SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor

Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material w…

Sintesi e studio fotofisico di sistemi Eu@POSS: controllo dell’emissione attraverso isomeria cis-trans.

Light-induced trans-cis isomerization of terpyridine functionalized POSS nanostructures self-assembled in presence of Eu3+ ions

A joint experimental and ab initio study on the reactivity of several hydroxy selenides. Stereoselective synthesis of cis-disubstituted tetrahydrofurans via seleniranium ions

Abstract The reactivity of several hydroxy selenides bearing an ethereal chain with catalytic amounts of perchloric acid in dichloromethane was investigated. Results showed that the position of the oxygen atom with respect to the seleniranium ring was crucial in order to get a good yield of the cyclized product. The factors on which yields of the 5- endo cyclization of the seleniranium ions depend were analysed by ab initio (HF/3-21G ∗ ) studies. An explanation of the different coordinating ability, towards the positively charged selenium atom, of the allylic OMe and homoallylic OH-2 groups was given.

Diastereoselective synthesis of substituted 2-phenyltetrahydropyrans as useful precursors of aryl C-glycosides via selenoetherification

The cyclization of several substituted 5-phenyl-pent-4-en-1-ols with selenium electrophiles along some mechanistic considerations is discussed. In particular, an efficient diastereoselective synthesis of a 2,3,5,6-tetrasubstitued tetrahydropyran is reported. These findings open an interesting approach: the use of chiral selenium electrophiles for cyclization of chiral substrates. The cyclized products are useful starting material for the synthesis of D- or L-aryl C-glycosides.

Materiali ibridi a base di POSS-Imidazolio per la conversione della CO2 in carbonati ciclici

Lo sviluppo di catalizzatori per i processi di conversione della CO2 è una tematica che sta rivestendo un ruolo di rilevante importanza in ambito non soltanto accademico ma anche industriale grazie alla possibilità di trasformare un rifiuto, quale il diossido di carbonio, in una vasta gamma di prodotti. Nel presente lavoro, nuovi materiali ibridi costituiti da silsesquiossani poliedrici oligomerici (POSS) supportati su silice e funzionalizzati con sali di imidazolio sono stati progettati per la fissazione della CO2. 1 Tutti i solidi sono stati ampiamente caratterizzati e testati per la sintesi di carbonati ciclici tramite reazione tra CO2 ed epossidi in condizioni di reazione solvent-free (…

Bisoxazoline-Fullerene Hybrid Systems for Asymmetric Catalysis

Design of POSS-Imidazolium Supported Hybrids for the Conversion of Carbon Dioxide into Cyclic Carbonates

Nowadays, the design of heterogeneous catalysts for the conversion of CO2 into useful chemical products is attracting the attention of the scientific community. The catalytic processes involving carbon dioxide as C1 feedstock are of growing interest for the sustainable development.1 The synthesis of cyclic carbonates by coupling CO2 with epoxides is one of the most interesting pathways for the conversion of carbon dioxide in terms of both atom economy and final products applications. Moreover, ionic liquids emerged as one of the most active catalysts for the production of cyclic carbonates starting from CO2 and epoxides.2 Herein, a series of heterogeneous catalytic systems bearing imidazoli…

ChemInform Abstract: New Ionic Liquid-Modified Silica Gels as Recyclable Materials for L-Proline- or H-Pro-Pro-Asp-NH2-Catalyzed Aldol Reaction.

L-proline and the tripeptide H–Pro–Pro–Asp–NH2 (1) have been supported, by adsorption, onto the surface of modified silica gels functionalized with a monolayer of covalently attached 1,2-dimethyl-imidazolium chloride, tetrafluoroborate or hexafluorophosphate ionic moieties, respectively. Three different linkers were used to attach the ionic liquid moiety to the surface of these supports. The resulting materials have been used as catalysts for the aldol reaction between acetone and several substituted benzaldehydes. Good yields and enantioselectivities, comparable to or better than those obtained under homogeneous conditions, were obtained. These materials are easily recovered by filtration,…

ChemInform Abstract: Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under Flow Conditions.

3-Mercaptopropyl-modified silica-supported bis-imidazolium Pd-catalysts are developed and successfully utilized for Suzuki reactions.

