Pd–Schiff base complex supported on Fe3O4 magnetic nanoparticles: A new and highly efficient reusable catalyst for C–C bond formation in water

A protocol is introduced for the preparation of a new cage‐like Pd–Schiff base organometallic complex supported on Fe₃O₄ nanoparticles (Fe₃O₄@Schiff‐base‐Pd). The structure of the nanomagnetic catalyst was comprehensively characterized using Fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), energy‐dispersive X‐ray spectroscopy, Brunauer–Emmett–Teller measurements, scanning electron microscopy (SEM), transmission electron microscopy, X‐ray mapping, thermogravimetric analysis, vibrating sample magnetometry and inductively coupled plasma atomic emission spectroscopy. In the second stage, the catalytic activity of this catalyst was studied in the Suzuki and Heck cross‐coupling reactions in water as a green solvent. In this sense, simple preparation of the catalyst from commercially available materials, high catalytic activity, simple operation, short reaction times, high yields and use of green solvent are some advantages of this protocol. Finally, the nanocatalyst was easily recovered, using an external magnet, and reused several times without significant loss of its catalytic efficiency. In addition, the stability of the catalyst after recycling was confirmed using SEM, XRD and FT‐IR techniques.     

Immobilized Pd on (S)‐methyl histidinate‐modified multi‐walled carbon nanotubes: a powerful and recyclable catalyst for Mizoroki–Heck and Suzuki–Miyaura C–C cross‐coupling reactions in green solvents and under mild conditions

A stable and powerful heterogeneous palladium catalyst was synthesized using immobilized palladium on (S)‐methyl histidinate bonded onto the surface of multi‐walled carbon nanotubes. The catalyst was characterized using a combination of Fourier transform infrared and X‐ray photoelectron spectroscopies, transmission electron microscopy, X‐ray powder diffraction and inductively coupled plasma, thermogravimetric and elemental analyses. This new air‐ and moisture‐stable phosphine‐free palladium catalyst was found to be highly active and reusable in Mizoroki–Heck and Suzuki–Miyaura cross‐coupling reactions in poly(ethylene glycol) and aqueous ethanol as green solvents using an extremely small amount of palladium under mild conditions. Copyright © 2016 John Wiley & Sons, Ltd.     

Mono‐, bis‐ and tris‐piperidine fused imidazolinium salts: their in situ catalytic applications for C?C bond formation in aqueous solutions

The 1,5,6,7,8,8a‐hexahydroimidazo[1,5‐a]pyridine, 3, was quaternized with 2‐(bromomethyl‐1,3,5‐trimethylbenzene, 1,4‐bis(bromomethyl)‐2,3,5,6‐tetramethylbenzene, 2,4‐bis(bromomethyl)‐1,3,5‐trimethylbenzene, 1,3,5‐tris(bromomethyl)‐2,4,6‐trimethylbenzene and 1,3,5‐tris(bromomethyl)‐2,4,6‐triethylbenzene to obtain mono‐, bis‐ and tris‐imidazolinium salts (4–7) which were characterized by elemental analysis and NMR spectroscopy. In order to understand the effects of these changes on the N‐substituent and how they translate to catalytic activity, these new salts (4–7) with Pd(OAc)₂ were applied as in situ catalysts for Suzuki‐Miyaura and Heck‐Mirozoki cross‐coupling reactions of aryl chlorides and aryl bromides, respectively. The tris‐imidazolinium salts (7) were found to be more efficient than the related analogs 4–6. Copyright © 2009 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.     

Synthesis and characterization of MCM‐41‐Biurea‐Pd as a heterogeneous nanocatalyst and using its catalytic efficacy in C–C,C–N and C–O coupling reactions

MCM‐41‐Biurea‐Pd is introduced as a new, heterogeneous and reusable catalyst for C–C and C–heteroatom bond formation between various aryl halides, phenols and amines, in the presence of Ph₃SnCl (Stille reaction) in PEG‐400 as a green solvent at room temperature. The structure of the functionalized MCM‐41 was analysed using various techniques.     

Polymethyl methacrylate micro-spheres supported palladium: A new catalyst for Heck and Suzuki reactions

Polymethyl methacrylate (PMMA) micro-spheres, a kind of commercially available polymeric material was treated with PdCl₂ and formaldehyde giving a reagent with a palladium loading of 0.79 (wt.%). The Pd-PMMA catalyzed the highly efficient Heck and Suzuki reactions. The reactions can be performed under ligand-free conditions in an air atmosphere. The palladium catalyst is easily separated and can be reusable with negligible leaching of palladium.     

