Improved Stability and Catalytic Activity of Palladium Nanoparticle Catalysts using Phosphine‐Functionalized Imidazolium Ionic Liquids

Palladium nanoparticles (Pd NPs) stabilized by 6 different phosphine‐functionalized ionic liquids (PFILs) were synthesized in imidazolium‐based ionic liquids (ILs) using H_2(g) (4 bar) as a reductant. Characterization showed well‐dispersed particles of ∼3 nm (TEM) and confirmed the PFIL stabilization of the NPs (XPS). The PFILs were composed of an imidazolium functionality separated from the phosphine group by a propyl or undecyl chain. The counter anions for both FILs and IL solvents were chosen from N‐bis(trifluoromethanesulfonyl)imide (Tf₂N⁻), trifluoromethanesulfonate (TfO⁻) or hexafluorophosphate (PF₆⁻). Colloidal suspensions of the Pd NPs were employed as biphasic hydrogenation catalysts for the reduction of the olefinic bond in styrene under mild conditions (50 °C, 4 bar H_2(g), 1.5 h). The PFIL‐stabilized Pd NPs were effective hydrogenation catalysts and showed superior activity and recyclability over NPs synthesized in the absence of PFILs. Poisoning tests of the Pd NP catalysts and characterization of the electronic properties of the phosphine were also performed.     

Recyclable Tridentate Stable Palladium(II) PCP‐Type Catalysts Supported on Silica for the Selective Synthesis of Lactones

Five‐ or seven‐membered ring lactones are synthesized, in good selectivity and high yields, by the cyclocarbonylation reaction of 2‐allylphenols, using a tridentate diphosphinoaryl ligand (PCP‐type) palladium(II) catalyst immobilized on silica ( A ) and silica supported dendrimers ( B, C and D ). These immobilized catalysts, which are highly active and can be recycled by simple filtration in air, and reused with only moderate loss of activity, combine the advantages of heterogeneous and homogeneous catalysts. These complexes are also stable towards oxygen and moisture.     

Palladium(0) Nanoparticles on Glass‐Polymer Composite Materials as Recyclable Catalysts: A Comparison Study on their Use in Batch and Continuous Flow Processes

Palladium particles were generated by reduction of palladate anions bound to an ion exchange resin inside microreactors. The size and distribution of the palladium particles differed substantially depending on the degree of cross‐linking and the density of ion exchange sites on the polymer/glass composites, the latter parameter having a larger influence than the former. The polymer phase of the composite materials was used for the loading with clusters composed of palladium particles which are 1 to 10 nm in diameter. The reactivity and stability of six different palladium‐doped polymer/glass composite samples for transfer hydrogenations was investigated both under conventional and microwave heating in the batch mode as well as under continuous flow conditions using the cyclohexene‐promoted transfer hydrogenation of ethyl cinnamate as a model reaction. Regarding the heating method it was found that catalysts that are composed of larger metal particles perform better under microwave irradiating conditions whereas samples with smaller particle sizes perform better under conventional heating. Comparing batch experiments with flow‐through experiments the latter technique gives better conversion. Reusability was better in microwave heated experiments than in traditional heating.     

Synthesis of V‐MCM‐41 Catalysts and Their Application in CO2‐Assisted Isobutane Dehydrogenation

A series of V‐MCM‐41 were in situ synthesized. The textual properties and vanadium species were systematically characterized. The results showed that the catalysts could still maintain a mesoporous structure and high specific surface area. The vanadium species were highly dispersed on the surface, with the coexistence of polymeric vanadium species. Isobutane dehydrogenation was performed by employing CO₂ as a soft oxidant. The results revealed an almost linear relationship between the activity and surface vanadium sites. Isolated vanadium species were more active for isobutane dehydrogenation. The isobutane dehydrogenation reaction in the presence of CO₂ could proceed simultaneously through oxidative dehydrogenation and non‐oxidative dehydrogenation followed by the reverse water gas shift reaction.     

脱硫催化剂(2-羧基酞菁钯键合MCM-41)的合成及表征

为了降低空气中逐渐增多的硫化物,首先合成了2-羧基酞菁钯,然后将其键合在MCM-41的表面,运用红外光谱、粉末衍射、扫描隧道显微镜对其进行了表征,最后测定了它的催化活性。结果表明:当MCM-41表面键合2-羧基酞菁钯之后,对噻吩的去处率达到了98%。     

Up to 96% Enantioselectivities in the Hydrogenation of Fluorine Substituted (E)‐2,3‐Diphenylpropenoic Acids over Cinchonidine‐Modified Palladium Catalyst

