Carboxymethylcellulose‐supported palladium nanoparticles generated in situ from palladium(II) carboxymethylcellulose as an efficient and reusable catalyst for ligand‐ and base‐free Heck–Matsuda and Suzuki–Miyaura couplings

A novel palladium(II) carboxymethylcellulose (CMC‐Pd^II) was prepared by direct metathesis from sodium carboxymethylcellulose and PdCl₂ in aqueous solution. Its catalytic activities were explored for Heck–Matsuda reactions of aryldiazonium tetrafluoroborate with olefins, and Suzuki–Miyaura couplings of aryldiazonium tetrafluoroborate with arylboronic acid. Both reactions proceeded at room temperature in water or aqueous ethanol media without the presence of any ligand or base, to provide the corresponding cross‐coupling products in good to excellent yields under atmospheric conditions. The CMC‐Pd^II and carboxymethylcellulose‐supported palladium nanoparticles (CMC‐Pd⁰) formed in situ in the reactions were characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, inductively coupled plasma atomic emission spectrometry, and scanning and transmission electron microscopies. The homogeneous nature of the CMC‐Pd⁰ catalyst was confirmed via Hg(0) and CS₂ poisoning tests. Moreover, the CMC‐Pd⁰ catalyst could be conveniently recovered by simple filtration and reused for at least ten cycles in Suzuki–Miyaura reactions without apparently losing its catalytic activity. The catalytic system not only overcomes the basic drawbacks of homogeneous catalyst recovery and reuse but also avoids the need to fabricate palladium nanoparticles in advance. Copyright © 2015 John Wiley & Sons, Ltd.     

An improved preparation of mesoporous silica‐supported Pd as sustainable catalysts for phosphine‐free Suzuki–Miyaura and Heck coupling reactions

An improved and eco‐friendly procedure has been developed to generate mesoporous silica‐supported palladium nanoparticles (SiO₂@PdNP) that could be used as a sustainable heterogeneous Pd catalyst for phosphine‐free Suzuki–Miyaura and Heck coupling reactions with excellent turnover number and turnover frequency. The presence of Pd on the silica surface was detected by X‐ray diffraction and the structural morphology of SiO₂@PdNP was obtained by transmission electron microscopy. The heterogeneous catalytic system is recyclable and leaching of the metal after the reaction is not apparently observed. Copyright © 2013 John Wiley & Sons, Ltd.     

A highly water‐dispersible and magnetically separable palladium catalyst based on functionalized poly(ethylene glycol)‐supported iminophosphine for Suzuki–Miyaura coupling in water

A magnetically separable Fe₃O₄@poly(ethylene glycol) (PEG)–iminophosphine palladium complex was successfully prepared by reacting a palladium complex containing the ligand 2‐(diphenylphosphino)benzaldehyde with amino‐functionalized PEG‐coated iron oxide nanoparticles. The novel catalyst was characterized using inductively coupled plasma atomic emission and Fourier transform infrared spectroscopies, transmission electron microscopy, vibrating sample magnetometry, X‐ray diffraction and thermogravimetric analysis. It showed high activity for the Suzuki–Miyaura coupling reaction in pure water. Furthermore, it was found that the highly water‐dispersible catalyst can be recovered by applying an external magnetic field and used in five consecutive runs without significant decrease in activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Finely dispersed palladium on silk‐fibroin as an efficient and ligand‐free catalyst for Heck cross‐coupling reaction

A palladium–fibroin complex (Pd/Fib.) was prepared by the addition of sonicated fibroin fiber in water to palladium acetate solution. Pd (OAc)₂ was absorbed by fibroin and reduced with NaBH₄ at room temperature to the Pd(0) nanoparticles. Powder‐X‐ray diffraction, scanning electron microscopy–energy‐dispersive X‐ray spectroscopy, Fourier transform‐infrared, CHN elemental analysis and inductively coupled plasma‐atomic emission spectroscopy were carried out to characterize the Pd/Fib. catalyst. Catalytic activity of this finely dispersed palladium was examined in the Heck coupling reaction. The catalytic coupling of aryl halides (‐Cl, ‐Br, ‐I) and olefins led to the formation of the corresponding coupled products in moderate to high yields under air atmosphere. A variety of substrates, including electron‐rich and electron‐poor aryl halides, were converted smoothly to the targeted products in simple procedure. Heterogeneous supported Pd catalyst can be recycled and reused several times.     

