5 years ago

Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes

Catalytic Addition of Alcohols to Carbodiimides Mediated by Benzimidazolin-2-iminato Actinide Complexes
Moris S. Eisen, Matthias Tamm, Natalia Fridman, Heng Liu
The synthesis of methyl and methoxy substituted benzimidazolin-2-iminato actinide (IV) complexes (14), [(Bim2-MeOPh/MeN)AnN″3] and [(Bim5-MeDipp/MeN)AnN″3] (An = U, Th; N″ = N(SiMe3)2), was performed by the protonolysis of the actinide metallacycles with the respective neutral benzimidazolin-2-imine ligand precursors. Full characterization, including X-ray diffraction studies for all the complexes, is reported. Despite the high oxophilicity of the actinide metal centers, these complexes displayed extremely high activities in the catalytic addition of aliphatic and aromatic alcohols to carbodiimides, under very mild conditions, providing a facile and highly efficient strategy for the construction of carbon–oxygen bonds. Various kinds of diols and triols can also be used in this intermolecular insertion, representing a large substrate scope for the application of these organoactinide precatalysts.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00432

DOI: 10.1021/acs.organomet.7b00432

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