Multilayered supported ionic liquids as catalysts for chemical fixation of carbon dioxide

Multilayered, covalently supported ionic liquid phase (mlc-SILP) materials were synthesized by using a new approach based on the grafting of bis-vinylimidazolium salts on different types of silica or polymeric supports. The obtained materials were characterized and tested as catalysts in the reaction of supercritical carbon dioxide with various epoxides to produce cyclic carbonates. The material prepared by supporting a bromide bis-imidazolium salt on the ordered mesoporous silica SBA-15 was identified as the most active catalyst for the synthesis of cyclic carbonates and displayed improved productivity compared with known supported ionic liquid catalysts. The catalyst retained its high act…

Cover Feature: Tuneable Emission of Polyhedral Oligomeric Silsesquioxane Based Nanostructures that Self‐Assemble in the Presence of Europium(III) Ions: Reversible trans ‐to‐ cis Isomerization (ChemPlusChem 3/2020)

A study on the stability of carbon nanoforms–polyimidazolium network hybrids in the conversion of co2 into cyclic carbonates

Three different carbon nanoforms (CNFs), single-walled and multi-walled carbon nanotubes (SWCNTs, MWCNTs) and carbon nanohorns (CNHs), have been used as supports for the direct polymerization of variable amounts of a bis-vinylimidazolium salt. Transmission electron microscopy confirmed that all CNFs act as templates on the growth of the polymeric network, which perfectly covers the nanocarbons forming a cylindrical (SWCNTs, MWCNTs) or spherical (CNHs) coating. The stability of these hybrid materials was investigated in the conversion of CO2 into cyclic carbonate under high temperature and CO2 pressure. Compared with the homopolymerized monomer, nanotube-based materials display an improved c…

White light emitting silsesquioxane based materials: the importance of a ligand with rigid and directional arms

The synthesis of a novel polyhedral oligomeric silsesquioxane functionalized with eight rigid and directional terpyridine-based arms (Ter-POSS) was successfully achieved via a Sonogashira reaction. The POSS based ligand was extensively characterized using different techniques including 1H, 13C and 29Si NMR as well as UV-Vis and fluorescence spectroscopies. The assembly of these nano-caged units in the presence of different transition metal ions (Fe2+, Zn2+ and Cu2+) as well as of a cation from the lanthanides (Eu3+) was investigated using absorption and emission spectroscopies. The final materials display an evident emission in different regions of the visible spectrum as a function of the …

Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under Flow Conditions

Highly cross-linked imidazolium-based materials, obtained by radical oligomerization of bis-vinylimidazolium salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer-Emmett-Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy). The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds in high yields working with only 0.1 mol% of …

Thiazolium-based catalysts for the etherification reaction of benzylic alcohols under solvent-free condition

Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction me…

Correction: Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions

Correction for ‘Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions’ by Francesco Giacalone et al., J. Mater. Chem. A, 2016, 4, 17193–17206.

Supported Imidazolium Functionalized POSS Hybrids as Palladium Platform for C-C Cross-Couplings

Lo sviluppo di catalizzatori per i processi di conversione della CO2 è una tematica che sta rivestendo un ruolo di rilevante importanza in ambito non soltanto accademico ma anche industriale grazie alla possibilità di trasformare un rifiuto, quale il diossido di carbonio, in una vasta gamma di prodotti. Nel presente lavoro, nuovi materiali ibridi costituiti da silsesquiossani poliedrici oligomerici (POSS) supportati su silice e funzionalizzati con sali di imidazolio sono stati progettati per la fissazione della CO2. 1 Tutti i solidi sono stati ampiamente caratterizzati e testati per la sintesi di carbonati ciclici tramite reazione tra CO2 ed epossidi in condizioni di reazione solvent-free (…

Imidazolium-Functionalized Carbon Nanohorns for the Conversion of CO2 Unprecedented Increase of Catalytic Activity after Recycling

Carbon nanohorns (CNHs) were selected as a novel catalytic platform for the design of imidazolium based hybrid materials able to promote the conversion of carbon dioxide into cyclic carbonates. Several heterogeneous catalysts were prepared using a one-step procedure based on the radical polymerization of various bis-vinylimidazolium salts in the presence of pristine CNHs. The as-synthesized materials were tested for the fixation of CO2 into epoxides. The excellent catalytic performances were evaluated in terms of turnover number and productivity. The versatility of the above hybrids was proved using several epoxides as substrate. Catalysts recyclability was successfully verified for several…

Studies on the Stereoselective Selenolactonization, Hydroxy and Methoxy Selenenylation of α- and β-Hydroxy Acids and Esters. Synthesis of δ- and γ-Lactones.

