Actinide-Mediated Catalytic Addition of E-H Bonds (E=N, P, S) to Carbodiimides, Isocyanates, and Isothiocyanates

Unprecedented catalytic reactivity of actinide coordination complexes toward heterocumulenes, such as carbodiimides, isocyanates, and isothiocyanates is reported. The mono(imidazolin-2-iminato) thorium(IV) complex [Th(Im^DippN){N(SiMe₃)₂}₃] (1) was applied as a precatalyst for the addition of E-H (E=N, P, S) bonds to the Y≡C≡X core (Y=R₂N; X=NR₂, O, S) of carbodiimides, isocyanates, and isothiocyanates. The respective insertion products were obtained in high yields under mild reaction conditions, with complex 1 displaying high tolerance toward functional groups and heteroatoms. New reactivity: The mono(imidazolin-2-iminato) thorium complex [Th(Im^DippN){N(SiMe₃)₂}₃] was successfully applied as an active catalyst for the addition of E-H (E=N, P, S) bonds across the central Y≡N≡C≡X linkage of carbodiimides, isocyanates and isothiocyanates, yielding the respective insertion products in high yields and under mild reaction conditions.