N‐heterocyclic carbene–palladium(II) complex supported on magnetic mesoporous silica for Heck cross‐coupling reaction

Magnetic mesoporous silica was prepared via embedding magnetite nanoparticles between channels of mesoporous silica (SBA‐15). The prepared composite (Fe₃O₄@SiO₂‐SBA) was then reacted with 3‐chloropropyltriethoxysilane, sodium imidazolide and 2‐bromopyridine to give 3‐(pyridin‐2‐yl)‐1H‐imidazol‐3‐iumpropyl‐functionalized Fe₃O₄@SiO₂‐SBA as a supported pincer ligand for Pd(II). The functionalized magnetic mesoporous silica was further reacted with [PdCl₂(SMe₂)₂] to produce a supported N‐heterocyclic carbene–Pd(II) complex. The obtained catalyst was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray analysis, vibrating sample magnetometry, Brunauer–Emmett–Teller surface area measurement and X‐ray diffraction. The amount of the loaded complex was 80.3 mg g^?1, as calculated through thermogravimetric analysis. The formation of the ordered mesoporous structure of SBA‐15 was confirmed using low‐angle X‐ray diffraction and transmission electron microscopy. Also, X‐ray photoelectron spectroscopy confirmed the presence of the Pd(II) complex on the magnetic support. The prepared magnetic catalyst was then effectively used in the coupling reaction of olefins with aryl halides, i.e. the Heck reaction, in the presence of a base. The reaction parameters, such as solvent, base, temperature, amount of catalyst and reactant ratio, were optimized by choosing the coupling reaction of 1‐bromonaphthalene and styrene as a model Heck reaction. N‐Methylpyrrolidone as solvent, 0.25 mol% catalyst, K₂CO₃ as base, reaction temperature of 120°C and ultrasonication of the catalyst for 10 min before use provided the best conditions for the Heck cross‐coupling reaction. The best results were observed for aryl bromides and iodides while aryl chlorides were found to be less reactive. The catalyst exhibited noticeable stability and reusability.     

Palladium–S‐propyl‐2‐aminobenzothioate immobilized on Fe3O4 magnetic nanoparticles as catalyst for Suzuki and Heck reactions in water or poly(ethylene glycol)

A moisture‐ and air‐stable heterogenized palladium catalyst was synthesized by coordination of palladium with S‐propyl‐2‐aminothiobenzamide supported on Fe₃O₄ magnetic nanoparticles. The prepared nanocatalyst was characterized using Fourier transform infrared, energy‐dispersive X‐ray and inductively coupled plasma atomic emission spectroscopies, X‐ray diffraction, vibrating sample magnetometry, transmission and scanning electron microscopies, dynamic laser scattering and thermogravimetric analysis. This catalyst could be dispersed homogeneously in water or poly(ethylene glycol) and further applied as an excellent nano‐organometal catalyst for Suzuki and Heck reactions. The catalyst was easily separated with the assistance of an external magnet from the reaction mixture and reused for several consecutive runs without significant loss of its catalytic efficiency or palladium leaching. The leaching of catalyst was examined using hot filtration and inductively coupled plasma atomic emission spectroscopy. Also, the effects of various reaction parameters on the Suzuki and Heck reactions are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Heck and Suzuki–Miyaura couplings catalyzed by nanosized palladium in polyaniline

A novel route to prepare polyaniline (PANI)‐supported Pd(0) nanoparticles by a one‐pot chemical route is presented. Nanosized Pd(0) particles were first prepared by reduction of Pd(OAc)₂ using t‐BuONa activated sodium hydride in refluxing THF. A ligand exchange with aniline on t‐BuONa‐stabilized Pd(0) particles yielded aniline‐stabilized particles. Pd(0)/PANI nanocomposites were finally obtained by polymerizing aniline‐stabilized Pd(0) particles using ammonium persulfate. Nanocomposites were characterized by transmission electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. Results show that this one‐pot experimental route is successful in producing hybrid materials constituted of Pd(0) nanoparticles stabilized by PANI due to the strong binding of PANI amine groups to Pd(0) particles. TEM images of the nanohybrids show that metal particles with diameters of ca. 4.9 nm are homogeneously dispersed in PANI. The preliminary results indicate that the Pd(0) particles supported on PANI behave as efficient heterogeneous catalysts in the Heck and Suzuki–Miyaura reactions of aryl iodides. Copyright © 2005 John Wiley & Sons, Ltd.     

