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PubMed1996

X-ray diffraction studies of oxidized high-palladium alloys.

OBJECTIVE: The purpose of this study was to use x-ray diffraction (XRD) to obtain new information about the oxide layers on four representative oxidized high-palladium alloys. METHODS: Cast specimens of two Pd-Cu-Ga alloys and two Pd-Ga alloys, with both polished and etched surfaces and air-abraded surfaces, were subjected to oxidation procedures recommended by the manufacturers. The specimens were analyzed by x-ray diffraction using CuK alpha radiation, and the peaks were compared to appropriate Joint Committee on Powder Diffraction Standards (JCPDS). RESULTS: The surface preparation procedure had a profound effect on the phases present in the oxide layers. For the specimens that had been polished and etched, CuGa2O4 and beta-Ga2O3 were detected on the 79Pd-10Cu-9Ga-2Au alloy, whereas SnO2 and CuGa2O4 were detected on the 76Pd-10Cu-5.5Ga-6Sn-2Au alloy. The oxide layers on both Pd-Cu-Ga alloys contained Cu2O1 and the oxide layer on the 76Pd-10Cu-5.5Ga-6Sn-2Au alloy may contain beta-Ga2O3. The principal phase in the oxide layers on both Pd-Ga alloys that had been polished and etched was ln2O3, which exhibited extreme preferred orientation. No other phase was detected in the oxide layer on the 85Pd-10Ga-2Au-1Ag-1 ln alloy, whereas beta-Ga2O3 was found in the oxide layer on the 75Pd-6Ga-6Au-6Ag-6.5ln alloy. For the air-abraded specimens, beta-Ga2O2 was not present in the oxide layers on the Pd-Cu-Ga alloys, and beta-Ga2O3 was the major phase in the oxide layers on the Pd-Ga alloys. Palladium oxide(s) in varying amounts were detected for both surface preparations of the Pd-Cu-Ga alloys and for the air-abraded Pd-Ga alloys. Except for the 76Pd-10Cu-5.5Ga-6Sn-2Au alloy, the oxide layer caused minimal change in the lattice parameter of the palladium solid solution compared to that for the as-cast alloy. SIGNIFICANCE: Knowledge of the phases found in the oxide layers on these high-palladium alloys is of fundamental importance for interpreting differences in the adherence of dental porcelain to the metal substrates under static and dynamic conditions, and may provide guidance in the development of new high-palladium alloys with improved metal-ceramic bonding.

Copper↗

PubMed2001

Determination of palladium in human urine by high-performance liquid chromatography and ultraviolet detection after ultraviolet photolysis and selective solid-phase extraction.

The high-performance liquid chromatographic method with UV detection described below permits the selective determination of traces of palladium in human urine. After UV photolysis, during which the complete organic matrix was destroyed, the palladium was selectively enriched by solid-phase extraction (SPE). The reversed-phase C18 SPE column material was loaded with the ligand N,N-diethyl-N'-benzoylthiourea (DEBT) which shows an excellent complexing capacity for palladium in acidic solutions and at room temperature. The Pd(DEBT)2 complex was eluted with ethanol. After isocratic separation on the analytical column (MeOH/H2O 98:2 (v/v)), the complex was detected at 274 nm. The detection limit was 10 ng Pd/l. The relative standard deviations (RSD) of the within-series imprecision were in the range between 11% (75 ng Pd/l) and 7% (180 ng Pd/l). The between-day imprecision was 11% (75 ng Pd/l) and 5% (180 ng Pd/l). The recovery rates ranged between 94 and 96%. Using this method, urine samples of 44 persons from the general population were analysed. Only in one urine sample could palladium be detected. For comparison, 10 persons with occupational palladium exposure were examined. The urinary concentrations ranged from <10 to 2,538 ng/l.

Calibration↗

PubMed1997

Genotoxicity of platinum and palladium compounds in human and bacterial cells.

