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At least 19 recordsLinked to original sources
PubMed2003

Phosphorescence spectra and triplet state lifetimes of palladium octaethylporphyrin, palladium octaethylchlorin and palladium 2,3-dimethyloctaethylisobacteriochlorin at 77 K.

The phosphorescence spectra and triplet state lifetimes of palladium octaethylporphyrin (PdOEP), palladium octaethylchlorin (PdOEC) and palladium 2,3-dimethyloctaethylisobacteriochlorin (PdOEiBC) in n-octane Shpolskii matrices at 77 K are reported. The lifetime and T(1)/S(0) origin energy of each complex are: PdOEP, 1.90+/-0.04 ms, 15162 cm(-1); PdOEC, 0.43+/-0.03 ms, 12547 cm(-1) and PdOEiBC, 0.59+/-0.03 ms, 12863 cm(-1).

Luminescence↗
PubMed2004

Cs2Pd3(P2O7)2 and Cs2Pd3(As2O7)2: a 3D palladium phosphate with a tunnel structure and a 2D palladium arsenate containing strings of palladium atoms.

Cs(2)Pd(3)(P(2)O(7))(2) (1) and Cs(2)Pd(3)(As(2)O(7))(2) (2) have been synthesized by molten flux reactions and characterized by single-crystal X-ray diffraction. The structure of 1 consists of discrete Pd(II)O(4) squares which are linked by P(2)O(7) groups via corner-sharing to generate a 3D framework containing 12-ring channels in which Cs(+) cations are located. Compound 2 adopts a 2D layer structure with the interlayer space filled with Cs(+) cations. Within a layer there are PdO(4) squares and As(2)O(7) groups fused together via corner-sharing. Adjacent layers are stacked such that strings of Pd atoms are formed. The PdO(4) squares show eclipsed and staggered stacks with alternate short and long Pd...Pd distances. The two compounds adopt considerably different structures although they have the same general formula: Cs(2)Pd(3)(X(2)O(7))(2). Compound 2 is the first palladium arsenate reported. Crystal data for 1: orthorhombic, space group Cmc2(1) (No. 36), a = 7.6061(4) A, b = 14.2820(7) A, c = 14.1840(7) A, and Z = 4. Crystal data for 2: tetragonal, space group P4/n (No. 85), a = 16.251(1) A, c = 5.9681(5) A, and Z = 4.

Journal Article↗
PubMed1996

Biological effects of palladium and risk of using palladium in dental casting alloys.

In dentistry, palladium is a very common component of dental casting alloys of all types, and its use has increased over the past several decades in response to the increased cost of gold. However, there have been recent controversies, particularly in Germany, over possible adverse biological effects of using palladium in dental alloys. Therefore, the purpose of this paper is to review the known biological effects of palladium and the likelihood that these effects can be caused by dental alloys which contain palladium. In an ionic form and at sufficiently high concentrations, palladium has toxic and allergic effects on biological systems. Palladium allergy almost always occurs in individuals who are sensitive to nickel. The carcinogenic potential of the palladium ion is still unclear, although there is some evidence that it is capable of acting as a mutagen. However, there are no well documented cases of adverse biological reactions to palladium in the metallic state. Furthermore, in spite of the potential adverse biological effects of palladium ions, the risk of using palladium in dental casting alloys appears to be extremely low because of the low dissolution rate of palladium ions from these alloys.

Animals↗
PubMed2002

Potentiodynamic polarization study of the in vitro corrosion behavior of 3 high-palladium alloys and a gold-palladium alloy in 5 media.

