Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear CuNa-Cage. Synthesis, Unique Structure, and Catalytic Activity.

Self-assembly synthesis of mixed-ligand (silsesquioxane/acetate) complex allows to isolate record high nuclear copper(II) Cu-cage (1). In the presence of two additional sodium ions, a unique molecular architecture, with triple combination of ligands (cyclic and acyclic silsesquioxanes as well as acetates), has been formed. The structure was established by single-crystal X-ray diffraction based on the use of synchrotron radiation.

An octanuclear 3-phenyl-5-(2-pyridyl)pyrazolate/phenylsilsesquioxane complex: synthesis, unique structure, and catalytic activity.

The first metallasilsesquioxane bearing pyrazolylpyridine ligands, the Cu-based complex 1, adopts a cage-like structure with two zigzag-type copper tetramers sandwiched by two cyclic Si silsesquioxane ligands. The four 3-phenyl-5-(2-pyridyl)pyrazolate ligands in 1 exhibit dual (chelating and bridging) modes of ligation. Compound 1 is very active in the oxidation of alkanes and alcohols.

Cu-Methylsilsesquioxane Cage Decorated with Cu(dppe) Moieties for Mild Oxidative Functionalization of Alkanes.

We report a high nuclear (Cu) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic Cu(dppe) moieties and an anionic silsesquioxane cage of an unprecedented Cu structural type. The Cu cage fragment exhibits a unique () combination of Si-cyclic/Si-acyclic silsesquioxane ligands and () encapsulation of two different chloride and carbonate species.

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

The synthesis of a high nuclear (CuNa) complex 1 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 CuNa-silsesquioxane cage demonstrates a nontrivial combination of two pairs of Si-cyclic/Si-acyclic silsesquioxane ligands and a fusion of two SiCuNa fragments, combined the central ninth copper ion.

Rational (supra)molecular design and catalytic activity of cage-like Cu-based phenylsilsesquioxanes.

An extended (, 19 distinct species) family of cage-like Cu-phenylsilsesquioxanes allowed us to accentuate the general regularities behind their structural organization. Influencing factors, namely the (i) size of external alkali metal ions (from Li to Cs) and (ii) nature of bridging linkers (including the smallest possible ones, like a water molecule) on the self-assembly/supramolecular assembly of such Cu-building blocks have been thoroughly explored. A CuK-based complex has been evaluated as a precatalyst in the oxidation of alkanes (cyclohexane, -heptane, methylcyclohexane) and alcohols.