Engineered mesoporous ionic‐modified γ‐Fe2O3@hydroxyapatite decorated with palladium nanoparticles and its catalytic properties in water

A new mesoporous organic–inorganic nanocomposite was formulated and then used as stabilizer and support for the preparation of palladium nanoparticles (Pd NPs). The properties and structure of Pd NPs immobilized on prepared 1,4‐diazabicyclo[2.2.2]octane (DABCO) chemically tagged on mesoporous γ‐Fe₂O₃@hydroxyapatite (ionic modified (IM)‐MHA) were investigated using various techniques. The synergistic effects of the combined properties of MHA, DABCO and Pd NPs, and catalytic activity of γ‐Fe₂O₃@hydroxyapatite‐DABCO‐Pd (IM‐MHA‐Pd) were investigated for the Heck cross‐coupling reaction in aqueous media. The appropriate surface area and pore size of mesoporous IM‐MHA nanocomposite can provide a favourable hard template for immobilization of Pd NPs. The loading level of Pd in the nanocatalyst was 0.51 mmol g^?1. DABCO bonded to the MHA surface acts as a Pd NP stabilizer and can also lead to colloidal stability of the nanocomposite in aqueous solution. The results reveal that IM‐MHA‐Pd is highly efficient for coupling reactions of a wide range of aryl halides with olefins under green conditions. The superparamagnetic nature of the nanocomposite means that the catalyst to be easily separated from solution through magnetic decantation, and the catalytic activity of the recycled IM‐MHA‐Pd showed almost no appreciable loss even after six consecutive runs.     

Preparation of FePd‐RGO Bimetallic Composites with High Catalytic Activity for Formic Acid Electro‐Oxidation

FePd‐RGO composites through the growth of uniformly dispersed iron‐palladium bimetallic nanoparticles (NPs) on reduced graphene oxide (RGO) nanosheets were prepared by a two‐step method. The firstly formed Fe is used as the seed for the subsequent Pd growth. The formation of Fe NPs on RGO in the first step is performed by an in‐situ reduction reaction with the reducer ethylene glycol under oil bath at 180°C. NPs in the as‐prepared FePd‐RGO have an average particle size of 6.5 nm, and Pd is added to one side of Fe which leads to the formation of Fe‐Pd bimetallic interfaces. As compared with the commercial Pd black at the same loading, the composites have higher electro‐catalytic activity, better electrochemical stability and higher resistance to CO poisoning for formic acid electro‐oxidation.     

Magnetite tethered mesoionic carbene‐palladium (II): An efficient and reusable nanomagnetic catalyst for Suzuki‐Miyaura and Mizoroki‐Heck cross‐coupling reactions in aqueous medium

In this paper, a highly active, air‐ and moisture‐stable and easily recoverable magnetic nanoparticles tethered mesoionic carbene palladium (II) complex (MNPs‐MIC‐Pd) as nanomagnetic catalyst was successfully synthesized by a simplistic multistep synthesis under aerobic conditions using commercially available inexpensive chemicals for the first time. The synthesized MNPs‐MIC‐Pd nanomagnetic catalyst was in‐depth characterized by numerous physicochemical techniques such as FT‐IR, ICP‐AES, FESEM, EDS, TEM, p‐XRD, XPS, TGA and BET surface area analysis. The prepared MNPs‐MIC‐Pd nanomagnetic catalyst was used to catalyze the Suzuki–Miyaura and Mizoroki–Heck cross‐coupling reactions and exhibited excellent catalytic activity for various substrates under mild reaction conditions. Moreover, MNPs‐MIC‐Pd nanomagnetic catalyst could be easily and rapidly recovered by applying an external magnet. The recovered MNPs‐MIC‐Pd nanomagnetic catalyst exhibited very good catalytic activity up to ten times in Suzuki–Miyaura and five times in Mizoroki–Heck cross‐coupling reactions without considerable loss of its catalytic activity. However, MNPs‐MIC‐Pd nanomagnetic catalyst shows notable advantages such as heterogeneous nature, efficient catalytic activity, mild reaction conditions, easy magnetic work up and recyclability.     