The enantioselective hydrogenation of methoxy‐ and fluorine‐substituted (E)‐2,3‐diphenylpropenoic acid derivatives was studied over cinchonidine‐modified, supported palladium catalysts in the absence and presence of benzylamine as additive. The fluorine substituent in the appropriate position was even more efficient than the methoxy group in increasing the optical purity of the saturated product. High enantioselectivities, up to 96%, were obtained in the hydrogenation of some disubstituted derivatives, unprecedented in the hydrogenation of prochiral unsaturated carboxylic acids over modified heterogeneous catalyst. The best optical purities were reached in the hydrogenation of derivates bearing a para‐substituent on the β phenyl and an ortho‐substituent on the α phenyl ring, respectively. The influence of the substituent on the β phenyl ring was attributed to the increase in the efficiency of the modifier‐substrate interaction by electronic effects or to a decrease in the adsorption strength of the substituted acid over modified surface sites. The beneficial effect of the ortho‐substituent on the α phenyl ring was assumed to be due to the additional interaction of this substituent with the modifier on the surface, its steric hindrance contributing only in a small part to the observed effect. These suggestions were supported by results obtained in the hydrogenations of some methyl‐substituted derivatives.     

Assisted Tandem Palladium(II)/Palladium(0)‐Catalyzed C‐ and N‐Arylations of Quinoxalin‐2(1 H)‐ones in Water

A straightforward assisted tandem palladium(II)‐ and palladium(0)‐catalyzed direct C‐3 and N‐4 arylation of quinoxalin‐2(1 H)‐ones with boronic acids and aryl halides in water as safe and cheap solvent is reported. This environmentally friendly catalytic protocol is compatible with a wide range of functional groups and allows construction of various biologically important quinoxalin‐2(1 H)‐one backbones.

     

Recoverable Palladium Catalysts for Suzuki–Miyaura Cross‐ Coupling Reactions Based on Organic‐Inorganic Hybrid Silica Materials Containing Imidazolium and Dihydroimidazolium Salts

The systems formed by palladium acetate [Pd(OAc)₂] and hybrid silica materials prepared by sol‐gel from monosilylated imidazolium and disilylated dihydroimidazolium salts show catalytic activity in Suzuki–Miyaura cross‐couplings with challenging aryl bromides and chlorides. They are very efficient as recoverable catalysts with aryl bromides. Recycling is also possible with aryl chlorides, although with lower conversions. In situ formation of palladium nanoparticles has been observed in recycling experiments.     

A Study of Two Highly Active,Air‐Stable Iron(III)‐μ‐Oxo Precatalysts: Synthetic Scope of Hydrophosphination using Phenyl‐ and Diphenylphosphine

The importance of phosphines in synthetic chemistry cannot be underestimated. Catalytic hydrophosphination offers an ideal method to prepare P−C bonds without the need for harsh reaction conditions or stoichiometric amounts of waste by‐product. We herein report our studies into two biocompatible iron(III) complexes in hydrophosphination chemistry using diphenylphosphine under mild and benign reaction conditions (room temperature, solvent‐free) and our extended exploration of hydrophosphination with phenylphosphine, which can be tuned to operate in the absence of catalyst under thermal conditions for single hydrophosphination or solvent‐free with an iron(III) precatalyst to generate the products of double hydrophosphination.

     

Supported Palladium Catalysts for Suzuki Reactions: Structure‐Property Relationships,Optimized Reaction Protocol and Control of Palladium Leaching

Palladium on metal oxides and on activated carbon with particular properties (high palladium dispersion, low degree of reduction, water content) are shown to be highly active (tunrover number, TON=20,000; turnover frequency, TOF=16,600), selective and robust catalysts for Suzuki cross‐couplings of aryl bromides and activated aryl chlorides. Catalysts and reaction protocol offer combined advantages of high catalytic efficiency under ambient conditions (air and moisture), easy separation and reuse and quantitative recovery of palladium. The palladium concentration in solution during the reaction correlates clearly with the progress of the reaction and indicates that dissolved molecular palladium is in fact the catalytically active species. Dissolved palladium is redeposited onto the support at the end of the reaction. Additional minimization of the palladium content in solution (down to 0.1 ppm) could be achieved by simple procedures which meet the requirements of pharmaceutical industry.     

