An ionic Cu9Na4-phenylsilsesquioxane/bis(triphenylphosphine)iminium complex: synthesis, unique structure, and catalytic activity.

The synthesis of a high nuclear (Cu9Na4) complex 1via the self-assembly of copper(II) phenylsilsesquioxane induced by complexation with bis(triphenylphosphine)iminium chloride (PPNCl) was successfully achieved. This complex, which includes two bis(triphenylphosphine)iminium PPN+ cations, represents the first example of a metallasilsesquioxane/phosphazene compound. The Cu9Na4-silsesquioxane cage demonstrates a nontrivial combination of two pairs of Si6-cyclic/Si4-acyclic silsesquioxane ligands and a fusion of two Si10Cu4Na2 fragments, combined via the central ninth copper ion. The catalytic efficacy of the copper(II) compound (1) was evaluated through the peroxidative oxidation of toluene using tert-butyl hydroperoxide (t-BuOOH) as the oxidant. The primary oxidation products were benzaldehyde (BAL), benzyl alcohol (BOL), and benzoic acid (BAC), with BAC being the predominant product, especially in acetonitrile (NCMe). The formation of cresols, indicating oxidation at the aromatic ring, was observed only in water and under microwave irradiation (MW) in NCMe. Remarkably, the highest total yield of 40.3% was achieved in water with an acidic additive at 80 °C, highlighting the crucial role of the acid additive in enhancing reaction efficiency and selectivity. This study underscores our copper(II) complex as a highly effective catalyst for toluene oxidation, demonstrating its significant potential for fine-tuning reaction parameters to optimize yields and selectivity. The unprecedented structure of the complex and its promising catalytic performance pave the way for further advancements in the fields of metallasilsesquioxane chemistry and catalysis.