Synthesis and structural study of new metallasilsesquioxanes of potassium and uranium.

The first metallasilsesquioxanes comprising potassium and uranium have been synthesized and structurally characterized by single-crystal X-ray diffraction. (Cy7Si7O12)2K6(DME)4 (2; Cy = cyclohexyl) is a centrosymmetric dimer, in which the two silsesquioxide ligands are interconnected by μ3- and μ4-bridging siloxide moieties. (Cy7Si7O12)2UVI (3) represents the first metallasilsesquioxane complex of an actinide element, featuring a U atom that is coordinated by two tridentate silsesquioxide ligands in a distorted octahedral fashion. The different structural effects of the large metal atomic radii are discussed.