Abstract
New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)6(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)6(NaCl)(C4H8O2)13(PhCN)2(H2O)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.
Highlights
Cage-like metallasilsesquioxanes (CLMSs) [1,2,3,4,5,6,7,8,9,10,11,12,13], being a family of polyhedra with inorganic cores and organic environments, have been thoroughly investigated in the line of their potential application in catalysis [14,15,16,17]
Some of us reported on ability of 1,4-dioxane molecules to serve as bridging linkers, combining individual into an system [20], weaswere interested in Recently, some ofCLMSs us reported onentire abilitysupramolecular of 1,4-dioxane molecules toand serve bridging linkers, the synthesis of new dioxane-CLMS
We have tested the catalytic effect of compound in oxidations with and alcohols [38,39,40,41,42,43,44] by peroxides
Summary
Cage-like metallasilsesquioxanes (CLMSs) [1,2,3,4,5,6,7,8,9,10,11,12,13], being a family of polyhedra with inorganic (metal silicate-like) cores and organic environments, have been thoroughly investigated in the line of their potential application in catalysis [14,15,16,17]. To use the advantage of good solubility of cage metallasilsesquioxanes in organic solvents and the ability of bringing unusual effects in the catalytic act due to specific structures of catalytic centers [19]. To use the advantage of good solubility of cage metallasilsesquioxanes in organic solvents and the ability of bringing unusual effects in copper-containing) the catalytic act duetypes to specific structures of catalytic centers [19]. Results on first examination of new Ni(II)-CLMS under oxidation conditions
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