Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes† †Electronic supplementary information (ESI) available: Full synthetic and experimental details, spectroscopic data for 1H NMR, SQUID and UV/vis and detailed X-ray crystallographic data in CIF format. CCDC 1020771–1020776. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02602k Click here for additional data file. Click here for additional data file.

We report the syntheses, electronic properties, andmolecular structures of a series of monoand dinuclear uranium(IV) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand (ArO)3N) 3 . The mononuclear complexes [((ArO)3N)U(DME)(EH)] (E 1⁄4 S, Se, Te) can be obtained from the reaction of the uranium(III) starting material [((ArO)3N)U(DME)] in DME via reduction of H2E and the elimination of 0.5 equivalents of H2. The dinuclear complexes [{((ArO)3N)U}2(m-EH)2] can be obtained by dissolving their mononuclear counterparts in noncoordinating 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.