Dimeric ortho‐palladated homoveratrylamine as an efficient homogeneous catalyst for copper‐free Sonogashira cross‐coupling reaction

The catalytic activity of ortho‐palladated [Pd{C6H2(CH2CH2NH2)‐(OMe)2,3,4}(m‐Br)]2, a complex of homoveratrylamine in the copper‐free Sonogashira coupling reaction has been investigated. This complex is a catalyst that is efficient, stable and non‐sensitive to air and moisture in the Sonogashira reaction. In this homogeneous catalytic system, various aryl halides were efficiently coupled with phenylacetylene in mostly moderate to good yields in N‐methylpyrrolidone at 100 °C under copper‐free conditions. Copyright © 2012 John Wiley & Sons, Ltd.     

Palladium–cadmium sulfide nanopowder at oil–water interface as an effective catalyst for Suzuki–Miyaura reactions

A simple and effective strategy is described for the synthesis of Pd–CdS nanopowder by the reduction of an organopalladium(II) complex, [PdCl₂(cod)] (cod = cis ,cis ‐1,5‐cyclooctadiene), in the presence of CdS quantum dots (QDs) at a toluene–water interface. We investigated the impact of addition of CdS QDs on catalytic activity of Pd nanoparticles (NPs). The Pd–CdS nanopowder functions as an efficient catalyst for Suzuki–Miyaura reactions for the formation of carbon–carbon bonds. There is a high electron density on Pd NPs and due to their high electron affinity they behave as an electron scavenger from CdS increasing the rate of oxidative addition, which is the rate‐determining step of the catalytic cycle, and, just as we expect, the C─C coupling reaction with the Pd–CdS nanopowder is faster and occurs in less time than that with Pd nanocatalysts. Compared to classical reactions, this method consistently has the advantages of short reaction times, high yields in a green solvent, reusability of the catalyst without considerable loss of catalytic activity and low cost, and is a facile method for the preparation of the catalyst.     

An efficient,mild and selective Ullmann‐type N‐arylation of indoles catalysed by Pd immobilized on amidoxime‐functionalized mesoporous SBA‐15 as heterogeneous and recyclable nanocatalyst

A wide range of N‐arylated indoles were selectively synthesized through intermolecular C(aryl)? N bond formation from the corresponding aryl iodides and indoles through Ullmann‐type coupling reactions in the presence of a catalytic amount of Pd immobilized on amidoxime‐functionalized mesoporous SBA‐15 (SBA‐15/AO/Pd(0)) under mild reaction conditions. These cross‐coupled products were obtained in excellent yields under mild conditions at extremely low palladium loading (ca 0.3 mol%), and the heterogeneous catalyst can be readily recovered by simple filtration and reused seven times with loss in its activity. Copyright © 2015 John Wiley & Sons, Ltd.     

C‐S cross‐coupling reaction using novel and green synthesized CuO nanoparticles assisted by Euphorbia maculata extract

In the present study, biosynthesis of CuO nanoparticles using a rapid, eco‐friendly, cost‐effective and efficient method has been reported employing aqueous Euphorbia maculata extract as mild, renewable and non‐toxic reducing and capping agents without adding any surfactants. The biogenic and green method has some benefits compared to conventional physical and chemical methods. It is simple, cheap and environmentally friendly. The biosynthesized CuO NP displayed a color change pattern (from sky blue to black) on preparation and presented its respective broad peak at 365 nm, which was analyzed by UV–Vis spectroscopy. Using the FT‐IR analysis, biomolecules in E. maculata extract which are responsible for bioreduction activity and synthesize of CuO NP, were identified. The XRD, EDX and FESEM results confirmed the successful synthesis of CuO nanoparticles of 18 nm sizes, with spherical and sponge crystal structure. The catalytic activity of biosynthesized CuO NPs was studied in C‐S cross‐coupling reaction. This method has the advantages of high yields, easy work‐up, and simple reusability. The recovered CuO NP can be reused four times without any considerable loss of its catalytic activity.     

