The reaction of Cp2*UCl2 with HNSPh2 produces Cp2*UCl2(HNSPh2), which is the first structurally characterized complex of a sulfilimine. The hydrolysis of Cp2*UCl2(HNSPh2) with HNSPh2 · H2O yields a tetrauranium cluster whose heavy atom structure has been determined by x‐ray diffraction and which is formulated as a UIV/UV complex: [Cp*(Cl)(HNSPh2)U(μ3‐O)(μ2‐O)2U(Cl)(HNSPh2)2]2.

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Two imido derivatives of U(IV), Cp*2UCl(NSPh2) (1; Cp* = pentamethylcyclopentadienyl) and Cp*2U(NSPh2)2 (2), have been prepared in high yield from Cp*2UCl2 and LiNSPh2. Alternatively, 1 and 2 can be synthesized by treating Cp*2UCl[(CH2)2PPh2] with anhydrous HNSPh2. Cp*2U(NSPh2)2 is the first structurally characterized uranium bis(sulfilimide) complex. Its short U−N distance suggests significant uranium−imido multiple-bond character.