Structure of the {U13} polyoxo cluster U13O8Cl x (MeO)38–x (x = 2.3, MeO = methoxide)

Abstract

The structure of a new type of polyoxo cluster complex that contains thirteen uranium atoms, {U13}, is reported. The complex crystallized from methanol containing tetravalent uranium (UIV) with a basic organic ligand, and was characterized as dichloridooctacosa-μ2-methanolato-octakis(methanolato)octa-μ4-oxido-tridecauranium, [U13(CH3O)35.7Cl2.3O8] or [U13(μ4-Ooxo)8Cl x (MeO)38–x ] (x = 2.3, MeO = methoxide) (I), by single-crystal X-ray diffraction. The characterized {U13} polyoxo cluster complex (I) possesses a single cubic uranium polyhedron at the centre of the cluster core. To the best of our knowledge, this is the very first example of a polyoxo actinide complex that bears a single cubic polyhedron in its structure. The cubic polyhedron in I is well comparable in shape with those in bulk UO2. The U—O bonds in the cubic polyhedron of I are, however, significantly shorter than those not only in bulk UO2 but also in another analogue in the {U38} cluster. This shortening of U—O bonds, together with BVS calculations and the overall negative charge (2−) of I, suggests that the central uranium atom in I, which forms the single cubic coordination polyhedron, is presumably oxidized to the pentavalent state (UV) from the original tetravalent state (UIV). Complex I is, hence, the first example of a polyoxo cluster possessing a single cubic coordination polyhedron of UV.