Silica–acetylacetone‐supported palladium nanoparticles as an efficient and reusable catalyst in the Heck–Mizoroki C–C cross‐coupling reaction

The preparation of palladium nanoparticles supported on acetylacetone‐modified silica gel and their catalytic application for Heck olefination of aryl halides were investigated. The catalyst was characterized using X‐ray diffraction, X‐ray photoelectron spectroscopy, and transmission and scanning electron microscopies. The supported palladium nanoparticles are demonstrated to be a highly active and reusable catalyst for the Heck reaction. Several reaction parameters, including type and amount of solvent and base, were evaluated. The heterogeneity of the catalytic system was investigated with results indicating that there is a slight palladium leaching into the reaction solution under the applied reaction conditions. Despite this metal leaching, the catalyst can be reused nine times without significant loss of catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Magnetic iron oxide nanoparticles–N‐heterocyclic carbene–palladium(II): a new,efficient and robust recyclable catalyst for Mizoroki–Heck and Suzuki–Miyaura coupling reactions

A new and efficient nanoparticle–N‐heterocyclic carbene–palladium complex was synthesized and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy‐dispersive X‐ray analysis, X‐ray diffraction, transmission electron microscopy, elemental analysis, inductively coupled plasma analysis and vibrating sample magnetometry. This catalytic system was found to be a highly active catalyst in the Mizoroki–Heck and Suzuki–Miyaura cross‐coupling reactions. These reactions were best performed in dimethylformamide and water, respectively, in the presence of only 0.054 mol% of palladium under mild conditions. Moreover, the catalyst could be recovered easily and reused at least ten times without any considerable loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Biaryl formation via Suzuki and Stille coupling reactions using palladium nanoparticle/polymeric N‐heterocyclic carbene grafted silica as recyclable and efficient catalyst

Palladium nanoparticles supported on polymeric N‐heterocyclic carbene grafted silica as an efficient organic–inorganic hybrid catalyst is introduced. Pd⁰ nanoparticle formation, which is stabilized by the polymeric N‐heterocyclic carbene ligands and ionic liquid units, was confirmed using X‐ray photoelectron spectroscopy. Scanning electron microscopy images showed microparticles of modified silica while transmission electron microscopy images displayed a fine distribution of Pd nanoparticles. The modified structure was applied successfully in biaryl formation via Suzuki and Stille coupling reactions. Various biaryls were generated through the reaction of phenylboronic acid or tetraphenyltin with a variety of haloarenes via cross‐coupling reactions. This catalyst showed promising activity after being recycled several times. Copyright © 2016 John Wiley & Sons, Ltd.     

Palladium nanoparticles deposited on a graphene–benzimidazole support as an efficient and recyclable catalyst for aqueous‐phase Suzuki–Miyaura coupling reaction

Graphene oxide was functionalized with benzimidazole for palladium immobilization. The resultant graphene–benzimidazole‐supported palladium composite (G‐BI‐Pd) was characterized using infrared and Raman spectroscopies, transmission electron microscopy and energy‐dispersive X‐ray spectroscopy. G‐BI‐Pd showed excellent catalytic activity and fast reaction kinetics in the aqueous‐phase Suzuki–Miyaura reaction of aryl iodides and bromides with phenylboronic acid under relatively mild conditions (5–25 min, 80 °C). The catalyst can be used several times without any significant loss of its catalytic activity.     