Ultra‐small and highly dispersed Pd nanoparticles inside the pores of ZIF‐8: Sustainable approach to waste‐minimized Mizoroki–Heck cross‐coupling reaction based on reusable heterogeneous catalyst

The rapid development of nanomaterials, particularly advanced hybrid nanoparticles, has made new opportunities for the design and fabrication of high‐performance metal‐based catalysts. However, generating metal nanoparticles of desired size without aggregation is an important challenge for enhancing the catalytic activity of metal nanoparticles supported in the host matrix. In this work, a hybrid nanoporous material, namely Pd nanoparticles@N‐heterocyclic carbene@ZIF‐8, with a high internal surface area was successfully prepared using a dispersed anionic sulfonated N‐heterocyclic carbene–Pd(II) precursor inside the cavities of zeolitic imidazolate framework (ZIF‐8) using an impregnation approach followed by reduction with NaBH₄. The anionic sulfonated N‐heterocyclic carbene was found to be a superb ligand for the stabilization of Pd nanoparticles in the pores of ZIF‐8. The resulting system was applied to the Mizoroki–Heck cross‐coupling reaction, in which the catalyst showed high catalytic activity under mild reaction conditions.     

Heck coupling reaction using monomeric ortho‐palladated complex of 4‐methoxy‐ benzoylmethylenetriphenylphosphorane under microwave irradiation

The activity of [Pd(C₆H₄CH₂ NH₂‐κ²‐C‐N)PPh₃MOBPPY]OTf complex, A (MOBPPY = 4‐methoxybenzoylmethylenetriphenyl‐ phosphoraneylide), was investigated in the Heck–Mizoroki C? C cross‐coupling reaction under conventional heating and microwave irradiation conditions. The complex is an active and efficient catalyst for the Heck reaction of aryl halides. The yields were excellent using a catalytic amount of [Pd(C₆H₄CH₂ NH₂‐κ²‐C‐N)PPh₃MOBPPY]OTf complex in N‐methyl‐2‐pyrrolidinone (NMP) at 130 °C and 600 W. In comparison to conventional heating conditions, the reactions under microwave irradiation gave higher yields in shorter reaction times. Copyright © 2010 European Peptide Society and John Wiley & Sons, Ltd.     

Mesoporous Silica MCM‐41 Supported N‐Heterocyclic Carbene‐Pd Complex for Heck and Sonogashira Coupling Reactions

Heterocyclic carbene‐Pd complex was anchored onto the mesoporous silica MCM‐41 which exhibits high catalytic activity in Heck reaction under phosphine free reaction conditions for the reaction of iodo/bromoarenes with olefinic compounds such as butyl acrylate, isopropyl acrylate and styrene. This catalytic system also showed high activity for Sonogashira coupling reaction of various aryl halides under copper, phosphine and solvent‐free reaction conditions. The air and thermally stable catalyst were reused several times without significant loss of its activity. High efficiency of the catalyst along with its recycling ability and the rather low Pd‐loading demonstrated in both Heck and Sonogashira coupling reactions are the merits of the presented catalyst system.     

N‐Heterocyclic carbene/phosphite synergistically assisted Pd/C‐catalyzed Suzuki coupling of aryl chlorides

An N‐heterocyclic carbene and phosphite synergistically enhanced Pd/C catalyst system has been developed for Suzuki coupling of aryl chlorides and aryl boronic acids from commercially available Pd/C with sterically demanding N,N′‐bis(2,6‐diisopropylphenyl)imidazolylidene and trimethylphosphite. A remarkable increase in catalytic activity of Pd/C was observed when used along with 1 equiv. N,N′‐bis(2,6‐diisopropylphenyl)imidazolium chloride and 2 equiv. phosphite with respect to palladium in appropriate solvents that were found to play a crucial role in Pd/C‐NHC‐P(OR)₃‐catalyzed Suzuki coupling. A dramatic ortho‐substitution effect of carbonyl and nitrile groups in aryl chlorides was observed and explained by a modified quasi‐heterogeneous catalysis mechanism. The Pd/C catalyst could be easily recovered from reaction mixtures by simple filtration and only low palladium contamination was detected in the biparyl products. A practical process for the synthesis of 4‐biphenylcarbonitrile has therefore been developed using the N‐heterocyclic carbene/phosphite‐assisted Pd/C‐catalyzed Suzuki coupling. Copyright © 2013 John Wiley & Sons, Ltd.     