STATEMENT OF PROBLEM: Corrosion of cast alloy restorations may lead to their failure or adversely affect their biocompatibility. Although some documentation of the corrosion behavior of the high-palladium dental alloys exists, questions remain about their corrosion resistance and mechanisms. PURPOSE: This study compared the in vitro corrosion characteristics of 3 high-palladium alloys and 1 gold-palladium alloy in simulated body fluid and oral environments. MATERIAL AND METHODS: Two Pd-Cu-Ga alloys and 1 Pd-Ga alloy were selected; an Au-Pd alloy served as the control. The corrosion behavior for the as-cast and simulated porcelain-firing (heat-treated) conditions of each alloy (N = 5) was evaluated in 0.9% NaCl, 0.09% NaCl, and Fusayama solutions. Heat-treated specimens of each alloy (N = 5) were also tested in N(2)-deaerated 0.09% NaCl and Fusayama solutions (pH 4). After immersion in the electrolyte for 24 hours, the open-circuit potential (OCP) was measured, and linear polarization was performed from -20 mV to +20 mV (vs. OCP) at a scanning rate of 0.125 mV/s. Cyclic polarization was performed from -300 mV to +1000 mV and back to -300 mV (vs. OCP) at a scanning rate of 1 mV/s. Data were evaluated with analysis of variance and the Ryan-Einot-Gabriel-Welsch multiple-range test (alpha=.05). RESULTS: The OCP of each alloy varied with the condition (as-cast or heat-treated) and electrolyte used. Corrosion resistance was similar for the 4 alloys tested. For cyclic polarization, all alloys showed active-passive or spontaneous passive behavior in nearly all electrolytes. During some reverse scans, the 3 high-palladium alloys displayed 3 or 5 anodic peaks. No positive hysteresis was observed for any of the alloy/electrolyte combinations evaluated. CONCLUSION: The corrosion resistances of the 3 high-palladium alloys in simulated body fluid and oral environments were comparable to that of the gold-palladium alloy. The similar corrosion resistance for the 3 high-palladium alloys was attributed to their high noble metal content and theorized stable structure at the submicron level. Selective corrosion of different phases and elements, surface enrichment of palladium, and adsorption of species are possible corrosion mechanisms. The cyclic polarization results suggest that none of the 4 alloys would be prone to pitting or crevice corrosion under in vivo conditions, but crevice conditions should nonetheless be avoided for these alloys in the oral environment.

Adsorption↗
PubMed2006

Synthesis of palladium nanoparticles by sonochemical reduction of palladium(II) nitrate in aqueous solution.

The sonochemical synthesis of stable palladium nanoparticles has been achieved by ultrasonic irradiation of palladium(II) nitrate solution. The starting solutions were prepared by the addition of different concentrations of palladium(II) nitrate in ethylene glycol and poly(vinylpyrrolidone) (PVP). The resulting mixtures were irradiated with ultrasonic 50 kHz waves in a glass vessel for 180 min. The UV-visible absorption spectroscopy and pH measurements revealed that the reduction of Pd(II) to metallic Pd has been successfully achieved and that the obtained suspensions have a long shelf life. The protective effect of PVP was studied using Fourier transform infrared (FT-IR) spectroscopy. It has been found that, in the presence of ethylene glycol, the stabilization of the nanoparticles results from the adsorption of the PVP chain on the palladium particle surface via the coordination of the PVP carbonyl group to the palladium atoms. The effect of the initial Pd(II) concentration on the Pd nanoparticle morphology has been investigated by transmission electron microscopy. It has been shown that the increase of the Pd(II)/PVP molar ratio from 0.13 x 10(-3) to 0.53 x 10(-3) decreases the number of palladium nanoparticles with a slight increase in particle size. For the highest Pd(II)/PVP value, 0.53 x 10(-3), the reduction reaction leads to the unexpected smallest nanoparticles in the form of aggregates.

Free Radicals↗
PubMed1996

Microstructure and segregation behavior of palladium in silver-copper-palladium alloys.

It has been reported that the addition of palladium can modify the microstructure and improve the properties of Ag-Cu eutectic alloy as well as admixed Cu-rich amalgam. The purpose of this work was to study the microstructure and segregation behavior of palladium in a series of Ag-Cu-Pd alloys. All microstructural and microchemical results consistently indicated a strong tendency for palladium to form the ordered Cu3Pd superlattice in the copper-rich phase of the present ternary alloys. Transmission electron microscopic examination indicated that, in addition to the large Cu-rich particles, numerous small (typically tens of nanometers) Cu-rich particles were distributed in the Ag-rich phase. In the alloys containing 10 and 15 wt% Pd, the Cu3Pd superlattice had an L1(2)-type crystal structure. In the alloy containing 20 wt% Pd, the Cu3Pd had a periodic (regular) APB structure. The solubility of palladium in the Cu-rich phase was always much larger than that in the Ag-rich phase. The ratio of the palladium concentration in the copper-rich phase to that in the silver-rich phase decreased with the overall palladium content.

Chemical Phenomena↗
PubMed2002

(R)-Di-mu-acetato-kappa 2 O:O'-bis[[2-(1-aminoethyl)phenyl-kappa 2 C1,N]palladium(II)], (R)-di-mu-chloro-bis[[2-(1-aminoethyl)phenyl-kappa 2 C1,N]palladium(II)] and [SP-4-4]-(R)-[2-(1-aminoethyl)phenyl-kappa 2 C1,N]chloro(pyridine-kappa N)palladium(II).

