Inter- and Intramolecular Hydroamination with a Uranium Dialkyl Precursor

The same uranium dibenzyl complex supported by a ferrocene-diamide ligand was used as a precatalyst for both inter- and intramolecular hydroamination reactions. Mechanistic and reactivity studies were undertaken to determine whether the two types of reactions follow the same pathway. The experimental results indicate that more than one mechanism may be operating and that the change in mechanism may be dependent on the type of reaction (inter- versus intramolecular) and/or the type of substrate (primary versus secondary amine). In addition, the synthesis and characterization of a bridging-imide diuranium(IV) complex and of benzyl- and anilide-aryloxide uranium(IV) complexes are reported, and their role in hydroamination reactions is discussed.