A highly active multi‐usable palladium pyridylfluorene film‐based catalyst for C–C cross‐coupling reactions

The two terminal pyridyl nitrogen atoms of 2,7‐bis(4‐pyridyl)fluorene ( 1 ) were coordinated to Pd(II) ions to give self‐assembled, multilayer films using the layer‐by‐layer (LbL) method. The films were prepared by alternately dipping the substrate, pre‐coated with a polyethyleneimine layer, in aqueous solutions of PdCl₂ and ethanol solutions of 1 . The resulting films were characterized using UV–visible absorption spectroscopy, atomic force microscopy (AFM), X‐ray photoelectron spectroscopy, scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectroscopy (ICP‐AES). UV–visible spectra and SEM images show almost uniform growth of the film in a near ideal LbL manner. AFM images show that nanostructured aggregates of Pd(II) complexes form on the surface. With an increase in the number of Pd(II)/ 1 bilayers, more particulate aggregates are distributed on the surface. When released from the substrate, the Pd(II) complex nanostructure shows high catalytic activity for Suzuki–Miyaura and Mizoroki–Heck cross‐coupling reactions. The catalyst loading is as low as 9.1 × 10^?3 mol% Pd, as measured using ICP‐AES, and high turnover numbers of up to 1.08 × 10⁴ are obtained. Copyright © 2015 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.     

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.     

Pd(0) complex of fuberidazole modified magnetic nanoparticles: A novel magnetically retrievable high-performance catalyst for Suzuki and Stille C-C coupling reactions

Fuberidazole has been successfully immobilized onto nano-Fe₃O₄ supported (3-chloropropyl)trimethoxysilane (3-CPTS) leading to a novel functionalized magnetic nanoparticle (FB/MNP). The Pd(0) complex, Pd-FB/MNP, was prepared by grafting Pd (OAc)₂ on FB/MNP and subsequent reduction of a synthesized Pd (II) complex using NaBH₄. Pd-FB/MNP has been characterized by FT-IR, SEM, TGA, XRD, ICP, EDS, BET and VSM. The Pd(0) complex proved to be an efficient phosphine- and halide-free recyclable heterogeneous catalyst for Suzuki as well as for Stille C-C coupling reactions showing high catalytic activity (up to 98%). Its catalytic activity in both reactions has been studied in PEG-400 as a green solvent. Besides, the selectivity of aryl iodide and aryl bromide over aryl chloride is observed during the C-C coupling reaction. The catalyst could be recovered easily from the reaction mixture using an external magnet device and recycled several times without considerable loss in activity. Additionally, the results of a palladium leaching test of the nano-catalyst demonstrate that no leaching of Pd took place during the C-C coupling process making the procedure environmentally friendly.     

A highly stable and efficient magnetically recoverable and reusable Pd nanocatalyst in aqueous media heterogeneously catalysed Suzuki C–C cross‐coupling reactions

Surface modification of Fe₃O₄ nanoparticles with triethoxyethylcyanide groups was used for the immobilization of palladium nanoparticles to produce Fe₃O₄/Ethyl‐CN/Pd. The catalyst was characterized using Fourier transform infrared, wavelength‐dispersive X‐ray, energy‐dispersive X‐ray and X‐ray photoelectron spectroscopies, field‐emission scanning electron and transmission electron microscopies, and X‐ray diffraction, vibrating sample magnetometry and inductively coupled plasma analyses. In this fabrication, cyano groups played an important role as a capping agent. The catalytic behaviour of Fe₃O₄/Ethyl‐CN/Pd nanoparticles was measured in the Suzuki cross‐coupling reaction of various aryl halides (Ar? I, Ar? Br, Ar? Cl) with phenylboronic acid in aqueous phase at room temperature. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture by applying an external magnet device and recycled seven times without any significant loss in activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Orthopalladated complexes of phosphorus ylide: Poly(N‐vinyl‐2‐pyrrolidone)‐stabilized palladium nanoparticles as reusable heterogeneous catalyst for Suzuki and Heck cross‐coupling reactions