Abstract The diastereoselective synthesis of hydroxy substituted γ- and δ-lactones was accomplished following two approaches. A 5- or 6-endo cyclization promoted by electrophilic selenium reagents of α- or β-hydroxy acids and a 5- or 6-exo cyclization of hydroxy esters obtained through a diastereoselective hydroxy selenenylation reaction of α- or β-hydroxy esters. Moreover, the diastereoselective methoxy selenenylation of the above compounds was investigated showing a case in which the compound that was unreactive in the hydroxy selenenylation conditions gave, in the methoxy selenenylation conditions, the deprotected diol. The usefulness of the methoxy selenenylation procedure was proven by…

Front Cover Picture: SBA‐15/POSS‐Imidazolium Hybrid as Catalytic Nanoreactor: the role of the Support in the Stabilization of Palladium Species for C−C Cross Coupling Reactions. (Adv. Synth. Catal. 16/2019)

Hybrid catalysts for CO 2 conversion into cyclic carbonates

The conversion of carbon dioxide into valuable chemicals such as cyclic carbonates is an appealing topic for the scientific community due to the possibility of valorizing waste into an inexpensive, available, nontoxic, and renewable carbon feedstock. In this regard, last-generation heterogeneous catalysts are of great interest owing to their high catalytic activity, robustness, and easy recovery and recycling. In the present review, recent advances on CO 2 cycloaddition to epoxide mediated by hybrid catalysts through organometallic or organo-catalytic species supported onto silica-, nanocarbon-, and metal-organic framework (MOF)-based heterogeneous materials, are highlighted and discussed.

Imidazolium-Functionalized Carbon Nanohorns for the Conversion of Carbon Dioxide

Six new hybrid materials composed of carbon nanohorns (CNHs) and highly cross-linked imidazolium salts were easily synthesized using a one-step procedure based on the radical oligomerization of bis-vinylimidazolium salts (bVImiX) in the presence of pristine CNHs. The hybrid materials were characterized and employed as the sole catalysts for the conversion of carbon dioxide into cyclic carbonate by reaction with epoxides. The solids displayed excellent turnover number and productivity. Moreover, four catalysts were investigated in recycling experiments. Two catalysts containing an octyl linker between the imidazolium units and a bromide or an iodide anion showed no loss in activity after thr…

Imidazolium functionalized carbon nanotubes for the synthesis of cyclic carbonates: reducing the gap between homogeneous and heterogeneous catalysis

Single walled carbon nanotubes (SWCNTs) were functionalized with imidazolium salts bearing vinyl functionalities. An extremely high loading of active species was achieved through a straightforward one-pot procedure involving self-assembly of the imidazolium moieties followed by radical initiated polymerization of the double bonds. The materials were extensively characterized by transmission electron microscopy, Raman spectroscopy, nitrogen physisorption and combustion chemical analysis. The imidazolium functionalized SWCNTs displayed excellent catalytic activity for the reaction of CO2 and epoxides to produce cyclic carbonates as demonstrated by the excellent turnover numbers (TON). Moreove…

Catechol-Functionalized Carbon Nanotubes as Support for Pd Nanoparticles

Carbon nanotubes have been covalently functionalized with catechol moieties through the formation of the corresponding aryl radicals obtained by reacting 4-aminocatechol with isoamyl nitrite. The functionalized multiwalled carbon nanotubes have been in turn used to immobilize Pd(II) ions on its surface forming catechol-Pd complexes, which were reduced to Pd nanoparticles (NPs). The so-obtained hybrid material has been characterized by means of thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). This latter technique allowed to estimate the nanoparticle size (5.7 +/- 2.8 nm) wh…

Stereocontrolled approach to δ- and γ-lactones and 1,3-diols. The role of X− ion in the selenolactonization

Abstract Two complementary approaches have been realized for the stereoselective synthesis of 4,6-disubstituted δ-lactones and 1,3- anti and syn diols. In the 6- endo selenolactonization the role of the X − ion on the stereoselectivity is shown. Moreover, the highly stereoselective transformation of the 6- endo δ-lactone to the 5- exo γ-lactone is reported.

