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

Abstract

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)).