The phosphorus ylide [Ph₃PCHC(O)C₆H₄‐NO₂–4] reacted with Pd(OAc)₂ to give the C,C‐orthometallated complex [Pd{κ²(C,C)‐C₆H₄PPh₂C(H)CO(C₆H₄‐NO₂–4)}(μ‐OAc)]₂, which underwent bridge exchange reaction with NaN₃, NaCl, KBr and KI, respectively, to afford the binuclear C,C‐orthopalladated complexes [Pd{κ²(C,C)‐C₆H₄PPh₂C(H)CO(C₆H₄‐NO₂–4)}(μ‐X)]₂ (X = N₃ ( 1 ), Cl ( 2 ), Br ( 3 ) and I ( 4 )). The complexes were identified using spectroscopy (infrared and NMR), CHNS technique and single‐crystal X‐ray structure analysis. Thereafter, palladium nanoparticles with narrow size distribution were easily prepared using the refluxing reaction of iodo‐bridged orthopalladated complex 4 with poly(N ‐vinyl‐2‐pyrrolidone) (PVP) as the protecting group. The PVP‐stabilized palladium nanoparticles were characterized using a variety of techniques including X‐ray diffraction, transmission and scanning electron microscopies, energy‐dispersive X‐ray spectroscopy, inductively coupled plasma analysis and Fourier transform infrared spectroscopy. The catalytic activity of the PVP‐stabilized palladium nanoparticles was evaluated in the Suzuki reaction of phenylboronic acid and the Heck reaction of styrene with aryl halides of varying electron densities. This catalyst exhibited excellent catalytic activity for Suzuki cross‐coupling reactions in ethanol–water. Notably, aryl chlorides which are cheaper and more accessible than their bromide and iodide counterparts also reacted satisfactorily using this catalyst. After completion of reactions, the catalyst could be separated using a simple method and used many times in repeat cycles without considerable loss in its activity.     

Cobalt supported on dendronized magnetic nanoparticles: A new highly efficient and recyclable catalyst for the Mizoroki–Heck cross‐coupling reaction

Polyamidoamine (PAMAM) is one of the most interesting types of hyperbranched polymers that carry a large number of amino groups on its surface. PAMAM has gained significant attention from synthetic organic chemists due to its structural characteristics, controllable structure, inner porosity, and ability to trap a wide range of ions and molecules. So, in this work, the PAMAM dendrimer was synthesized, grafted onto the surface of magnetite nanoparticles, and the resulting hybrid nanoparticles were then employed as suitable host for immobilizing cobalt nanoparticles. The newly developed catalyst was well characterized by Fourier transform‐infrared, X‐ray diffraction, thermogravimetric analysis, field emission‐scanning electron microscopy, transmission electron microscopy, atomic absorption spectroscopy, element mapping and energy‐dispersive X‐ray analysis. The efficiency of the as‐prepared nanocatalyst was evaluated for the Mizoroki–Heck cross‐coupling reactions. The MNP@PAMAM‐Co represented perfect catalytic efficiency and high selectivity for the Mizoroki–Heck cross‐coupling reaction compared with previously reported catalysts. The catalyst separation from the reaction mixture was easily achieved with the assistance of an external magnetic field, and its recycling was also investigated for five consecutive runs. Hot filtration confirmed no leaching of the active metal during the Heck coupling.     

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.     

Immobilized palladium nanoparticles on MNPs@A‐N‐AEB as an efficient catalyst for C‐O bond formation in water as a green Solvent

Palladium nanoparticles immobilized on the magnetic nanoparticles@2‐amino‐N‐(2‐aminoethyl) benzamide (MNPs@A‐N‐AEB.Pd⁰) have been presented as an efficient, and reusable magnetically heterogeneous catalyst for the C‐O coupling reaction, namely Ullmann condensation reactions in an aqueous medium. This heterogeneous catalyst shows superior reactivity for the C‐O arylation of different aryl halide (chloride, bromide, and iodide) with phenol derivatives to afford the desired products in good to excellent yields within short reaction time. Moreover, the catalyst can be easily recovered and reused for seven runs without loss of catalytic activity. The catalyst was characterized by several techniques, such as FT‐IR, SEM, TEM, EDS, XRD, TGA and ICP‐OES.     