Direct Coupling Reactions of Alkynylsilanes Catalyzed by Palladium(II) Chloride and a Di(2‐pyridyl)methylamine‐Derived Palladium(II) Chloride Complex in Water and in NMP

Symmetrical internal alkynes can be prepared either by diarylation of mono‐ and bis(trimethylsilyl)acetylene (TMSA and BTMSA) catalyzed by ligand‐less palladium(II) chloride or by a di(2‐pyridyl)methylamine‐derived palladium(II ) chloride complex 1 (typical 0.1–1 mol % of Pd loading) in water using pyrrolidine as base and tetra‐n‐butylammonium bromide as additive. Alternatively, this same process is performed in NMP in the presence of tetra‐n‐butylammonium acetate (TBAA) as base with even lower Pd loadings (0.001–1 mol % Pd). The same reaction conditions are applied to the synthesis of unsymmetrical internal alkynes by monoarylation of silylated terminal alkynes. Aryl iodides can be coupled with TMSA, BTMSA and silylated terminal alkynes under heating or at room temperature, whereas for aryl bromides couplings are performed under water reflux or at 110 °C in the case of NMP. Complex 1 can be reused during several cycles either in water or in NMP without loss of catalytic activity. These simple reaction conditions allow the preparation of internal alkynes without secondary products, most probably by succesive protiodesilylation‐Sonogashira coupling.     

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 palladium loading at 50 °C in ethanol/water under batch condition. Moreover, a flow apparatus, to optimize the efficiency of the isolation of the pure products and minimize waste (E‐factor), was investigated. For the first time the palladium catalyst and base (K₂CO₃) were placed in two separate columns allowing an easy recovery of the products with very low E‐factor values (<4). Waste production was reduced by over 99% compared to classic batch conditions. Because of the high Pd loading only 42 mg of catalysts were employed in the Suzuki reaction between 160 mmol of 4‐bromotoluene and 180 mmol of phenylboronic acid. No loss in activity was observed.     

Air‐Stable and Highly Active Dendritic Phosphine Oxide‐ Stabilized Palladium Nanoparticles: Preparation,Characterization and Applications in the Carbon‐Carbon Bond Formation and Hydrogenation Reactions

Dendrimer‐stabilized palladium nanoparticles were formed in the reduction of palldium bis(acetylacetonate) [Pd(acac)₂] in the presence of phosphine dendrimer ligands using hydrogen in tetrahydrofuran. The resulting Pd nanoparticles were characterized by TEM, ³¹P NMR and ³¹P MAS NMR. The results indicated that the dendritic phosphine ligands were oxidized to phosphine oxides. These dendrimer‐stabilized Pd nanoparticles were demonstrated to be efficient catalysts for Suzuki and Stille coupling reactions and hydrogenations. The dendritic wedges served as a stabilizer for keeping the nanoparticles from aggregating, and as a vehicle for facilitating the separation and/or the recycling of the Pd catalyst. In the case of the Suzuki coupling reaction, these Pd nanoparticles exhibited high catalytic efficiency (TON up to 65,000) and air stability as compared with the commonly used homogeneous catalyst tetrakis(triphenylphosphine)palladium [Pd(PPh₃)₄]. In addition, the results obtained from the bulky dendritic substrate suggest that the Pd nanoparticles might act as reservoir of catalytically active species, and that the reaction is actually catalyzed by the soluble Pd(0) and/or Pd(II) species leached from the nanoparticle surface.     

Water as an Ideal Solvent for the Synthesis of Easily Hydrolyzable Compounds: High‐Yield Preparation of 2‐Pyrrolecarbaldimines and their CVD/ALD‐Relevant Cu(II) Derivatives in H2O

Water was found to be an ideal solvent for the remarkably high‐yield, fast preparation of easily hydrolyzable 2‐pyrrolecarbaldimines. In the presence of Cu²⁺, the reaction afforded, in one step, the corresponding Cu(II) chelates which were demonstrated to meet the initial set of current microelectronics criteria for Cu metal deposition via a CVD/ALD process. Electronic effects of the substituent on the imino nitrogen of the Cu complexes were shown to strongly influence the coordination geometry at the Cu center.     

A novel porous nanocomposite of aminated silica MCM‐41 and nylon‐6: Isotherm,kinetic, and thermodynamic studies on adsorption of Cu(II) and Cd(II)

Porous amine‐modified MCM‐41/Nylon‐6 nanocomposite (NH₂‐MCM‐41/NY6 NC) was synthesized by a facile solution casting protocol, which was used as an effective adsorbent for the removal of Cu(II) and Cd(II) from aqueous media. The physicochemical properties of NH₂‐MCM‐41/NY6 NC were studied by scanning and transmission electron microscopies, thermogravimetric analysis, etc. The influence of pH, adsorbent dose, contact time and initial concentration on adsorption performance were investigated in detail. Kinetic and isotherm parameters were evaluated and the data fitted well to the pseudo‐second order and Freundlich isotherm model, respectively. The maximum adsorption capacities of Cu(II) and Cd(II) were about 35.84 and 27.5 mg·g^?1, respectively. The K_d of NH₂‐MCM‐41/NY6 NC for Cu(II) (> ) and Cd(II) (> ) ions uptake in aqueous solution, showed very good values. Thermodynamic parameters suggest that the adsorption is a spontaneous process with an endothermic nature. According to the results obtained, we conclude that this novel porous NH₂‐MCM‐41/NY6 NC could be used for the removal of heavy metal ions from an aqueous solution. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45383.     