Platinum and palladium belong to the group of platinum elements and thus share many chemical properties. Platinum coordination complexes are known to be carcinogenic and genotoxic in mammalian and bacterial cells. However, little is known about palladium genotoxicity. This study compares and evaluates the genotoxic potential of selected platinum and palladium metal salts in mammalian and bacterial cells using the cytokinesis-block micronucleus test (MNT) with human lymphocytes and the bacterial SOS chromotest. Carboplatin, cisplatin(II), transplantin(II), PtCl4(IV), and K2PtCl4(II) caused a significantly elevated genotoxicity in the MNT and the SOS chromotest. The platinum compounds PtCl2(II) and K2PtCl6(IV), and the divalent palladium salts PdCl2(II), K2PdCl4(II), Pd(NH3)2J2(II), Pd(NH3)4Cl2(II), and transpalladium(II) were not genotoxic in the MNT nor in the SOS chromotest. Therefore, evidence for palladium genotoxicity seems to be low in mammalian and bacterial cells.

Adult↗

PubMed2005

Selective quantification of trace palladium in road dusts and roadside soils by displacement solid-phase extraction online coupled with electrothermal atomic absorption spectrometry.

There is a growing concern about the effect of palladium on human health because of the toxicity and increasing occurrence of palladium as a result of its extensive use in automotive catalytic converters. Development of reliable analytical methodologies for the determination of palladium in environmental materials is of great importance for critical evaluation of the possible risks for human health. In this work, a displacement solid-phase extraction technique was developed and online coupled to electrothermal atomic absorption spectrometry (ETAAS) for selective and sensitive determination of trace palladium in environmental samples without need of any special selective complexing agents, selective sorbents, and masking agents. The developed methodology involved the online formation of copper pyrrolidine dithiocarbamate (Cu-PDC), and the resultant Cu-PDC was extracted onto a microcolumn packed with the sorbent from a cigarette filter. Trace Pd(II) was selectively preconcentrated through loading the sample solution onto the microcolumn by online displacement reaction between Pd(II) and the extracted Cu-PDC on the microcolumn. The retained analyte was subsequently eluted with 40 microL of ethanol for online ETAAS determination. Interferences from coexisting heavy metal ions with lower stability of their PDC complexes relative to Cu-PDC were minimized. The tolerable concentrations of Cd-(II), Fe(III), Co(II), Mn(II), Cr(III), and Zn(II) were up to 2, 6, 40, 2, 1.5, and at least 100 mg L(-1), respectively. Compared with conventional solid-phase extraction methodology, the developed displacement solid-phase extraction protocol gave 2-4 orders of magnitude improvement in the maximum tolerable concentrations of coexisting heavy metal ions. With the consumption of only 2.8 mL of sample solution, an enhancement factor of 52 and a detection limit (3sigma) of 18 ng L(-1) were achieved at a sample throughput of 30 samples h(-1). The precision (RSD, n = 13) was 2.5% at the 1 microg L(-1) level. The present methodology was successfully applied to selective determination of trace palladium in local road dusts and roadside soils.

Automation↗

PubMed2002

A new pathway for hydroamination. Mechanism of palladium-catalyzed addition of anilines to vinylarenes.

The mechanism of the hydroamination of vinylarenes with anilines catalyzed by phosphine-ligated palladium triflates was uncovered. eta3-Arylethyl diphosphine palladium triflate complexes, which result from migratory insertion of vinylarene into a palladium hydride triflate, were shown to be the resting state of the catalytic cycle. A series of these complexes has been isolated and fully characterized. The [(R)-Tol-BINAP][1-(2-naphthyl)ethyl]palladium triflate derivative 1a was crystallographically characterized. This complex reacted with aniline to form the N-phenethylaniline product in 83% yield. Reaction of the benzylic derivative [(R)-Tol-BINAP](eta3-benzyl)palladium triflate with aniline also formed the N-benzylaniline product in a high 87% yield. Predominant inversion of configuration from the reaction between 1a, which is enantiopure, and aniline showed that external attack of the amine on the eta3-arylethyl ligand occurred to form the product. This product from reaction of aniline with 1a is the opposite enantiomer to that obtained from the catalytic process. Thus, a minor diastereomer gives the major enantiomer in the catalytic cycle, and the major diastereomer gives the minor enantiomer. Consistent with this assertion, kinetic studies showed that the major diastereomer formed product with a rate constant roughly 3.5 times slower than the rate constant for the catalytic process that contains all diastereomers.