Preparation of a titania‐supported highly dispersed palladium nano‐catalyst and its application in Suzuki and Heck coupling reactions

In this work, palladium complexes nanoparticles in titania are prepared by a pH‐controlled adsorption and without pH‐controlled adsorption method. This method results in high‐dispersion palladium on the titania surface. We demonstrate the use of the titania‐supported palladium as an efficient catalyst for Suzuki and Heck reactions of a representative range of aryl bromides and chlorides. The reusability of catalyst was tested, and deactivation process of the catalyst was not observed after four recycles. The catalysts were characterized by FT‐IR, NMR, elemental analysis, field emission scanning electron microscopy, transmission electron microscopy and X‐ray diffraction. Copyright © 2013 John Wiley & Sons, Ltd.     

Silica‐supported 3‐4,5‐dihydroimidazol‐1‐yl‐propyltriethoxysilanedichloropalladium(II) complex: Heck and Suzuki cross‐coupling reactions

A novel mesoporous silica‐nanotube‐supported 3‐4,5‐dihydroimidazol‐1‐yl‐propyltriethoxysilanedichloropalladium(II) complex was prepared and characterized. 3‐4,5‐Dihydroimidazol‐1‐yl‐propyltriethoxysilanedichloropalladium(II) and mesoporous silica‐supported 3‐4,5‐dihydroimidazol‐1‐yl‐propyltriethoxysilanedichloropalladium(II) were tested for catalytic activity for Heck coupling reactions between styrene and several aryl halides and Suzuki coupling reactions between phenylboronic acid and several aryl halides. Copyright © 2003 John Wiley & Sons, Ltd.     

Pd‐SBT@MCM‐41: As an efficient,stable and recyclable organometallic catalyst for C‐C coupling reactions and synthesis of 5‐substituted tetrazoles

A palladium S‐benzylisothiourea complex was anchored on functionalized MCM‐41 (Pd‐SBT@MCM‐41) and applied as efficient and reusable catalyst for the synthesis of 5‐substituted 1H –tetrazoles using [2 + 3] cycloaddition reaction of various organic nitriles with sodium azide (NaN₃) in poly(ethylene glycol) (PEG) as green solvent. Also this catalyst was applied as an versatile organometallic catalyst for Suzuki cross‐coupling reaction of aryl halides and phenylboronic acid (PhB(OH)₂) or sodium tetraphenyl borate (NaB(Ph)₄). This nanocatalyst was characterized by thermal gravimetric analysis (TGA), X‐ray Diffraction (XRD), scanning electron microscopy (SEM), inductively Coupled Plasma (ICP) and N₂ adsorption–desorption isotherms techniques. Recovery of the catalyst is easily achieved by centrifugation for several consecutive runs.     

Palladium nanoparticles supported on agarose‐catalyzed Heck–Matsuda and Suzuki–Miyaura coupling reactions using aryl diazonium salts

In this article, palladium nanoparticles supported on agarose were used as an efficient catalyst for Heck–Matsuda and Suzuki–Miyaura coupling reactions of structurally different aryldiazonium tetrafluoroborate substrates in aqueous media. Heck–Matsuda reactions proceeded at 40°C whereas Suzuki‐Miyaura reactions were carried out at room temperature. Both reactions required low catalyst loading. The catalyst was also recycled for the model reaction for three runs. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of substituted biaryls via Suzuki,Stille and Hiyama cross‐coupling and homo‐coupling reactions by CN‐dimeric and monomeric ortho‐palladated catalysts

The catalytic activity of dimeric [Pd{C₆H₂(CH₂CH₂NH₂)–(OMe)₂,2,3}(μ‐Br)]₂ and monomeric [Pd{C₆H₂(CH₂CH₂NH₂)–(OMe)₂,2,3}Br(PPh₃)] complexes as efficient, stable and air‐ and moisture‐tolerant catalysts was investigated in the Suzuki, Stille and Hiyama cross‐coupling and homo‐coupling reactions of various aryl halides. Substituted biaryls were produced in excellent yields in short reaction times using catalytic amounts of these complexes. The monomeric complex was demonstrated to be more active than the corresponding dimeric catalyst for the cross‐coupling reaction of unreactive aryl bromides and chlorides. The combination of homogeneous metal catalysts and microwave irradiation gave higher yields of products in shorter reaction times. Copyright © 2013 John Wiley & Sons, Ltd.