Catalytic Addition of Alcohols into Carbodiimides Promoted by Organoactinide Complexes

The insertion of
alcohols into carbodiimides mediated by benzimidazolin-2-iminato actinide
complexes [(BimR1/R2N)­AnN″3] [N″ = N­(SiMe3)2] is presented
herein. Analysis of single-crystal data revealed that steric hindrance,
rather than electronic properties, plays an important role in determining
the accessibility for this insertion process. All actinide complexes
showed excellent activities under very mild conditions. Stoichiometric
reactions in combination with kinetic and thermodynamic studies allow
us to propose a plausible active species and a mechanism for the catalytic
cycle.