Amination↗

PubMed2003

Formation and structure of self-assembled monolayers of alkanethiolates on palladium.

The adsorption of n-alkanethiols onto polycrystalline thin films of palladium containing a strong (111) texture produces well-organized, self-assembled monolayers. The organization of the alkane chains in the monolayer and the nature of the bonding between the palladium and the thiol were studied by contact angle measurements, optical ellipsometry, reflection absorption infrared spectroscopy (RAIRS), and X-ray photoelectron spectroscopy (XPS). The XPS data reveals that a compound palladium-sulfide interphase is present at the surface of the palladium film. The RAIR spectra, ellipsometry data, and wetting properties show that the palladium-sulfide phase is terminated with an organized, methyl-terminated monolayer of alkanethiolates. The local molecular environment of the alkane chains transitions from a conformationally disordered, liquidlike state to a mostly all-trans, crystalline-like structure with increasing chain length (n = 8-26). The intensities and dichroism of the methylene and methyl stretching modes support a model for the average orientation of an ensemble of all-trans-conformer chains with a tilt angle of approximately 14-18 degrees with respect to the surface normal and a twist angle of the CCC plane relative to the tilt plane of approximately 45 degrees. The SAMs are stable in air, although the sulfur present at the surface oxidizes in air over a period of 2-5 days at room temperature. The differences in chain organization between SAMs formed by microcontact printing and by solution deposition are also examined by RAIRS and XPS.

Air↗

PubMed2004

"Inverse-electron-demand" ligand substitution: experimental and computational insights into olefin exchange at palladium(0).

The mechanism of olefin substitution at palladium(0) has been studied, and the results provide unique insights into the fundamental reactivity of electron-rich late transition metals. A systematic series of bathocuproine-palladium(0) complexes bearing trans-beta-nitrostyrene ligands (ns(X) = X-C(6)H(4)CH=CHNO(2); X = OCH(3), CH(3), H, Br, CF(3)), (bc)Pd(0)ns(X) (3(X)), was prepared and characterized, and olefin-substitution reactions of these complexes were found to proceed by an associative mechanism. In cross-reactions between (bc)Pd(ns(CH)()3) and ns(X) (X = OCH(3), H, Br, CF(3)), more-electron-deficient olefins react more rapidly (relative rate: ns(CF)()3 > ns(Br) > ns(H) > ns(OCH)()3). Density functional theory calculations of model alkene-substitution reactions at a diimine-palladium(0) center reveal that the palladium center reacts as a nucleophile via attack of a metal-based lone pair on the empty pi orbital of the incoming olefin. This orbital picture contrasts that of traditional ligand-substitution reactions, in which the incoming ligand donates electron density into an acceptor orbital on the metal. On the basis of these results, olefin substitution at palladium(0) is classified as an "inverse-electron-demand" ligand-substitution reaction.

Alkenes↗

PubMed2000

Separation and enrichment of palladium and gold in biological and environmental samples, adapted to the determination by total reflection X-ray fluorescence.

The reductive co-precipitation of trace and ultra-trace elements together with mercury followed by complete evaporation of the mercury makes it possible to determine palladium and gold by total reflection X-ray fluorescence. Both elements can be detected without interferences at optimal sensitivity in the pg range. Thus, detection limits of, e.g., 2.5 ng L-1 for palladium and 2.0 ng L-1 for gold, in urine, were obtained. The precision was determined to 0.04 at a palladium concentration of about 200 ng L-1 urine and to 0.19 at a gold concentration of only 18 ng L-1. The recovery for a urine sample spiked with known amounts of palladium and gold amounted to > 95%. Results of the combined procedure are given for the determination of palladium and gold in the urine of non-exposed and occupationally exposed persons and in some other environmentally relevant samples.

Environmental Pollutants↗

PubMed2005

A unifying mechanism for all high-temperature Heck reactions. The role of palladium colloids and anionic species.

