Reactivity of uranium(iii) with H(2)E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes

We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand ((Ad)ArO)(3)N)(3–). The mononuclear complexes [(((Ad)ArO)(3)N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [(((Ad)ArO)(3)N)U(III)(DME)] in DME via reduction of H(2)E and the elimination of 0.5 equivalents of H(2). The dinuclear complexes [{(((Ad)ArO)(3)N)U}(2)(μ-EH)(2)] can be obtained by dissolving their mononuclear counterparts in non-coordinating solvents such as benzene. In order to facilitate the work with the highly toxic gases, we created concentrated THF solutions that can be handled using simple glovebox techniques and can be stored at –35 °C for several weeks.