A heterometallic (Fe₆Na₈) cage-like silsesquioxane: synthesis, structure, spin glass behavior and high catalytic activity

Abstract

The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO1.5)20(FeO1.5)6(NaO0.5)8(n-BuOH)9.6(C7H8)] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation.

High Catalytic Activity of Heterometallic (Fe₆Na₇and Fe₆Na₆) Cage Silsesquioxanes in Oxidations with Peroxides

“…Symptomatically, the same combination of ligands was observed in previously reported Fe6Na8 compound [23]. In turn, compound II includes (Figure 4,B).…”

“…As a pair of metal ions, a Fe/Na combination has been chosen because of the following reasons. It is known that sodiumcontaining heterometallic cage siloxanes provide exceptional variety of architecture [14][15][16][17] as well as catalytic activities [16,17,19,20] and magnetic (spin glass) properties [21][22][23][24]. It is explained by the participation of specific siloxanolate [RSi(O)ONa] ligand in cage construction, giving rise to multiple metallasiloxane architectures [17].…”

“…This tactics has been rarely used for Fe,Na-silsesquioxane design. Furthermore, a unique example of such architecture, namely Fe6Na8 compound featuring a Lantern shape, was synthesized as its butanol/toluene complex by some of us very recently [23]. First results regarding the application of the approach "ratio/solvent choice" towards the synthesis of Fe,Na-silsesquioxanes are reported herein along with catalytic studies of the obtained complex under oxidation and amidation conditions.…”

Green route for selective gram‐scale oxidation of sulfides using tungstate/triazine‐based ionic liquid immobilized on magnetic nanoparticles as a phase‐transfer heterogeneous catalyst

“…[1] In addition, due to the increasing demand for oxidation products, today, great efforts are being made to design and prepare appropriate catalysts aiming to obtain products with more selectivity and higher yield, and especially minimizing the cost of production and environmental pollutions. [2] Among the oxidation reactions, selective oxidation of sulfides to sulfoxides has been significantly developed in recent years because sulfoxides are widely used for the synthesis of various chemicals in the laboratory and industry. [3] Oxidation of sulfides to sulfoxides usingtraditional methods and reagents, such as the use of potassium hydrogen carbonate, [4] m-chloroperbenzoic acid, [5] potassium permanganate, [6] NaIO 4 [7] and HNO 3 , [8] suffers from several disadvantages.…”

“…[26] Based on this strategy, in this paper, we present a simple route for the preparation of an oxidation catalyst composed of immobilized bis(aminoethylammonium)/WO 4 2− IL, derived from triazine, [27] on magnetic nanoparticles for the first time. The resulting system was used as a heterogeneous, magnetic and phase transfer catalyst for the selective oxidation of sulfides to sulfoxides in the presence of aqueous H 2 Fourier transform infrared (FT-IR) spectra of samples were taken using an ABB Bomen MB-100 FT-IR spectrometer. Thermogravimetric analysis (TGA) was conducted under a nitrogen atmosphere with a TGA Q 50 thermogravimetric analyser.…”