The Heck reaction has been the subject of intense investigation in the past decade. Many new types of catalysts have been developed in addition to the existing palladium/phosphine complexes. Prominent among these are palladacycles, pincers, several types of heterogeneous palladium catalysts, colloids and ligand-free palladium, usually in the form of Pd(OAc)2. Most of the newer types function only at higher temperatures, typically between 120 and 160 degrees C. It has been shown that irrespective of the catalyst precursor, none of these catalysts are stable at these high temperatures. They all have a tendency to form soluble palladium(0) colloids or nanoparticles, certainly with less reactive substrates such as aryl bromides or chlorides. The Heck reaction takes place by attack of the arylating agent on the palladium atoms in the outer rim of the nanoparticles. This leads to formation of monomeric or dimeric anionic palladium complexes that undergo the usual steps of the Heck mechanism as described by Amatore and Jutand.

Acetates↗

PubMed2002

Inductively coupled plasma-mass spectroscopy measurements of elemental release from 2 high-palladium dental casting alloys into a corrosion testing medium.

STATEMENT OF PROBLEM: The biocompatibility of high-palladium alloy restorations has been of some concern due to the release of palladium into the oral environment and sensitivity reactions in patients. PURPOSE: This study measured the in vitro elemental release from a Pd-Cu-Ga alloy and a Pd-Ga alloy into a corrosion testing medium. MATERIAL AND METHODS: Both alloys were cast into 12-mm-diameter x 1-mm-thick disks, subjected to heat treatment that simulated porcelain firing cycles, polished to a 0.05-mm surface finish, and ultrasonically cleaned in ethanol. Two specimens of each alloy were immersed 3 times (at 7, 70, and 700 hours) in an aqueous lactic acid/NaCl solution used for in vitro corrosion testing and maintained at 37 degrees C. The specimens were removed after each immersion time, and the elemental compositions of the solutions were analyzed with inductively coupled plasma-mass spectroscopy (ICP-MS). Elemental concentrations for the 2 alloys at each immersion time were compared with Student t test (alpha=.05). RESULTS: No significant differences in palladium release were found for the 7- and 70-hour solutions, but significant differences were found for the 700-hour solutions. Mean concentrations of palladium and gallium in the 700-hour solutions, expressed as mass per unit area of alloy surface, were 97 (Pd) and 46 (Ga) microg/cm(2) for the Pd-Cu-Ga alloy and 5 (Pd) and 18 (Ga) microg/cm(2) for the Pd-Ga alloy. CONCLUSION: Relative proportions of the elements in the solutions were consistent with the release of palladium and breakdown of microstructural phases found in the alloys. The results suggest that there may be a lower risk of adverse biological reactions with the Pd-Ga alloy than with the Pd-Cu-Ga alloy tested.

Biocompatible Materials↗

PubMed2006

Synthesis of N-o-methylphenyl-N'-(sodium p-aminobenzene-sulfonate) thiourea and its chromogenic reaction with palladium(II).

A new chromogenic reagent, N-o-methylphenyl-N'-(sodium p-aminobenzenesulfonate)thiourea (MSAT), has been synthesized and characterized by elemental analysis, (1)H-NMR, FT-IR and UV-Vis spectra. Based on the absorption spectrum of the colored complex of MSAT with palladium(II), a novel spectrophotometric method for the determination of palladium has been developed. In a pH 4.0 - 5.5 HAc-NaAc buffer solution, palladium(II) reacted with MSAT to form a stable yellow water-soluble complex with an apparent molar absorptivity of epsilon = 2.04 x 10(5) L mol(-1) cm(-1) at the maximum absorption of 318.0 nm. Beer's law was obeyed in the concentration range of 1.2 - 11.8 microg per 25 mL for palladium(II) with a correlation coefficient of 0.9997. The probable interfering ions and their tolerable limits have also been investigated in detail. The proposed method is simple, rapid, and sensitive, and has been applied to the determination of palladium in anode mud and ore samples with satisfactory results.

Hydrogen-Ion Concentration↗

PubMed1996

[The corrosion and electrochemical properties of new palladium-indium alloys for dentistry].