Green synthesis of supported palladium nanoparticles employing pine needles as reducing agent and carrier: New reusable heterogeneous catalyst in the Suzuki coupling reaction

A green method for the synthesis of supported Pd nanoparticles (NPs) using pine needle extract as the reducing agent and the extracted residue of pine needle (RPN) as the carrier is described. The Pd/RPN nanocomposites were characterized using Fourier transform infrared, UV–visible, inductively coupled plasma atomic emission and X‐ray photoelectron spectroscopies, transmission electron microscopy and X‐ray diffraction. The spherical Pd NPs had a mean particle size of 3.25 nm and were evenly distributed on the RPN surface. More importantly, the Pd/RPN nanocomposite, as a heterogeneous catalyst, presented superior catalytic activity for the Suzuki coupling reaction. The yield of the reaction of 4‐bromotoluene with phenylboronic acid catalyzed by Pd_0.03/RPN reached 98% with low Pd loading (0.1 mmol%) at room temperature for 30 min. In addition, the catalyst could be easily separated by centrifugation and reused at least six times without significant loss of activity.     

Recyclable Polymer‐Supported Nanometal Catalysts in Water

Two types of polymer‐supported nanometal catalysts with high catalytic activity and recyclability in water have been developed. One catalyst was composed of linear polystyrene‐stabilized metal nanoparticles (PS‐MtNPs). A palladium catalyst (PS‐PdONPs) was prepared in water by the thermal decomposition of Pd(OAc)₂ in the presence of polystyrene. The degree of immobilization of Pd, but not the size of the Pd nanoparticles, was dependent on the molecular weight and cross‐linking of the polystyrene. The PS‐PdONPs exhibited high catalytic activity for Suzuki, Heck, and Sonogashira coupling reactions in water and they could be recycled without loss of activity. Linear polystyrene was also suitable as a stabilizer for in situ generated PdNPs and PtNPs. The second catalyst was a polyion complex that was composed of poly[4‐chloromethylstyrene‐co‐(4‐vinylbenzyl)tributylammonium chloride] and poly(acrylic acid)‐stabilized PdNPs (PIC‐PdNPs). Aggregation and redispersion of PIC‐PdNPs were easily controlled by adjusting the pH value of the solution.     

Palladium‐catalyzed synthesis of 6‐allylcoumarins using organotin reagents as multicoupling organometallic nucleophiles

Derivatives of 6‐iodocoumarin undergoing a direct Stille cross‐coupling reaction with organotin compounds in the presence of a catalytic amount of Pd(PPh₃)₄ in dimethylformamide at 80°C is described in this study. It is the first report of the palladium‐catalyzed coupling of iodocoumarins with allyltributyltin under mild conditions to form alkylcoumarin compounds in good yields. © 2014 The Authors. Applied Organometallic Chemistry published by John Wiley & Sons, Ltd.     

Microwave‐Promoted Pd‐Catalyzed Synthesis of Dibenzofurans from Ortho‐Arylphenols

ortho‐Aryl phenols, synthesized via protecting group free Suzuki–Miyaura coupling of ortho‐halophenols and arene boronic acids, undergo a cyclization to dibenzofurans via oxidative C–H activation. The reaction proceeds under microwave irradiation in short reaction times using catalytic amounts of Pd(OAc)₂ without additional ligands.     