The title complexes, [Pd(2)(C(8)H(10)N)(2)(C(2)H(3)O(2))(2)], (I), [Pd(2)(C(8)H(10)N)(2)Cl(2)], (II), and [Pd(C(8)H(10)N)Cl(C(5)H(5)N)], (III), respectively, have been prepared as intermediates and the final product of a cyclopalladation reaction sequence, and their structures studied by single-crystal X-ray diffraction. Complexes (I) and (II) represent the first structurally characterized dinuclear cyclopalladation products of primary amines. For (I) and (III), pseudosymmetry relates two independent molecules in the asymmetric unit.

Journal Article↗
PubMed2004

(2,2'-Bipyridine-kappa2N,N')(1,1-cyclobutanedicarboxylato-kappa2O,O')palladium(II), (1,1-cyclobutanedicarboxylato-kappa2O,O')(1,10-phenanthroline-kappa2N,N')palladium(II) monohydrate and (1,1-cyclobutanedicarboxylato-kappa2O,O')(1,10-phenanthroline-kappa2N,N')palladium(II) dihydrate.

In the three title compounds, [Pd(C(6)H(6)O(4))(C(10)H(8)N(2))], (I), [Pd(C(6)H(6)O(4))(C(12)H(8)N(2))].H(2)O, (IIa), and [Pd(C(6)H(6)O(4))(C(12)H(8)N(2))].2H(2)O, (IIb), respectively, each Pd(II) atom has a similar distorted cis-planar four-coordination geometry, completed by two O atoms of a bidentate 1,1-cyclobutanedicarboxylate anion and two N atoms of either a 2,2'-bipyridine or a 1,10-phenanthroline ligand.

Journal Article↗
PubMed1992

Nuclear magnetic resonance of hydrogen sorbed by powdered palladium metal and alumina-supported palladium.

Hydrogen in 0.2 micron beta-palladium powder and in an alumina-supported palladium catalyst was investigated by NMR spectroscopy. The dependence of the shift on hydrogen pressure and the hydrogen-to-palladium (H/Pd) ratio in beta-palladium hydride was determined for 273 K < T < 368 K. The activation energy for the process affecting the hydrogen shift is 9.4(+/- 0.5) kcal mol-1, similar to the enthalpy of transition from the alpha- to beta-phase. NMR measurements of hydrogen in alumina-supported palladium show a similar behavior, which may allow one to use NMR shifts as a barometer of the state of the hydrogen in the metal.

Adsorption↗
PubMed2005

The electroanalytical detection of hydrazine: a comparison of the use of palladium nanoparticles supported on boron-doped diamond and palladium plated BDD microdisc array.

We show that both a random distribution of palladium nanoparticles supported on a BDD electrode or a palladium plated BDD microelectrode array can each provide a sensing platform for the electrocatalytic detection of hydrazine. The palladium nanoparticle modified electrode displays a sensitivity and limit of detection of 60 mA mol(-1) L and 2.6 microM respectively while the array has a sensitivity of 8 mA mol(-1) L with a detection limit of 1.8 microM. The beneficial cost implications of using palladium nano- or micro-particles in sensors compared to a palladium macroelectrode are evident. Interestingly the array of the nanoparticles shows similar sensitivity and limit of detection to the microelectrode array which probably indicates that the random distribution of the former leads to 'clumps' of nanoparticles that effectively act as microelectrodes.

Boron↗
PubMed2003

Origin of the regio- and stereoselectivity in palladium-catalyzed electrophilic substitution via bis(allyl)palladium complexes.

Palladium-catalyzed allylic substitution of aryl allyl chlorides with aromatic and heteroaromatic aldehydes was performed in the presence of hexamethylditin. This procedure involves palladium-catalyzed formation of transient allylstannanes followed by generation of a bis(allyl)palladium intermediate, which subsequently reacts with the aldehyde electrophile. The catalytic substitution reaction proceeds with high regio- and stereoselectivity. The stereoselectivity is affected by the steric and electronic properties of the allylic substituents. Various functionalities including NO(2), COCH(3), Br, and F groups are tolerated under the applied catalytic conditions. Density functional calculations at the B3PW91/DZ+P level of theory were applied to study the steric and electronic effects controlling the regio- and stereoselectivity of the electrophilic addition. The development of the selectivity was studied by modeling the various bis(allyl)palladium species occurring in the palladium-catalyzed substitution of cinnamyl chloride with benzaldehyde. It was found that the electrophilic attack proceeds via a six-membered cyclic transition state, which has a pronounced chair conformation. The regioselectivity of the reaction is controlled by the location of the phenyl group on the eta(1)-allyl moiety of the complex. The stereoselectivity of the addition process is determined by the relative configuration of the phenyl substituents across the developing carbon-carbon bond. The lowest energy path corresponds to the formation of the branched allylic isomer with the phenyl groups in anti configuration, which is in excellent agreement with the experimental findings.

