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. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)