Heterogeneous Palladium Catalysts Applied to the Synthesis of 2‐ and 2,3‐Functionalised Indoles

Heterogeneous palladium catalysts ([Pd(NH₃)₄]²⁺/NaY and [Pd]/SBA‐15) were applied to the synthesis of 2‐functionalised indoles, giving generally high conversions and selectivities (>89% yield) using only 1 mol % [Pd]‐catalyst under standard reaction conditions (polar solvent, 80 °C). For the synthesis of 2,3‐functionalised indoles by cross‐coupling arylation, the [Pd]/SBA‐15 catalyst was found to be particularly interesting, producing the expected compound with =35% yield after 12 days of reaction, which is comparable to the homogeneous catalyst, Pd(OAc)₂ (=48% yield). In the course of the study, the dual reactivity of the indole nucleus was demonstrated: aryl bromides gave clean C C coupling while aryl iodides led to a clean C N coupling.     

Hybrid Organic‐Inorganic Materials from Di‐(2‐pyridyl)methylamine‐Palladium Dichloride Complex as Recoverable Catalysts for Suzuki,Heck and Sonogashira Reactions

Hybrid silica materials containing the di‐(2‐pyridyl)methylamine‐palladium dichloride complex, prepared by sol‐gel cogelification, are efficient recyclable catalysts for Suzuki (aryl bromides and chlorides), Heck (aryl bromides) and Sonogashira reactions (aryl iodides and bromides). Formation of palladium(0) nanoparticles is observed in the Suzuki and Heck reactions but not in the Sonogashira coupling.     

Palladium(II)‐Catalyzed Hydration of Alkynylphosphonates to β‐Ketophosphonates

A highly efficient palladium(II)‐catalyzed hydration of a wide range of alkynylphosphonates to the corresponding β‐ketophosphonates has been developed to give high yields at 80 °C in 1, 4‐dioxane, with no acidic or alkaline cocatalysts required. The described catalytic system should provide an efficient alternative to highly toxic mercury‐catalyzed methodologies and be useful in synthetic programs.     

Palladium Nanoparticles Immobilized on Nano‐Silica Triazine Dendritic Polymer (Pdnp‐nSTDP): An Efficient and Reusable Catalyst for Suzuki–Miyaura Cross‐Coupling and Heck Reactions

A new catalyst based on palladium nanoparticles immobilized on nano‐silica triazine dendritic polymer (Pd_np‐nSTDP) was synthesized and characterized by FT‐IR spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X‐ray, transmission electron microscopy and elemental analysis. The size of the palladium nanoparticles was determined to be 3.1±0.5 nm. This catalytic system showed high activity in the Suzuki–Miyaura cross‐coupling of aryl iodides, bromides and chlorides with arylboronic acids and also in the Heck reaction of these aryl halides with styrenes. These reactions were best performed in a dimethylformamide (DMF)/water mixture (1:3) in the presence of only 0.006 mol% and 0.01 mol% of the catalyst, respectively, under conventional conditions and microwave irradiation to afford the desired coupling products in high yields. The Pd_np‐nSTDP was also used as an efficient catalyst for the preparation of a series of star‐ and banana‐shaped compounds with a benzene, pyridine, pyrimidine or 1,3,5‐triazine unit as the central core. Moreover, the catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity.     

Synthesis and characterization of tridentate phenoxy‐imine ligand [N,N,O] nickel(II) and palladium(II) complexes and their catalytic behaviors in vinyl polymerization of norbornene

In this study, new complexes LNiCl( 1 ), LNiBr( 2 ), LNiI( 3 ), and LPdCl( 4 ) (L = 4,6‐di‐tert‐butyl‐2‐(N‐(quinolin‐8‐yl)iminomethyl)phenolato) have been synthesized and characterized. X‐ray diffraction studies on Complexes 1 and 4 revealed that N, N, O, and halogen atoms coordinated to metal, with a nearly square planar geometries in all cases. All these complexes are robust and exhibit high activities for the addition polymerization of norbornene (NB) with methylaluminoxane as cocatalyst [up to 47.62 kg PNB(mmol of Ni)^?1h^?1] and also lead to various activities and molecular weights of polynorbornenes under different reaction conditions. It is noteworthy that Complexes 1 and 4 show better activity under higher reaction temperature of 80°C. However, Complex 2 showed lower activity, and Complex 3 was found nearly inert toward NB polymerization, probably, because of thermal instability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009