Synthesis and structure determination of a stable organometallic uranium(v) imine complex and its isolobal anionic U(IV)-ate complex

The reaction of one equivalent of Cp*₂UCl₂ with 2-(trimethylsilylimino)-1,3-di-tert-butylimidazoline in boiling toluene afforded a one electron oxidation of the uranium metal and the opening of the N-heterocyclic ring, resulting in the formation of an organometallic uranium(V) imine complex. This complex crystallized with one molecule of toluene in the unit cell, and its solid-state structure was determined by X-ray diffraction analysis. When the same reaction was performed in perdeuterated toluene, a myriad of organometallic complexes were obtained, however, when equimolar amounts of water were used in toluene, the same complex was obtained, and its solid state characterization shows two independent molecules in the unit cell with an additional water molecule. For comparison of the geometric parameters, the corresponding isolobal anionic uranium(IV) complex [Cp*₂UCl₃]^? was synthesized by the reaction of Cp*₂UCl₂ with 1,3-di-tert-butylimidazolium chloride, and the resulting U(IV)-ate complex was characterized by X-ray diffraction analysis.