ChemInform Abstract: Stereocontrolled Approach to δ- and γ-Lactones and 1,3-Diols. The Role of X- Ion in the Selenolactonization.

Abstract Two complementary approaches have been realized for the stereoselective synthesis of 4,6-disubstituted δ-lactones and 1,3- anti and syn diols. In the 6- endo selenolactonization the role of the X − ion on the stereoselectivity is shown. Moreover, the highly stereoselective transformation of the 6- endo δ-lactone to the 5- exo γ-lactone is reported.

Multi-layered, covalently supported ionic liquid phase (mlc-SILP) as highly cross-linked support for recyclable palladium catalysts for the suzuki reaction in aqueous medium

The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, sma…

Templating effect of carbon nanoforms on highly cross-linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles

Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and re…

Sustainable Approach to Waste-Minimized Sonogashira Cross-Coupling Reaction Based on Recoverable/Reusable Heterogeneous Catalytic/Base System and Acetonitrile Azeotrope

In this contribution, we present a chemically efficient and sustainable protocol for the palladium-catalyzed copper-free Sonogashira cross-coupling reaction, based on the use of a heterogeneous catalytic system. This consists in the combination of a palladium catalyst on highly cross-linked thiazolidine network on silica and a polystyrene-supported base. The solid catalyst/base system acts as a palladium scavenger avoiding leaching of the metal and consequent product contamination. The reaction can be conducted in safe and easily recoverable acetonitrile/water azeotrope as reaction medium. This proved to be an efficient greener alternative to the classic toxic aprotic media commonly used in…

Diastereoselective Synthesis of 2-Phenylselenenyl-1,3-anti-Diols and 2-Phenylselenenyl-1,3-anti-Azido-Alcohols via Hydroxy- and Azido-Selenenylation Reactions

A method to synthesize 2-phenylselenenyl-1,3-anti-diols and 2-phenyl- selenenyl-1,3-anti-azidoalcohols via hydroxy- or azido-selenenylation of trans-allylic alcohols is reported. Moreover, the first example of hydroxyl-selenenylation of an allylic azide is presented. Yields ranging from moderate to good and diastereomeric ratios up to 95:5 are achieved.

Oxidative degradation properties of Co-based catalysts in the presence of ozone

Four series of cobalt-based catalysts, such as bare Co3O4 and CoO, CoOx-CeO2 mixed oxides, CoOx supported over alumina and alumina-baria and CoMgAl and CoNiAl hydrotalcites have been synthesized and investigated for the oxidative degradation of phenol in the presence of ozone. Characterizations were obtained by several techniques in order to investigate the nature of cobalt species and their morphological properties, depending on the system. Analyses by XRD, BET, TPR, UV-visible diffuse reflectance spectroscopy and TG/DT were performed. The CoNiAl hydrotalcite exhibits, after 4 h of reaction, the highest phenol ozonation activity followed by Co(3 wt%)/Al2O3-BaO and CoMgAl. The samples Co(1 …

Cross-Linked Thiazolidine Network as Support for Palladium: A New Catalyst for Suzuki and Heck Reactions

A thiazolidine-based material was used for the first time as support for palladium. The support was prepared by starting from a highly cross-linked thiazolium-based material, obtained by radical oligomerization of a bisvinylthiazolium dibromide salt in the presence of 3-mercaptopropyl-modified silica SBA-15. Palladium was immobilized by treatment with tetrachloropalladate salt. Reduction with sodium borohydride afforded a thiazolidine-based material that acted as ligands for the Pd species. The thiazolidine-based palladium catalyst was fully characterized and, working in only 0.1 mol% amount, displayed good activity in the Suzuki-Miyaura and in the Heck reactions. Several biphenyl and alken…

Supported C60-IL-PdNPs as extremely active nanocatalysts for C-C cross-coupling reactions

A C60-ionic liquid hybrid has been covalently linked to three different solid supports, namely amorphous silica, SBA-15 and Fe2O3@SiO2, and the resulting materials have been employed as covalently supported ionic liquid phases (cSILP) in order to immobilize and stabilize palladium nanoparticles (PdNPs). These novel hybrid materials are based on a sort of "matryoshka" system (PdNPs@imidazolium-salt@C60@support) in which the imidazolium-based moieties have not been directly linked to the surface of the support, but they are present in an octopus-like spatial arrangement on the uniformly surface-distributed fullerenes. These materials have been fully characterized and successfully employed as …

ChemInform Abstract: Stereoselective Synthesis of Substituted Tetrahydropyran Rings via 6-exo and 6-endo Selenoetherification.