New palladium-based dental materials were examined in a wide spectrum of pH values from 3.8 to 9.6 at 37 degrees C for 315 h. Palladium dissolves in acid (pH 3.8) media with subsequent passivation (formation of complex compounds); areas of passiveness of palladium and its alloys for other pH values were found. The potentials of passiveness currents emerging in such cases were defined for all media, and corrosion curves of the alloys plotted. A film of palladium oxide appearing on the surface of the alloy was found to prevent further corrosion. High corrosion resistance in artificial saliva and high chemical inertness of palladium-indium alloy was revealed. The mechanisms of selective corrosion of the examined alloys and passiveness currents are discussed from the viewpoint of modern physical chemistry, and experimental data are explained. Use of such alloys in dentistry is shown to hold good promise.

Corrosion↗

PubMed2005

Aryl palladium carbene complexes and carbene-aryl coupling reactions.

Transmetalation of an aminocarbene moiety from [W(CO)5{C(NEt2)R}] to palladium leads to isolable monoaminocarbene palladium aryl complexes [{Pd(mu-Br)Pf[C(NEt2)R]}2] (R = Me, Ph; Pf = C6F5). When [W(CO)5{C(OMe)R}] is used, the corresponding palladium carbenes cannot be isolated since these putative, more electrophilic carbenes undergo a fast migratory insertion process to give alkyl palladium complexes. These complexes could be stabilized in the eta3-allylic form for R = 2-phenylethenyl or in the less stable eta3-benzylic fashion for R = Ph. Hydrolysis products and a pentafluorophenylvinylic methyl ether (when R = Me) were also observed. The monoaminocarbenes slowly decompose through carbene-aryl coupling to produce the corresponding iminium salts and, depending on the reaction conditions, the corresponding hydrolysis products. The electrophilicity of the carbene carbon, which is mainly determined by the nature of the heteroatom group, controls the ease of evolution by carbene-aryl coupling. Accordingly, no carbene-aryl coupling was observed for a diaminocarbene palladium aryl complex.

Journal Article↗

PubMedDate not supplied

Determination of palladium in gasoline by neutron activation analysis and automated column extraction.

Palladium in gasoline was determined by means of neutron activation analysis (NAA) and selective sorbent extraction. Unleaded gasoline consistent with DIN EN 228, RON 95 was irradiated at a thermal neutron flux of phith = 1.68 x 10(13)s(-1)cm(-2) and an epithermal neutron flux of 3.32 x 10(11)s(-1)cm(-2) for t(irr) = 12 h. The irradiated gasoline was digested with nitric acid and palladium was then separated as N,N-diethyl-N'-benzoylthiourea complex by an automated column pre-concentration procedure. The eluate of 50 microL was dried on a filter paper and the 88.03 keV photons resulting from the decay of 109Pd were detected in a low level HPGe spectrometer with an efficiency of 35.5%. Severe interferences with other matrix constituents, especially 82Br could be overcome and the detection limit for palladium was improved to 3.4 ng/L at a confidence level of 90%. Although the analytical procedure applied yielded the lowest detection limit for palladium obtained in gasoline up to now, no indications for the presence of palladium were found.

Journal Article↗

PubMed2000

Separation of trace amounts of palladium (II) with crown ether from hydrochloric acid and potassium thiocyanate media.

A new method for the separation of trace amounts of palladium from hydrochloric acid and potassium thiocyanate media has been established based on the formation of an ion-pair complex of palladium thiocyanate anion Pd(SCN)4(2-) and the cationic potassium complex of dicyclohexyl- 18-crown-6 (DC18C6) in chloroform. The effect of various factors (solvent, crown ether, potassium thiocyanate, hydrochloric acid, reagent concentration, shaking time, phase volume ratio, composition of the extracted species, foreign ions, etc.) on the extraction and back-extraction of palladium has been investigated. The method can be combined with subsequent FAAS determination of palladium. The procedure was applied to determine palladium traces in chloroplatinic acid and rhodium chloride.

Journal Article↗

PubMed2005

Synthesis and structure of a distorted octahedral palladium(II) complex coordinated with a tetrathioether ligand tethered with bulky substituents.

