Acetone Factor in the Design of Cu₄-, Cu₆-, and Cu₉-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features,...

The present study describes a new feature in the self-assembly of cagelike copperphenylsilsesquioxanes: the strong influence of acetone solvates on cage structure formation. By this simple approach, a series of novel tetra-, hexa-, or nonacoppersilsesquioxanes were isolated and characterized. In addition, several new complexes of Cu₄ or Cu₆ nuclearity bearing additional nitrogen-based ligands (ethylenediamine, 2,2'-bipyridine, phenanthroline, bathophenanthroline, or neocuproine) were produced. Single-crystal X-ray diffraction studies established molecular architectures of all of the synthesized products. Several coppersilsesquioxanes represent a novel feature of cagelike metallasilsesquioxane (CLMS) in terms of molecular topology. A Cu₄-silsesquioxane complex with ethylenediamine (En) ligands was isolated via the unprecedented self-assembly of a partly condensed framework of silsesquioxane ligands, followed by the formation of a sandwich-like cage. Two prismatic Cu₆ complexes represent the different conformers─regular and elliptical hexagonal prisms, "cylinders", determined by the different orientations of the coordinated acetone ligands ("shape-switch effect"). A heterometallic Cu₄Na₄-sandwich-like derivative represents the first example of a metallasilsesquioxane complex with diacetone alcohol ligands formed in situ due to acetone condensation reaction. As a selected example, the compound [(Ph₆Si₆O₁₁)₂Cu₄En₂]·(acetone)₂ was explored in homogeneous oxidation catalysis. It catalyzes the oxidation of alkanes to alkyl hydroperoxides with hydrogen peroxide and the oxidation of alcohols to ketones with tert-butyl hydroperoxide. Radical species take part in the oxidation of alkanes. Besides, [(Ph₆Si₆O₁₁)₂Cu₄En₂]·(acetone)₂ catalyzes the mild oxidative functionalization of gaseous alkanes (ethane, propane, n-butane, and i-butane). Two different model reactions were investigated: (1) the oxidation of gaseous alkanes with hydrogen peroxide to give a mixture of oxygenates (alcohols, ketones, or aldehydes) and (2) the carboxylation of C gaseous alkanes with carbon monoxide, water, and potassium peroxodisulfate to give C carboxylic acids (main products), along with the corresponding C oxygenates. For these reactions, the effects of acid promoter, reaction time, and substrate scope were explored. As expected for free-radical-type reactions, the alkane reactivity follows the trend C₂H₆ < C₃H₈ < n-C₄H₁₀ < i-C₄H₁₀. The highest total product yields were observed in the carboxylation of i-butane (up to 61% based on i-C₄H₁₀). The product yields and catalyst turnover numbers (TONs) are remarkable, given an inertness of gaseous alkanes and very mild reaction conditions applied (low pressures, 50-60 °C temperatures).