Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides

The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U­[N­(SiMe3)2]3 and [(Me3Si)2N]2An­[κ2-(N,C)-CH2Si­(CH3)2­N­(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon–nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide–oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.