Eight unsaturated alcohols were cyclized by selenoetherification in 6-exo or 6-endo manner to give substituted tetrahydropyran rings. Yields, regio- and stereoselectivities were discussed in terms of steric and electroniceffects such as Se-O interaction. For the first time examples of the use of silica gel in selenoetherification and the effect of the X - counter ion of PhSe + on the reaction course are discussed. These effects are related to the occurrence of Se-O interaction.

Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks

Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values,…

POSS nanostructures in catalysis

Polyhedral oligomeric silsesquioxanes (POSS) are organic-inorganic hybrid molecules piquing the interest of researchers thanks to their synergistic features. The great versatility of POSS nanostructures arises from the easy tunability of peripheral organic moieties combined with the high thermal and chemical stability of the inner inorganic core. In this review, we highlight the use of POSS nanostructures as molecular precursors for the synthesis of homogeneous and heterogeneous catalysts able to promote many processes including alkene epoxidation, C-C bond formation, CO2 conversion, "click reactions", hydrogenation, and ethylene polymerisation, among others. In this scenario, POSS units fo…

Catalizzatori a base di nanocorni di carbonio-liquidi ionici per la conversione della CO2

Nel presente lavoro sono stati impiegati nanocorni di carbonio (CNHs) come piattaforma catalitica per il design di nuovi materiali ibridi a base di sali di imidazolio per la conversione della CO2 in carbonati ciclici. A tale scopo sono stati preparati una serie di catalizzatori eterogenei mediante una procedura sintetica one-pot basata sulla polimerizzazione radicalica di vari sali di bis vinilimidazolio in presenza di nanocorni di carbonio. I suddetti materiali sono stati caratterizzati e testati con successo per la reazione di fissazione della CO2 in epossidi (Figura 1). Figura 1 Conversione della CO2 catalizzata da liquidi ionici supportati su CNHs Le performances catalitiche, valutate i…

Supported ionic liquids. New recyclable materials for the L-proline-catalyzed aldol reaction

New materials for L-proline recycling have been developed. These materials have been applied to the L-proline-catalyzed aldol reaction between acetone and several aldehydes. The L-proline has been supported on the surface of modified silica gels with a monolayer of covalently attached ionic liquid with or without additional adsorbed ionic liquid. Good yields and ee values, comparable with those obtained under homogeneous conditions, have been obtained especially with imidazolinium-modified and 4-methylpyridinium-modified silica gels. Moreover, these materials have been easily recovered by simple filtration and studies about their reuse have been carried out. These studies showed that these …

Carbon nanotube supported aluminum porphyrin-imidazolium bromide crosslinked copolymer

The increased awareness of the catastrophic consequences caused by the accumulation of greenhouse gases into the atmosphere has generated a large mobilization aimed at CO2 mitigation. Herein, in the spirit of the transformation of a waste as CO2 into value added products, we propose an efficient preparation of two different hybrid systems based on aluminum chloride tetrastyrylporphyrin (TSP-Al-Cl) and 1,4-butanediyl-3,3′-bis-1-vinylimidazolium dibromide copolymerized in the presence (MWCNT-TSP-AlCl-imi) and in absence (TSP-AlCl-imi) of multi-walled carbon nanotubes (MWCNTs) for the CO2 utilization in the synthesis of cyclic carbonates. The so-prepared materials have been thoroughly characte…

Synthesis and high-throughput testing of multilayered supported ionic liquid catalysts for the conversion of CO2 and epoxides into cyclic carbonates

Multilayered covalently supported ionic liquid phase (mlc-SILP) materials were synthesised by grafting different bis-vinylimidazolium salts on thiol-functionalised silica. These materials, which contain a cross-linked oligomeric network of imidazolium units, were characterised and tested as catalysts for the reaction of carbon dioxide with various epoxides to produce cyclic carbonates. The materials prepared by supporting a bis-imidazolium iodide salt with xylene or octane as a linker between the imidazolium units were identified as the most active catalysts and displayed high turnover numbers and improved productivity compared to known supported ionic liquid catalysts. The most promising m…

