Palladium, properties

Dentistry. Most casting alloys meet the composition and properties criteria of specification no. 5 of the American Dental Association (37) which prescribes four types of alloy systems constituted of gold—silver—copper with addition of platinum, palladium, and 2inc. Composition ranges are specified, as are mechanical properties and minimum fusion temperatures. Wrought alloys for plates also may include the same constituents. Similarly, specification no. 7 prescribes nickel and two types of alloys for dental wires with the same alloy constituents (see Dental materials). 

Impurities in cmde metal can occur as other metals or nonmetals, either dissolved or in some occluded form. Normally, impurities are detrimental, making the metal less useful and less valuable. Sometimes, as in the case of copper, extremely small impurity concentrations, eg, arsenic, can impart a harmful effect on a given physical property, eg, electrical conductivity. On the other hand, impurities may have commercial value. For example, gold, silver, platinum, and palladium, associated with copper, each has value. In the latter situation, the purity of the metal is usually improved by some refining technique, thereby achieving some value-added and by-product credit. 

The platinum-group metals (PGMs), which consist of six elements in Groups 8— 10 (VIII) of the Periodic Table, are often found collectively in nature. They are mthenium, Ru rhodium, Rh and palladium, Pd, atomic numbers 44 to 46, and osmium. Os indium, Ir and platinum, Pt, atomic numbers 76 to 78. Corresponding members of each triad have similar properties, eg, palladium and platinum are both ductile metals and form active catalysts. Rhodium and iridium are both characterized by resistance to oxidation and chemical attack (see Platinum-GROUP metals, compounds). 

Physical and Mechanical Properties. Whereas there are some similarities in the physical and chemical properties between corresponding members of the PGM triads, eg, platinum and palladium, the PGMs taken as a unit exhibit a wide range of properties (2). Some of the most important are summarized in Table 2. 

Ruthenium and osmium have hep crystal stmetures. These metals have properties similar to the refractory metals, ie, they are hard, britde, and have relatively poor oxidation resistance (see Refractories). Platinum and palladium have fee stmetures and properties akin to gold, ie, they are soft, ductile, and have excellent resistance to oxidation and high temperature corrosion. 

Hardness of the aimealed metals covers a wide range. Rhodium (up to 40%), iridium (up to 30%), and mthenium (up to 10%) are often used to harden platinum and palladium whose intrinsic hardness and tensile strength are too low for many intended appHcations. Many of the properties of rhodium and indium. Group 9 metals, are intermediate between those of Group 8 and Group 10. The mechanical and many other properties of the PGMs depend on the physical form, history, and purity of a particular metal sample. For example, electrodeposited platinum is much harder than wrought metal. 

Copper [7440-50-8] Cu, produces a reddish color and reduces the melting pokit of the alloy. It produces heat-treatable compositions with gold, platinum, and palladium that result ki kicreased hardness, strength, and generally improved physical properties. The tarnish resistance of the alloy is usually decreased. The gold—copper, Au—Cu, system is the fundamental system of many dental gold alloys. Copper has a useful range of 0—20 wt %. 

Electrical Properties. Electrical properties are important for the corrosion protection of chip-on-board (COB) encapsulated devices. Accelerated temperature, humidity, and bias (THB) are usually used to test the embedding materials. Conventional accelerating testing is done at 85°C, 85% relative humidity, and d-c bias voltage. Triple-track test devices with tantalum nitride (Ta2N), titanium—palladium—gold (Ti—Pd—Au) metallizations with 76... 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

The temperature rise in the inlet stage is limited by taking advantage of the unique properties of palladium combustion catalysts. Under combustion conditions, palladium can be either in the form of the oxide or the metal. Palladium oxide is a highly active combustion catalyst, whereas palladium metal is much less active. Palladium oxide is formed under oxidizing conditions... 

Table 27.1 Some properties of the elements nickel, palladium and platinum...

The mechanism by which this low oxidation state is stabilized for this triad has been the subject of some debate. That it is not straightforward is clear from the fact that, in contrast to nickel, palladium and platinum require the presence of phosphines for the formation of stable carbonyls. For most transition metals the TT-acceptor properties of the ligand are thought to be of considerable importance and there is... 

Shaw concluded that hydrogenation of 3-alkyl-4-aminomethylene isoxazol-5-ones (184) in the presence of palladium catalyst resulted in the saturation of either the endocyclic double carbon-nitrogen bond or the exocyclic double C—C bond with the retention of the heterocyclic nitrogen-oxygen bond. Recent data reported by Kochetkov et al. on the properties, and in particular on hydrogenation, of isoxazolid-5-ones - indicate, however, that Shaw had probably ob-... 

Whereas the utility of these methods has been amply documented, they are limited in the structures they can provide because of their dependence on the diazoacetate functionality and its unique chemical properties. Transfer of a simple, unsubstituted methylene would allow access to a more general subset of chiral cyclopropanes. However, attempts to utilize simple diazo compounds, such as diazomethane, have never approached the high selectivities observed with the related diazoacetates (Scheme 3.2) [4]. Traditional strategies involving rhodium [3a,c], copper [ 3b, 5] and palladium have yet to provide a solution to this synthetic problem. The most promising results to date involve the use of zinc carbenoids albeit with selectivities less than those obtained using the diazoacetates. 

Hydrogenation of carbonyls, or incipient carbonyls such as phenols (86), in lower alcohol solvents may result in the formation of ethers. The ether arises through formation of acetals or ketals with subsequent hydrogenolysis. The reaction has been made the basis of certain ether syntheses (45,97). Reaction of alcohols with carbonyls may be promoted by trace contamination, such as iron in platinum oxide (22,53), but it is also a property of the hydrogenation catalyst itself. So strong is the tendency of palladium-hydrogen to promote acetal formation that acetals may form even in basic media (61). 

The ease of formation of the carbene depends on the nucleophilicity of the anion associated with the imidazolium. For example, when Pd(OAc)2 is heated in the presence of [BMIM][Br], the formation of a mixture of Pd imidazolylidene complexes occurs. Palladium complexes have been shown to be active and stable catalysts for Heck and other C-C coupling reactions [34]. The highest activity and stability of palladium is observed in the ionic liquid [BMIM][Brj. Carbene complexes can be formed not only by deprotonation of the imidazolium cation but also by direct oxidative addition to metal(O) (Scheme 5.3-3). These heterocyclic carbene ligands can be functionalized with polar groups in order to increase their affinity for ionic liquids. While their donor properties can be compared to those of donor phosphines, they have the advantage over phosphines of being stable toward oxidation. 

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