Oxidation of hydrogen on palladium: Chemicurrents in the Schottky nanodiode

The oxidation of hydrogen on palladium was studied by the chemicurrents method using the nanosized catalytic Pd/n-Si Schottky diode. The chemicurrent was found to be generated when the reactions H₂+O₂ and H + O + H₂ + O₂ occurred on the palladium surface, occasionally in the auto-oscillation mode. A model was created that describes the complex kinetic behavior of the reaction. Mathematical modeling was performed and showed the possibility of complex auto-oscillations of chemicurrent similar to those obtained in experiments. The catalytic Schottky nanodiode method was shown to be effective for reaction visualization and can be used as a new physical method for investigating the chemical processes on the catalyst surface.     

MCM-41-supported bidentate phosphine palladium(0) complex as an efficient catalyst for the heterogeneous Stille reaction

A Stille coupling reaction of organostannanes with organic halides has been developed in the presence of a catalytic amount of MCM-41-supported bidentate phosphine palladium(0) complex (0.5 mol %) in DMF/H₂O (9:1) under air atmosphere in high yields. This polymeric palladium catalyst exhibits higher activity than Pd(PPh₃)₄ and can be reused at least 10 times without any decrease in activity.     

A quantum chemical consideration of ligand exchange in palladium(ii) aqueous and chloride complexes

The behavior of potassium tetrachloropalladate(II) in media simulating biological fluids has been studied. In aqueous solutions of NaCl, the aquation rate is higher than the rate of chloro ligand introduction into the internal coordination sphere of palladium. In HCl solutions, on the contrary, the process of palladium chloro complex formation predominates. The latter is apparently due to protonation of water molecules composing aqua complexes. By means of the ZINDO/1 method, the substitution of ligands – water molecules and hydronium ion – in planar complexes of palladium(II) by chloride ion has been investigated. All complexes containing H₂O and H₃O⁺ ligands, other than [Pd(H₂O)₄]²⁺, have intramolecular hydrogen bonds. In [Pd(H₂O)₃(H₃O)]³⁺ and trans-[Pd(H₂O)₂(H₃O)Cl]²⁺, a “non-classic” symmetric hydrogen bond O ··· H ··· O is established (ZINDO/1, RHF/STO-6G*). By the first three steps the substitution of hydronium ion in the internal sphere of palladium atom is more favorable thermodynamically, compared to water molecules. Logarithms of stepwise stability constants of palladium(II) chloride complexes correlate linearly to enthalpies (ZINDO/1, PM3) of water substitution by chloride ion.     

Recyclable and reusable NiCl2(PPh3)2/CuI/PEG‐400/H2O system for the sonogashira coupling reaction of aryl iodides with alkynes

A stable and highly efficient NiCl2(PPh₃)₂/CuI/PEG‐400/H₂O catalytic system for the Sonogashira reaction has been developed. In the presence of NiCl₂(PPh₃)₂ and CuI, the coupling reaction of aryl iodides with terminal alkynes was carried out smoothly in a mixture of poly(ethylene glycol) (PEG‐400) and water at 100°C with K₂CO₃ as base to afford a variety of arylacetylenes in good to excellent yields. The isolation of the products was readily performed by extraction with petroleum ether, and the NiCl₂(PPh₃)₂/CuI/PEG‐400/H₂O system could be easily recycled and reused six times without significant loss of catalytic activity. Our system not only avoids the use of easily volatile organic solvents but also solves the basic problem of catalyst reuse. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of protic agents on the catalytic activity of supported palladium catalysts in the copolymerization of ethylene with carbon monoxide

The influence of the addition of different amounts of MeOH, H₂O, and HCOOH on the activity of supported palladium catalyst in the copolymerization of CO with ethylene and the kinetic regularities of this reaction were studied for the first time. The maximum yield of the copolymer is attained when MeOH and H₂O or HCOOH and H₂O are simultaneously introduced into the reaction medium (toluene). The results obtained are consistent with the concepts about the role of protic agents in the formation of active intermediates and polymer molecules in the copolymerization of CO with ethylene in the presence of the homogeneous catalytic systems.     

