Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides

New hexanuclear nickel(II) silsesquioxane [(PhSiO(1.5))(12)(NiO)(6)(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO(1,5))(12)(NiO)(6)(NaCl)(C(4)H(8)O(2))(13)(PhCN)(2)(H(2)O)(2) and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.