Sustainable Catalysis: Rational Pd Loading on MIL‐101Cr‐NH2 for More Efficient and Recyclable Suzuki–Miyaura Reactions

Palladium nanoparticles have been immobilized into an amino‐functionalized metal–organic framework (MOF), MIL‐101Cr‐NH₂, to form Pd@MIL‐101Cr‐NH₂. Four materials with different loadings of palladium have been prepared (denoted as 4‐, 8‐, 12‐, and 16 wt %Pd@MIL‐101Cr‐NH₂). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier‐transform infrared (FTIR) spectroscopy, powder X‐ray diffraction (PXRD), N₂‐sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL‐101Cr‐NH₂, electron tomography was employed to reconstruct the 3D volume of 8 wt %Pd@MIL‐101Cr‐NH₂ particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high‐energy X‐rays (60 keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki–Miyaura cross‐coupling reaction. The best catalytic performance was obtained with the MOF that contained 8 wt % palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6 nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15 mol %). The material can be recycled at least 10 times without alteration of its catalytic properties.     

Polyacrylonitrile fiber mat‐supported palladium catalyst for Mizoroki–Heck reaction in aqueous solution

A novel palladium catalyst immobilized on polyacrylonitrile fiber mats (Pd/PAN) was prepared by electrospinning. The catalytic activity and recyclability of the microwave‐assisted Pd/PAN fiber mats were examined for the Mizoroki–Heck cross‐coupling of aryl iodides with three different acrylates in aqueous solution. The morphology of the prepared Pd/PAN fiber mats was characterized by scanning electron microscopy. The large size of the PAN fiber mat‐supported palladium catalyst enables much easier separation from the reaction mixture by simple filtration. Density functional theory calculation indicates that the chelation energy of palladium chloride (PdCl₂) with propionitrile (model of PAN) is considerable smaller than that of PdCl₂ with water, suggesting that the stability and reactivity of the Pd/PAN fiber mats catalyst could be improved through the surface derivatization with polar functional groups. Copyright © 2011 John Wiley & Sons, Ltd.     

One‐pot synthesis of magnetic palladium–NiFe2O4–graphene oxide composite: an efficient and recyclable catalyst for Heck reaction

A magnetically separable NiFe₂O₄@GO–Pd composite (GO = graphene oxide) was successfully prepared by a facile one‐pot hydrothermal strategy. This new kind of hybrid material was fully characterized using powder X‐ray diffraction, Raman spectroscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy and vibrating sample magnetometry. Structural characterizations confirmed the formation of NiFe₂O₄ and Pd nanocrystals, and the close anchoring between nanoparticles and GO sheets. Additionally, the as‐prepared NiFe₂O₄@GO–Pd nanocomposite was effectively employed in the palladium‐catalyzed Heck reaction in an ethanol–water system as a green solvent. The catalyst was completely recoverable with the simple application of an external magnetic field and with no obvious loss of catalytic activity even after six repeated cycles. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanopalladium on polyethylenimine–grafted starch: An efficient and ecofriendly heterogeneous catalyst for Suzuki–Miyaura coupling and transfer hydrogenation reactions

Functionalized natural polysaccharides are attractive supports for colloidal metal nanocatalysts due to their abundance, cheapness, biocompatibility and biodegradability. In this study, isocyanate–functionalized starch was prepared by treating with diisocyanate. Polyethylenimine grafted onto starch via the formation of urea linker. The palladium nanoparticles deposited starch PEIS@Pd(0) was obtained through a chelating–in situ reduction procedure. Characterization of these materials was done using Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X–ray diffraction, and inductive coupled plasma atomic emission spectrometry. The catalytic activity of PEIS@Pd(0) was then tested in two series of model reactions: Suzuki–Miyaura coupling and transfer hydrogenation. The catalyst could be recovered by simple filtration and was reused for five times without significant loss of catalytic activity, which confirmed the good stability of the catalyst.     

Fabrication of covalently functionalized mesoporous silica core–shell magnetite nanoparticles with palladium(II) acetylacetonate: application as a magnetically separable nanocatalyst for Suzuki cross‐coupling reaction of acyl halides with boronic acids

We report the preparation of supported palladium(II) acetylacetonate, Pd(acac)₂, coordinated by pendant acac groups, by reacting palladium acetate with acac‐functionalized doubly silica‐coated magnetic nanoparticles. The solid support consists of an amorphous silica‐coated (as magnetite protecting layer) magnetite core and a mesoporous silica shell. The magnetically separable palladium nanocatalyst is active for Suzuki cross‐coupling reaction of acyl halides with boronic acids. The catalyst is simply isolated from the reaction mixture that allows fast and efficient isolation of product and catalyst compared to traditional methods that generally make use of time‐ and solvent‐consuming procedures. Copyright © 2015 John Wiley & Sons, Ltd.     