Investigation of the state of palladium in the potassium palladium-11-tungstosilicate/alumina system by diffuse-reflectance IR spectroscopy

The influence of redox treatments on the state of palladium in the K₆[SiW₁₁PdO₃₉]·11H₂O/γ-Al₂O₃ system was investigated by diffuse-reflectance IR (DRIFT) spectroscopy using CO as a probe molecule. The K₆[SiW₁₁PdO₃₉]·11H₂O heteropoly-compound (HPC) and starting γ-Al₂O₃ support were studied for comparison. It was shown that palladium is present in HPC mainly in the form of Pd²⁺ ions. Treatment of HPC in an H₂ flow results in complete reduction of palladium to Pd⁰. The HPC is unstable in redox cycles at temperatures above 373 K. When the HPC was supported on alumina, the Keggin units were stabilized on the support surface and Pd⁺ formed in the oxidized sample. The supported K₆[SiW₁₁PdO₃₉]·11H₂O/γ-Al₂O₃ catalyst displays higher thermal stability and does not decompose during redox treatments at temperatures up to 723 K. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 7, pp. 1271–1275. July, 1999.     

Mixed-ligand palladium(II) complexes with amino acids,cytosine, and adenine

pH titration shows that 1 : 1 : 1 mixed-ligand complexes are formed in the systems palladium(II)-Cyt-Glu-H₂O (loggB = 19.73) and palladium(II)-Cyt-Lys-H₂O (logβ = 16.20). Complexes Pd(C₅H₅N₅)(C₅H₈NO₄)Cl, Pd(C₅H₅N₅)(C₆H₁₃N₂O₂)Cl, Pd(C₄H₅N₃O)(C₆H₁₃N₂O₂)Cl, and Pd(C₄H₅N₃O)(C₅H₈NO₄)Cl are synthesized and characterized by chemical analysis, X-ray powder diffraction, and thermogravimetry. The coordination mode of amino acids, cytosine, and adenine to the palladium(II) ion is determined.     

Preparation and catalytic properties of NR-stabilized palladium colloids

Palladium colloids revealing narrow particle size distributions can be obtained by chemical reduction using tetra–alkylammonium hydrotriorganoborates. Combining the stabilizing agent [NR] with the reducing agent [BEt₃H^?] provides a high concentration of the protecting group at the reduction centre. Alternatively, NR₄X (X = halogen) may be coupled to the metal salt prior to the reduction step: addition of N(octyl)₄Br to Pd(ac)₂ in THF, for example, evokes an active interaction between the stabilizing agent and the metal salt. Reduction of NR-stabilized palladium salts with simple reducing agents such as hydrogen at room temperature yields stable palladium organosols which may be isolated in the form of redispersible powders. The anion of the palladium salt is crucial for the success of the colloid synthesis. Electron microscopy shows that the mean particle size ranges between 1.8 and 4.0 nm. An X–ray–photoelectron spectrscopic examination demonstrated the presence of zerovalent palladium. These palladium colloids may serve as both homogeneous and heterogeneous hydrogenation catalysts. Adsorption of the colloids onto industrially important supports can be achieved without agglomeration of palladium particles. The standard activity of a charcoal catalyst containing 5% of colloidal palladium determined through the cinnamic acid standard test was found to exceed considerably the activity of the conventional technical catalysts. In addition, the lifespan of the catalyst containing a palladium colloid, isolated from the reduction of [N(octyl)₄]₂PdCl₂Br₂ with hydrogen, is superior to conventionally prepared palladium/charcoal (Pd/C) catalysts. For example, the activity of a conventional Pd/C catalyst is completely suppressed after 38×10³ catalytic cycles per Pd atom, whereas the colloidal Pd/C catalyst shows activity even after 96times;10³ catalytic cycles.     

Influence of chelate ring size on the properties of phosphine-sulfonate palladium catalysts

Phosphine-sulfonate based palladium is one of the most extensively studied catalyst systems in olefin polymerization.This type of catalyst features six-membered chelate ring size,and can enable the copolymerizations of ethylene with a wide variety of polar monomers.In this contribution,we decide to investigate the influence of chelate ring size on the properties of phosphinesulfonate palladium catalysts.As such,a series of phosphine-sulfonate ligands and the corresponding seven-membered ring Pd(II)complexes[κ~2-(P,O)-2-(CH_2-PR_1R_2)-4-methylphenyl-sulfonato]Pd(Me)(DMSO)(Pd1,R_1=R_2=Cy,Pd2,R_1=R_2=o-Me O-C_6H_4;Pd3,R_1=Ph,R_2=2-[2,6-(Me O)_2C_6H_3]C_6H_4;DMSO=dimethyl sulfoxide)were designed,prepared and characterized.These palladium complexes are moderately active when they were applied in ethylene polymerization and copolymerizations with methyl acrylate and butyl vinyl ether.However,their properties are greatly reduced from those of the classic six-membered ring phosphine-sulfonate palladium complex Pd2′.The experimental results indicate that the bigger chelate ring size can increase the ligand flexibility and damage the catalytic properties for the phosphine-sulfonate type palladium catalysts.     

