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 Dipp N){N(SiMe 3 ) 2 } 3 ] ( 1 ) was applied as a precatalyst for the addition of EH (E=N, P, S) bonds to the YCX core (Y=R 2 N; X=NR 2 , 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.