Synthesis of 2,4,6-trisubstituted tetrahydropyrans via 6-exo selenoetherification of unsaturated alcohols

Stereoselectivity, regioselectivity and yields in the 6-exo selenoetherification of four unsaturated diols were found to depend on the stereochemistry of the diols and on the presence of an oxygen atom close to the intermediate seleniranium ring. Silica gel was useful in order to obtain good yields. Reactions performed both under kinetic and thermodynamic control led to the same products. Stereoselectivity, regioselectivity and yields in the 6-exo selenoetherification of four unsaturated diols were found to depend on several factors such as the stereochemistry of the diols, the nature of the R group, the nature of the counter anion of the PhSe+ species and the presence of silica gel.

Imidazolium Based Cross-Linked Nanostructures from POSS molecular bricks for the Efficient Conversion of Carbon Dioxide

Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular bricks for the synthesis of imidazolium cross-linked networks as heterogeneous catalyst for the conversion of carbon dioxide into cyclic carbonates via reaction with epoxides. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid state NMR, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates and outstanding productivity values. Several epoxides were r…

POSS-Al-porphyrin-imidazolium cross-linked network as catalytic bifunctional platform for the conversion of CO2 with epoxides

Two heterogeneous catalysts were prepared with the aim of following the promising path of CO2 fixation into epoxides. The synthetic procedure involves a radical copolymerization of an octavinylsilsesquioxane as inorganic core building block and tetrastyrylporphyrin aluminum chloride monomer (TSP-AlCl) in presence (POSS-TSP-AlCl-imiBr) or in absence (POSS-TSP-AlCl) of a bis-vinylimidazolium bromide salt (bis-imiBr), in order to investigate if the bifunctional heterogeneous material can display better catalytic performance than the separate species. All the solids were fully characterized and tested in the synthesis of cyclic carbonates starting from CO2 and several epoxides. The synergic coo…

Synthesis of a Hydrothermally Stable, Periodic Mesoporous Material Containing Magnetite Nanoparticles, and the Preparation of Oriented Films

Magnetite nanoparticles modified covalently with triethoxysilane having a quaternary dicetyl ammonium ion are used together with tetraethylorthosilicate as building blocks to prepare a mesoporous material. Cetyltrimethylammonium bromide is used as a structure-directing agent under conditions typically used for mesoporous MCM-41 silicas. The resulting mesoporous material (MAG-MCM-41), containing up to 15 wt % of magnetite is characterized by transmission electron microscopy (TEM), isothermal gas adsorption, and X-ray diffraction. In contrast to siliceous MCM-41, mesoporous MAG-MCM-41 exhibits a remarkable hydrothermal stability. The magnetic properties of MAG-MCM-41 are characterized by DC a…

Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2

Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic spec…

A polyhedral oligomeric silsesquioxane-based catalyst for the efficient synthesis of cyclic carbonates

Polyhedral oligomeric silsesquioxane functionalized with imidazolium chloride peripheries (POSS-Imi) was successfully synthesized through a novel synthesis protocol. The solid was extensively characterized via1H NMR, 13C NMR and IR spectroscopy as well as combustion chemical analysis, mass spectrometry and transmission electron microscopy. Moreover, an in-depth investigation through 29Si NMR was performed. POSS-Imi was used for the first time as a catalyst for the conversion of CO2 and epoxides into cyclic carbonates with excellent results in terms of both yield and selectivity. The catalyst displayed improved catalytic performance with respect to unsupported 1-butyl-3-methylimidazolium chl…

Tuneable Emission of Polyhedral Oligomeric Silsesquioxane Based Nanostructures that Self-Assemble in the Presence of Europium(III) Ions: Reversible trans-to-cis Isomerization

[EN] Hybrid nanostructures with switchable and reversible "blue-red-green" emission were efficiently synthesized. These nanostructures comprise polyhedral oligomeric silsesquioxanes (POSS) that behave as a nanocage that can be functionalized with terpyridine-based organic ligands, which can be easily complexed with europium (III) ions. The complexes were characterized by UV-Vis and fluorescence spectroscopy and their stoichiometry was also confirmed by H-1 NMR spectroscopy. In the presence of the Eu(III) ions, the octafunctionalized nanocages self-assemble to form 3D architectures that display an intense red-emission, especially in the solid state. The presence of an alkenyl group bridging …

New Hybrid Organic-inorganic Multifunctional Materials Based on Polydopamine-like Chemistry

Taking inspiration from the chemistry of dopamine, a simple and economic synthetic approach toward the synthesis of a series of silica-based polydopamine-like materials has been developed. Mild conditions and easy manipulation are the strongest aspects of this methodology. Such hybrid materials were successfully used as recyclable catalysts for Knoevenagel reactions.

Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane-Imidazolium Tetrachloro- palladate Salt as a Precatalyst for the Suzuki-Miyaura Reaction in Water

A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of …

Polyhedral Oligomeric Silsesquioxane Based Catalyst for the Efficient Synthesis of Cyclic Carbonates

In this work, the synthesis of a novel imidazolium-based polyhedral oligomeric silsesquioxane (POSS-mim-Cl) material is presented. The new nanometer-size organosilica based compound was employed for chemical fixation of CO2 into epoxide under homogeneous conditions. The target reaction was represented by the obtention of cyclic carbonates starting from epoxides and CO2. Particularly, styrene oxide was chosen as reference substrate. In addition, different parameters (solvent, temperature, pressure of CO2, and mass of the catalyst) were modified to find the best condition for CO2 conversion. The catalyst POSS-mim-Cl displayed good catalytic performances, the best results being obtained at 40 …

Design of novel imidazolium based nanostructures for sustainable catalytic applications

Evidences of release and catch mechanism in the Heck reaction catalyzed by palladium immobilized on highly cross-linked-supported imidazolium salts

Abstract Palladium (10 wt%) on a highly cross-linked imidazolium-based material was used as catalyst in 0.1 mol% in the Heck reaction between several alkenes and aryl iodides. Products were obtained from good to high yields. Deeper investigations showed a release of Pd species in solution and their capture by the imidazolium-based support. When a sixfold amount of support was employed the re-captured Pd species (0.5–0.6 wt%) were not anymore catalytically active. This result represents a new interesting aspect of this work since the highly cross-linked imidazolium-based material can act also as Pd scavenger avoiding the release of the metal in solution. Important differences between Heck an…

Stereoselective synthesis of substituted tetrahydropyran rings via 6-exo and 6-endo selenoetherification

Eight unsaturated alcohols were cyclized by selenoetherification in 6-exo or 6-endo manner to give substituted tetrahydropyran rings. Yields, regio- and stereoselectivities were discussed in terms of steric and electroniceffects such as Se-O interaction. For the first time examples of the use of silica gel in selenoetherification and the effect of the X - counter ion of PhSe + on the reaction course are discussed. These effects are related to the occurrence of Se-O interaction.

Modified Carbon Nanoforms Systems for Asymmetric Catalysis

Reconsidering TOF calculation in the transformation of epoxides and CO2 into cyclic carbonates

Abstract The combination of Lewis acids and Lewis bases, currently defined as catalysts and co-catalysts (or promoter) respectively, in the reaction between epoxides and CO2 to give cyclic carbonates, is discussed, starting from examples in which the Lewis base was used in larger amount with respect to the Lewis acid. In these cases, turnover frequency (TOF) values have been usually calculated taking into account solely the amount of the Lewis acid employed. The occurrence of two distinct reaction pathways, one catalysed by the sole Lewis base and the other one catalysed by the Lewis acid/Lewis base couple, in which the Lewis acid alone does not play a catalytic role, should bring researche…

New ionic liquid-modified silica gels as recyclable materials for L-proline- or H-Pro-Pro-Asp-NH2-catalyzed aldol reaction

l-proline and the tripeptide H-Pro-Pro-Asp-NH2 (1) have been supported, by adsorption, onto the surface of modified silica gels functionalized with a monolayer of covalently attached 1,2-dimethyl-imidazolium chloride, tetrafluoroborate or hexafluorophosphate ionic moieties, respectively. Three different linkers were used to attach the ionic liquid moiety to the surface of these supports. The resulting materials have been used as catalysts for the aldol reaction between acetone and several substituted benzaldehydes. Good yields and enantioselectivities, comparable to or better than those obtained under homogeneous conditions, were obtained. These materials are easily recovered by filtration,…