A highly efficient and recyclable silica-supported palladium catalyst for alcohol oxidation reaction

A silica supported palladium catalyst (SiO₂@APTES-Pd) showed excellent activity and reusability for selective oxidation of alcohols to corresponding carbonyl compounds with H₂O₂ as oxidant under base free environment. A wide range of alcohols including aliphatic alcohols are tolerated as substrates with a low loading of palladium (0.1 mol %).     

A green and efficient method for synthesis of benzimidazoles using nano‐Fe3O4 in PEG‐400/H2O aqueous system under ambient conditions at room temperature

In this paper, a green and facile protocol was described which was efficient for synthesis of benzimidazoles using nano‐Fe₃O₄ catalyst with continuous bubbling of air as the oxidant in PEG‐400/H₂O aqueous system at room temperature. This protocol afforded the target products in good to excellent yields and the catalytic system could be recycled and reused without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical and spectroscopic studies of a new palladium(II) complex with N -acetyl-L-cysteine

Chemical and spectroscopic studies of a new palladium(II) N-acetyl-L-cysteine complex are described. Elemental analyses for the solid complex are consistent with the formula [Pd(C₅H₈NO₃S)₂]?·?H₂O or [Pd(NAC)₂]?·?H₂O. Solid-state ¹³C nuclear magnetic resonance (NMR), UV–Visible (UV–Vis) and infrared (IR) spectroscopic analyses are consistent with coordination of the ligand to palladium(II) through the nitrogen and sulfur atoms in a square-planar geometry. Thermogravimetric and differential thermal analyses confirmed the composition; final residue was identified as metallic palladium.     

Acid-base and coordination properties of some palladium(II)porphyrins

The speciation and reactions of palladium(II) complexes with meso-tetraphenylporphine (H₂TPP) and meso-tetraphenyl-β-octaethylporphine (H₂TetPOEP) were studied in H₂SO₄-H₂O and H₂SO₄-HOAc protic solvents. H-associated species of PdTPP and PdTetPOEP were found to exist in sulfuric acid with concentrations of 16.33–17.38 and 17.48–18.22 mol/L, respectively. The kinetics of one-electron oxidation of complexes in the coordinated aromatic macrocycle were studied. A third-order rate equation was determined, and the mechanism of the oxidation reaction was substantiated with kinetically significant stages of dioxygen coordination, electron transfer from the macrocyclic aromatic system to dioxygen, and H-association equilibrium between the complex and sulfuric acid. The effects of peripheral ethyl substituents in the macrocyclic ligand on the reactivity of palladium(II)porphyrins were revealed.     

Selective Synthesis of a Hexagonal Co(Ⅱ)-Substituted Sodium Zincophosphate via a Simple and Novel Route

A simple and novel route was provided for the preparation of the hexagonal Co(II)‐substituted sodium zincophosphate (CoZnPO‐HEX), which was obtained with ZnSO₄·7H₂O, CoCl₂·6H₂O and Na₃PO₄·12H₂O as raw materials and polyethylene glycol‐400 (PEG‐400) as a surfactant via a one‐step solid‐state reaction at low heating temperature (60°C), and characterized with X‐ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), diffuse reflectance spectra, thermogravimetric analysis and the 1st derivative of thermogravimetric analysis (TG/DTG) and transmission electron microscopy (TEM). The experimental results showed that the CoZnPO‐HEX was selectively formed via this reaction at ambient temperature in the presence of PEG‐400.     

Preparation of Ammonium Cerium Phosphate via Low-heating Solid State Reaction and Its Catalysis for Benzyl Acetate Synthesis

Ammonium cerium phosphate was prepared with (NH₄)₃PO₄·3H₂O and Ce(SO₄)₂·4H₂O as raw materials and PEG‐400 as surfactant via a solid state reaction at low‐heating temperature. The characterization result of XRD indicates that the molecular formula of the product was (NH₄)₂Ce(PO₄)₂·H₂O. The synthesis of benzyl acetate was carried out with H₂SO₄/ammonium cerium phosphate as catalyst, and uniform experimental design as well as data mining technology was applied to the experiments, in which the effect of the reaction time, the molar ratio of acid to alcohol and the amount of catalyst on the conversion yield of acetic acid were studied. When benzalcohol was 0.10 mol, under the optimal reaction conditions, i.e. reaction time of 174 min, 2.02 of molar ratio of acid to alcohol and 0.5 g of catalyst, the esterification rate of acetic acid was 97.9%. The ammonium cerium phosphate had potential for industry application since it not only was feasible and simple in synthesis technics, but also had good catalysis activity for the synthesis of benzyl acetate.     

