Elemental chalcogen reactions of a tetravalent uranium imidophosphorane complex: cleavage of dioxygen

Herein we report the first example of a mononuclear uranium complex, [U4+(NP(pip)3)4] (1-U), that selectively reduces dioxygen to produce a terminal oxo complex, [U6+O(NP(pip)3)4] (2-U; [NP(pip)3]1− is tris(piperidinyl)imidophosphorane). Reactions between 1-U and the heavier elemental chalcogens, S8 or Se0, result in six-coordinate U(VI) complexes, [U6+(κ2-E3)(NP(pip)3)4] (E = S (3-U) or Se (4-U)).