Biochar as heterogeneous support for immobilization of Pd as efficient and reusable biocatalyst in C–C coupling reactions

Biochar is a stable and carbon‐rich solid which has a high density of carbonyl, hydroxyl and carboxylic acid functional groups on its surface. In this work, the surface of biochar nanoparticles (BNPs) was modified with 3‐choloropropyltrimtoxysilane and further 2‐(thiophen‐2‐yl)‐1H‐benzo[d]imidazole was anchored on its surface. Then, palladium nanoparticles were fabricated on the surface of the modified BNPs and further the catalytic application was studied as recyclable biocatalyst in carbon–carbon coupling reactions such as Suzuki–Miyaura and Heck–Mizoroki cross‐coupling reactions. The structure of the catalyst was characterized using scanning electron microscopy, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, X‐ray diffraction and atomic absorption spectroscopy. The catalyst can be reused several times without a decrease in its catalytic efficiency. In addition to the several advantages reported, application of biochar as catalyst support for the first time is a major novelty of the present work.     

In situ stabilization of Pd(0) nanoparticles into a mixture of natural carbohydrate beads: A novel and highly efficient heterogeneous catalyst system for Heck coupling reactions

A convenient, mild and cost‐effective synthesis of palladium nanoparticles stabilized by a mixture of natural carbohydrate beads (gum arabic and pectin) as a new bio‐organometallic catalyst is reported. Powder X‐ray diffraction, transmission and scanning electron microscopies and energy‐dispersive X‐ray and UV–visible spectroscopies were employed to characterize this supported Pd nanoparticles/gum arabic/pectin catalyst. The nanocatalyst exhibited efficient activity in Mizoroki–Heck cross‐coupling reactions between various aryl halides and n ‐butyl acrylate under solvent‐free conditions. The catalyst can easily be recovered from the reaction system and reused several times with high yields. The products were obtained in short reaction times with excellent yields.     

New bis(N‐heterocyclic carbene) palladium complex immobilized on magnetic nanoparticles: as a magnetic reusable catalyst in Suzuki‐Miyaura cross coupling reaction

A new bis(N ‐heterocyclic carbene) (NHC) palladium complex supported on silica coated magnetic nanoparticles (MNPs) was prepared using the reaction of synthesized Pd‐NHC complex with MNPs. The Pd‐NHC complex was prepared using the reaction of a hydroxyl‐functionalized bis‐imidazolium ionic liquid. The Pd‐NHC organometallic complex was used as a heterogeneous recyclable and active catalyst in the Suzuki‐Miyaura reaction and various aryl halides were coupled with arylboronic acids in order to synthesize diverse biaryls in good to excellent yields. The prepared catalyst was characterized by use of some different microscopic and spectroscopic techniques including elemental analysis, FT‐IR spectroscopy, diffuse reflectance UV–Vis spectrophotometery, scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM) and X‐ray diffraction (XRD). The Pd‐NHC catalyst system is a magnetic reusable catalyst and it can be separated from the reaction mixture using an external magnetic field. The catalyst was reusable in the Suzuki‐Miyaura coupling reaction at least for 6 times without significant decreasing in its catalytic activity.     

Sulfonated palladium(II) N‐heterocyclic carbene complex immobilized on nano–micro size poly(4‐vinylpyridinium chloride) for Suzuki‐Miyaura cross‐coupling reaction

The sulfonated palladium(II) N‐heterocyclic carbene complex Pd^II(NHC)SO₃^?, supported on poly(4‐vinylpyridinium chloride), was used as a heterogeneous, recyclable and active catalyst for the Suzuki–Miyaura reaction. This catalyst was applied for coupling of various aryl halides with phenylboronic acid and the corresponding products were obtained in excellent yields and short reaction times. The catalyst was characterized using Fourier transform infrared and diffuse reflectance UV–visible spectroscopies, scanning electron microscopy and elemental analysis. After each reaction, the catalyst was recovered easily by simple filtration and reused several times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.