Suzuki-Miyaura cross-coupling reaction of aryl bromides and chlorides with phenylboronic acid under aerobic conditions catalyzed by palladium complexes with thiosemicarbazone ligands

For the first time, palladium complexes with salicylaldehyde thiosemicarbazones were applied as catalyst precursors to the Suzuki-Miyaura reaction. These air and moisture stable phosphine-free systems efficiently catalyze the cross-coupling of aryl bromides and chlorides (from electron rich to electron poor) with phenylboronic acid in DMF/H₂O at 100 °C for 24 h, using Na₂CO₃ as base, without addition of free ligand or any promoting additive, and under aerobic conditions no significant homocoupling of phenylboronic acid to unsubstituted biphenyl was observed.     

Thermoanalytical and spectroscopic studies of the synthesis of suppokted palladium catalyst in A H2/PdCl2/SiO2 parent system

A 5 wt% Pd/SiO₂ catalyst was synthesized by heating PdCl₂-impregnated SiO₂ in H₂ at 300°C for 2 h. It was found that the metal particle dispersion is improved when the reduction step is preceded by calcination at 300°C for 2h. Thermogravimetry of the impregnated support in air, N₂ and H₂ atmospheres was used to monitor the interactions occurring during the various preparative steps (i.e. drying, calcination and reduction) of the catalyst. The solid prduct of each preparative step was characterized by X-ray diffractometry and UV/Vis diffuse reflectance spectroscopy. The results indicate that following the drying step (at 110°C in air) the palladium occurs in two detectable forms: PdCl₂ particles and Si?O?Pdⁿ⁺ surface species. The calcination appears to transform the PdCl₂ particles into the latter surface species. The H₂-reduction eventually converts the surface species into finely-dispersed Pd° metal particles (average size=8–14 nm). No other reduction products, such as Pd_ySi_x, were detected.     

MCM‐41‐supported mercapto palladium(0) complex: an efficient and recyclable catalyst for the heterogeneous Stille coupling reaction

The Stille cross‐coupling reaction of organostannanes with aryl halides was achieved in the presence of a catalytic amount of MCM‐41‐supported mercapto palladium(0) complex (1 mol%) in DMF? H₂O (9:1) under air atmosphere in good to high yields. This MCM‐41‐supported palladium catalyst can be reused at least 10 times without any decrease in activity. Copyright © 2009 John Wiley & Sons, Ltd.     

On the interaction of palladium with olefinic systems

We have performed all electron Hartree–Fock gradient calculations and geometry optimizations on systems composed of one to three palladium atoms and: CH₃ cation and anion, C₂H₄, C₂H₃NH₂, C₄H₄, NH₃, and (NH₃) + (C₂H₄). Several basis set considerations are discussed and the binding energies of Pd to these small molecules are reported. We find the counterpoise correction to the binding energies of these systems to be large. We also present MP2 calculations of the palladium binding energy with a large uncontracted palladium spd basis set in the PdC₂H₄ and PdNH₃ systems. The binding interaction between ethylene and palladium results in a mixing of the 4d–π* and 5s–π orbitals, and, is dissociative to the ethylene. The palladium-butadiene and palladium-cyclobutene relative stabilites and structures are interesting since these molecules could form from acetylene on a palladium surface. We find the Pd-butadiene cyclic structure to be 43 kcal/mol more stable than the Pd-cyclobutene product.     

Efficient cyanation of aryl halide with K4[Fe(CN)6]⋅3H2O catalyzed by a P–O bidentate chelate palladium complex under air

Cyanation of aryl halide with K₄[Fe(CN)₆]?3H₂O has been carried out in the presence of a high‐activity catalyst: an air‐stable P–O bidentate chelate palladium complex. This method is applicable to both activated and deactivated aryl halides, and even a variety of aromatic nitriles are obtained in good yields under aerobic conditions. Copyright © 2014 John Wiley & Sons, Ltd.