Well‐dispersed N‐heterocyclic carbene–palladium complex anchored onto poly(acrylic acid)/poly(vinyl alcohol) nanofibers: Novel,superior and ecofriendly nanocatalyst for the Suzuki–Miyaura cross‐coupling reaction

Polymeric nanocomposite@Pd is one of the crown jewels for the catalysis of cross‐coupling reactions. This Pd nanocomposite on various polymeric supports has been well established to catalyze cross‐coupling reactions, but its preparation supported on the surface of nanofibers has been largely overlooked. Herein, we report the preparation of a poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) nanofiber‐supported N‐heterocyclic carbene–Pd complex. The first step involves the preparation of PAA/PVA nanofibers using the electrospinning process. The second step comprises the reaction of water‐soluble poly(ethylene glycol)‐imidazole with modified PAA/PVA nanofibers followed by introduction of PdCl₂ to achieve successfully the desired nanocomposite. The catalytic activity of this nanocomposite was examined in the expeditious synthesis of biaryl compounds using the Suzuki–Miyaura cross‐coupling reaction under mild reaction conditions. The composite offers multiple features such as good hydrophilic properties, high surface area, admirable potential in repeatability tests and being recyclable for several runs without significant loss in its activity under the optimum reaction conditions. Our results showed the superior applicability of this novel nanocatalyst in terms of conversion reaction, yields and turnover frequencies. The structure of the catalyst was characterized using a variety of techniques.     

Ordered PdCu‐Based Nanoparticles as Bifunctional Oxygen‐Reduction and Ethanol‐Oxidation Electrocatalysts

The development of superior non‐platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen‐reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells, but still a great challenge. Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu‐based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo. Under the dual tuning on the composition and intermetallic phase, the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol‐oxidation reaction (EOR) than those of disordered PdCuM NPs, the commercial Pt/C and Pd/C catalysts. The density functional theory (DFT) calculations reveal that the improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on the Pd surface owing to the smaller atomic size of Cu, Co, and Ni.     

An improved practical Pd/C‐catalyzed Sonogashira cross‐coupling reaction for the synthesis of liquid crystals of trans‐cyclohexyltolans

An improved practical synthesis of liquid crystals of trans‐cyclohexyltolans by Sonogashira cross‐coupling reaction of 1‐iodo‐4‐(trans‐4‐alkylcyclohexyl)benzene with aromatic terminal alkynes in the presence of Pd/C (palladium on activated carbon) as low as 0.03 mol% of Pd and CuI (2 mol%) in a mixture solvent of acetone–water (5:2 in volume) is described. The liquid crystals could be obtained in high yields as a solid with excellent purity by simple filtration, and the filtrate could be reused several times while still retaining high catalytic activity. Copyright © 2010 John Wiley & Sons, Ltd.     

Amine‐bridged bis(phenol) ligands for efficient Pd‐catalyzed aqueous C‐C coupling reactions

The influence of ring size ( 5 or 6 ), chain length ( 1 , 2 or 3 ) and bulkiness of N‐aryl substituents in amine‐bridged bis(phenol) ligands ( 1 , 2 , 3 ) on palladium‐catalyzed aqueous C‐C coupling reactions were revealed. The homocoupling of arylboronic acid can be completed in neat water with the aid of a catalytic amount of p‐toluenesulfonyl chloride (TsCl) in a very short time under anaerobic or aerobic conditions. Interestingly, the same catalytic system was efficient for Suzuki–Miyaura reaction in aqueous acetone under aerobic conditions in the absence of TsCl. The crystal structures of ligand 1 and three unsymmetrical fluorine‐substituted biaryl derivatives were also reported. Copyright © 2013 John Wiley & Sons, Ltd.     

Highly efficient polymer‐stabilized palladium heterogeneous catalyst: Synthesis,characterization and application for Suzuki–Miyaura and Mizoroki–Heck coupling reactions

A suitable approach to stabilize palladium nanoparticles (Pd NPs), with an average diameter of 3–4 nm, on magnetic polymer is described. A new magnetic polymer containing 4′‐(4‐hydroxyphenyl)‐2,2′:6′,2″‐terpyridine (HPTPy) ligand was prepared by the polymerization of itaconic acid (ITC) as a monomer and trimethylolpropane triacrylate (TMPTA) as a cross‐linker and fully characterized. Pd NPs embedded on the magnetic polymer were successfully applied in Suzuki–Miyaura and Mizoroki–Heck coupling reactions under low palladium loading conditions, and provided the corresponding products with excellent yields (up to 98%) and high catalytic activities (TOF up to 257 hr^?1). Also, the catalyst can be easily separated and reused for at least consecutive five times with a small drop in catalytic activity.