2 + 2 + 2] Cycloaddition of Terminal Alkynes from Simple Actinide Precatalysts

A catalyzed conversion of terminal alkynes into dimers, trimers, and trisubstituted benzenes has been developed using the actinide amides U­[N­(SiMe₃)₂]₃ (1) and [(Me₃Si)₂N]₂An­[κ²-(N,C)-CH₂Si­(CH₃)­N­(SiMe₃)] (An = U (2), Th (3)) as precatalysts. These complexes allow for preferential product formation according to the identity of the metal and the catalyst loading. While these complexes are known as valuable precursors for the preparation of various actinide complexes, this is the first demonstration of their use as catalysts for C–C bond forming reactions. At high uranium catalyst loading, the cycloaddition of the terminal alkyne is generally preferred, whereas at low loadings, linear oligomerization to form enynes is favored. The thorium metallacycle produces only organic enynes, suggesting the importance of the ability of uranium to form stabilizing interactions with arenes and related π-electron-containing intermediates. Kinetic, spectroscopic, and mechanistic data that inform the nature of the activation and catalytic cycle of these reactions are presented.