Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides

Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO1.5)(18)(CuO)(9)] 1, hexa- [(MeSiO1.5)(10)(HO0.5)(2)(CuO)(6)(C-12,H8N2)(2)-(MeSiO1.5)(10)(HO0.5)(1.33)(CH3COO0.5)(0.67)(CuO)(6)(Ci(2)H(8)N(2))(2)] 2, (MeSiO1.5)(10)(CuO)(6)(MeO0.5)(2)(C10H8N2)(2)] 3, and trinuclear [(MeSiO1.5)(8)(CUO)(3)(C10H8N2)(2)], 4, were obtained in 44%, 27%, 20%, and 16% yields, respectively. Nuclearity and Structural fashion of products was controlled by the choice of solvent system and ligand, specifically assisting the assembling of cage. Structures of 1-4 were determined by single-crystal X-ray diffraction analysis. Compounds 1 and 4 are the first cage metallasilsesquioxanes, containing nine and three Cu ions, respectively. Product I is the first observation of nonanuclear metallasilsesquioxane ever. Unique architecture of 4 represents early unknown type of molecular geometry, based on,condensed pentamembered siloxane cycles: Topological analysis of metal dusters in products. 1-4 is provided. Complex 1 efficiently catalyzes oxidation of alcohols with tert-butylhydropermade TBHP to ketones or alkanes with H2O2 to alkyl hydroperoxides in acetonitrile.