Journal Article↗
PubMed2004

Palladium-catalyzed electrophilic allylation reactions via bis(allyl)palladium complexes and related intermediates.

The synthetic scope of the allyl-palladium chemistry can be extended to involve electrophilic reagents. The greatest challenge in these reactions is the catalytic generation of an allyl-palladium intermediate incorporating a nucleophilic allyl moiety. A vast majority of the published reactions that involve palladium-catalyzed allylation of electrophiles proceed via bis(allyl)palladium intermediates. The eta(1)-moiety of the bis(allyl)palladium intermediates reacts with electrophiles, including aldehydes, imines, or Michael acceptors. Recently, catalytic electrophilic allylations via mono-allylpalladium complexes were also presented by employment of so-called "pincer complex" catalysts.

Journal Article↗
PubMed2005

Mesoporous palladium-the surface electrochemistry of palladium in aqueous sodium hydroxide and the cathodic reduction of nitrite.

The voltammetry of nanostructured palladium layers electrodeposited from a hexagonal liquid crystal phase onto platinum microdiscs show well defined peaks for the adsorption/desorption of hydrogen and surface oxidation/reduction in 2 M NaOH. These peaks are more clearly resolved than at smooth palladium and reveal the complications associated with hydrogen adsorption/desorption on palladium in aqueous alkaline solutions. The reduction of nitrite at the nanostructured palladium is also reported and it is shown that it occurs via a mechanism involving a chemical reaction between adsorbed hydrogen and adsorbed nitrite ion.

Adsorption↗
PubMed1992

Patch testing with pure palladium metal in patients with sensitivity to palladium chloride.

During a 15-month period, 536 patients being investigated for suspected contact dermatitis were patch tested with the European standard series and palladium chloride 1% pet. 13 patients (2.4%) had a positive allergic response to palladium chloride and all 13 were also allergic to nickel. 12 of these 13 patients consented to further patch testing with discs of pure palladium metal foil, and none reacted. We have shown previously that palladium chloride patch test material contains traces of nickel, and propose an explanation for these results in terms of the additive effect of allergens when tested in combination.

Adult↗
PubMed2001

Rate and mechanism of the reversible formation of cationic (eta3-allyl)-palladium complexes in the oxidative addition of allylic acetate to palladium(0) complexes ligated by diphosphanes.

The oxidative addition of the allylic acetate, CH2=CH-CH2-OAc, to the palladium(o) complex [Pd0(P,P)], generated from the reaction of [Pd(dba)2, with one equivalent of P,P (P,P = dppb = 1,4-bis(diphenylphosphanyl)butane, and P,P = dppf = 1,1'-bis(diphenylphosphanyl)ferrocene), gives a cationic (eta3-allyl)palladium(II) complex, [(eta3-C3H5)Pd(P,P)+]. with AcO as the counter anion. This reaction is reversible and proceeds through two successive equilibria. The overall equilibrium constants have been determined in DMF. Compared with PPh3, the overall equilibrium lies more in favor of the cationic (eta3-allyl)palladium(II) complex when bidentate P,P ligands are considered in the order: dppb > dppf > PPh3. The reaction proceeds via a neutral intermediate complex [(eta2-CH=CH-CHCH2-OAc)Pd0(P,P)], which has been kinetically detected. The rate constants of the successive steps have been determined in DMF by UV spectroscopy and conductivity measurements. The overall complexation step of the Pd0 by the allylic acetate C=C bond is faster than the oxidative addition/ionization step which gives the cationic (eta3-allyl)palladium(II) complex.

Journal Article↗
PubMed1996

Chemistry of Bis(aryloxo)palladium(II) Complexes with N-Donor Ligands: Structural Features of the Palladium-to-Oxygen Bond and Formation of O-H.O Bonds.