A new type of an o-phenylene-bridged tetrathioether ligand tethered with extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) groups, at its terminal sulfur atoms, TbtS[(o-phenylene)S]3Tbt (1), was synthesized by taking advantage of the coupling reaction of thiols with iodobenzenes using Cu2O in 2,4,6-trimethylpyridine. Complexation of 1 with Na2PdCl4 gave the corresponding dichloropalladium(II) complex, [PdCl2(1)] (7). The X-ray structural analysis of 7 indicated that the central palladium metal is in a distorted octahedral environment, where the two inner sulfur atoms of 1 and the two chlorine atoms form a square planar arrangement around the palladium metal and the two terminal sulfur atoms of 1 weakly coordinate to the palladium center at the axial positions. In addition, a phenyl analogue of 1, PhS[(o-phenylene)S]3Ph (2), was synthesized by a method similar to that for 1. Reaction of 2 with Na2PdCl4 gave the corresponding dichloropalladium(II) complex, [PdCl2(2)] (8). X-ray crystallography of 8 showed a type of the structure different from the distorted octahedral structure in 7, i.e., a square planar arrangement around the central palladium atom with the one terminal sulfur atom of 2, its neighboring sulfur atom, and the two chlorine atoms. The results of the NMR studies on 8 in a CDCl3 solution were not consistent with the results of the X-ray crystallography and suggested the coordination of the two inner sulfur atoms of 2 to the palladium metal, although a possibility of the existence of the rapid interconversion among isomers could not be excluded.

Journal Article↗

PubMed1996

Pd.H-C Interactions. Preparation and Structure of Orthometalated Tetranuclear Complexes of Palladium(II) and Platinum(II).

The reaction of 2-(1-naphthyl)benzothiazoline with palladium(II) acetate leads to helical mononuclear and orthometalated tetranuclear products. The molecular structures of mononuclear palladium(II) [Pd(H1-nabz)(2)] (1) (H(2)1-nabz = 2-N-(1-naphthylmethylideneamino)benzenethiolate), tetranuclear palladium(II) [Pd(4)(1-nabz)(4)] (2) and tetranuclear platinum(II) [Pt(4)(1-nabz)(4)] (3) have been determined by single-crystal X-ray diffraction method. Crystal data for complex 1 are as follows: a = 14.208(3) Å, b = 18.227(4) Å, c = 14.398(8) Å; beta = 94.55(3) degrees; V = 3717.0(23) Å(3); space group = P2(1)/n, Z = 4. Crystal data for the complex 2 are as follows: a = b = 15.798(3) Å, c = 23.728(4) Å; V = 5921.7(20) Å(3); space group = I4(1)/a, Z = 16 for the Pd(1-nabz) unit. Crystal data for the complex 3 are as follows: a = b = 15.496(2) Å, c = 24.348(3) Å; V = 5846.3(20) Å(3); space group = I4(1)/a, Z = 16 for the Pt(1-nabz) unit. The mononuclear palladium(II) complex reveals short ortho-hydrogen.palladium distances of 2.66(7) and 2.48(7) Å. These short distances and (1)H NMR studies provide a M.H-C interaction which can be regarded as a three-center four-electron interaction. The molecular structures of 2 and 3 confirm the formation of unusual tetranuclear compounds featuring a rare C,N,S-tridentate ligand derived from orthometalation of pendant side arm. The structural and chemical properties of the mononuclear palladium(II) complex 1 clearly suggest that 1 is a potential intermediate in the formation of the tetranuclear complex 2 by orthometalation reactions.

Journal Article↗

PubMed2001

Mechanism of olefin cyclopropanation by diazomethane catalyzed by palladium dicarboxylates: a density functional study.

The reaction of diazomethane with ethylene in the presence of palladium diformate has been studied through density functional calculations. Several mechanistic paths leading to the formation of cyclopropane have been studied. The results obtained show that the reaction of palladium diformate with diazomethane is more favorable than the reaction with ethylene. The reaction with diazomethane may lead to two different isomeric complexes: a methylene-inserted complex and a palladium-carbene complex. Insertion of methylene is the most favorable process, but the resulting complex is not suitable for cyclopropanation. The reaction with two additional diazomethane molecules makes the formation of the bismethylene-inserted palladium-carbene complex favorable. Attack of ethylene on this palladium-carbene complex leads to the formation of cyclopropane.

Journal Article↗