Catalytic insertion of E–H bonds (E C, N, P, S) into heterocumulenes by amido–actinide complexes

We report herein the actinide-mediated insertion of E–H bonds (E 1⁄4 C, N, P, S) into various heterocumulenes including carbodiimides, isocyanates, and isothiocyanates. The precatalysts are prepared by a simple, one-pot procedure using readily available starting materials, and challenging insertions are achieved with excellent selectivity in short reaction times. Spectroscopic data are utilised to propose the active catalytic mechanism and derive thermodynamic activation parameters, which are described in this study. The only example of an actinide-mediated C–H bond insertion into a carbon– heteroatom bond is presented within this study.