Reaction of palladium acetate with 2 equiv of sodium phenoxide in the presence of a chelate diamine ligand affords the complexes [Pd(OPh)(2)(N approximately N)] (N approximately N = bpy (1), tmeda (2), teeda (3), dpe (4), dmap (5)). These yellow to orange bis(phenoxo)palladium(II) complexes are thermally stable at room temperature in the solid state as well as in solution. Addition of an excess of pentafluorophenol to 1, 2, 4, and 5 affords crystalline complexes [Pd(OC(6)F(5))(2)(N approximately N)] (N approximately N = bpy (6), tmeda (7), dpe (8), dmap (9)). Crystals of 1 and 6 have been subjected to X-ray diffraction studies. Crystals of 1 are orthorhombic, space group P2(1)2(1)2(1) (no. 19), with a = 6.7655(6) Å, b = 16.0585(10) Å, c = 16.7275(13) Å, and Z = 4. Crystals of 6 are triclinic, space group P&onemacr; (no. 2), with a = 7.567(4) Å, b = 12.708(3) Å, c = 12.912(5) Å, alpha = 61.51(3) degrees, beta = 74.74(4) degrees, gamma = 88.78(4) degrees, and Z = 2. The molecular structures of 1 and 6 show them to be square-planar complexes, and the main structural difference between these complexes is the orientation of the aromatic rings. In 6 the OC(6)F(5) ligands are almost parallel in a face-to-face orientation (pi-pi stacking interactions), whereas in 1 the OC(6)H(5) units are skewed away from each other. An unexpected "mixed" alkoxo(aryloxo) complex [Pd(OCH(CF(3))(2))(OPh)(bpy)].HOPh (10) is formed when 1 is reacted with 1,1,1,3,3,3-hexafluoro-2-propanol. The molecular structure of 10 shows O-H.O hydrogen bonding (O.O = 2.642(8) Å) between the hydroxyl hydrogen of phenol and the oxygen atom of the phenoxide ligand as well as an additional C-H.O contact (C.O) = 2.95(1) Å), which can be regarded as the initial stage of a base-assisted beta-hydrogen elimination. Crystals of 10 are monoclinic, space group P2(1)/c, with a = 8.3241(14) Å, b = 11.0316(17) Å, c = 26.376(3) Å, alpha = 93.01(1) degrees, Z = 4. Spectroscopic data of complexes 1-10 indicate that the oxygen atom of the aryloxide or alkoxide ligand is extremely electron-rich, leading to high polarization of the palladium-to-oxygen bond. The bis(phenoxide) complexes 1, 2, and 4 associate with two molecules of phenol through O-H.O hydrogen bonds to form adducts [Pd(OPh)(2)(N approximately N)].2HOPh (N approximately N = bpy (11), tmeda (12), dpe (13)). The palladium complexes 6-9 with OC(6)F(5) groups show no tendency to form adducts with alcohols.

Journal Article↗
PubMed2005

Palladium(II)-catalyzed enyne coupling reaction initiated by acetoxypalladation of alkynes and quenched by protonolysis of the carbon-palladium bond.

[reaction: see text] Divalent palladium-catalyzed inter- and intramolecular enyne coupling reactions initiated by acetoxypalladation of alkynes were developed. The reaction involves the acetoxypalladation of the alkyne, followed by the insertion of the alkene and the protonolysis of the carbon-palladium bond. The protonolysis of the carbon-palladium bond in the presence of bidentate nitrogen containing ligands is the key step in completing the Pd(II) catalytic cycle. The nitrogen-containing ligands, like halides, served to favor the protonolysis of the carbon-palladium bond over the beta-H elimination in the Pd(II)-mediated reactions. The intermolecular coupling reactions provide an efficient method for synthesizing gamma,delta-unsaturated carbonyls. The intramolecular coupling reactions offer a method to construct a variety of synthetically important carbo- and heterocycles. The asymmetric version of such a cyclization was developed with moderate enantioselectivity when employing pymox (pyridyl monooxazoline) as the ligand.

Journal Article↗
PubMed2004

Diacetato-kappa2O-bis[(S)-1-(4-fluorophenyl)ethylamine-kappaN]palladium(II) and di-mu-acetato-kappa4O:O'-bis[[(S)-2-(1-aminoethyl)-5-fluorophenyl-kappa2C1,N]palladium(II)] benzene hemisolvate.

Complexes of the composition trans-[Pd(L)2(OAc)2] have been postulated as intermediates during cyclopalladation. The first structural characterization of such a precursor has now been achieved and its role in the reaction sequence has been established. Diacetato-kappa2O-bis[(S)-1-(4-fluorophenyl)ethylamine-kappaN]palladium(II), [Pd(O2CMe)2(4-FC6H3CHMeNH2)2] or [Pd(C2H3O2)2(C8H10FN)2], (I), was obtained from palladium(II) acetate and (S)-NH2CHMeC6H3F-4 in a 1:2 molar ratio. The intermediate was then reacted with additional palladium(II) acetate to give the acetate-bridged dinuclear complex di-mu-acetato-kappa4O:O'-bis[[(S)-2-(1-aminoethyl)-5-fluorophenyl-kappa2C1,N]palladium(II)] benzene hemisolvate, [Pd(4-FC6H3CHMeNH2)2(mu-O2CMe)]2.0.5C6H6 or [Pd2(C8H9FN)2(C2H3O2)2].0.5C6H6, (II).

Journal Article↗