Copper with iridium

We plan to make studies on palladium-copper, iridium-copper, and platinum-copper catalysts to extend our investigation of the effect of varying miscibility of the components on the structural features of the bimetallic clusters present. With these additional systems, the whole range from complete immiscibility to total miscibility of copper with the Group VIII metal will be encompassed. 

Asymmetric allylboration, characteristics, 9, 197 Asymmetric allylic alkylation, allylic alcohols with copper, 11, 99 with iridium, 11, 105 with molybdenum, 11, 109 with nickel, 11, 102 with non-palladium catalysts, 11, 98 with platinum, 11, 103 reaction systems, 11, 112 with rhodium, 11, 104 with ruthenium, 11, 108 with tungsten, 11, 111... 

Zeolites as excellent stabilizing agents for Pd(II) or well dispersed Pd(0) were then used as a carrier for this reaction (35). It was shown that the activity of the catalyst depended chiefly on the ability of the transition metal ion to undergo easily redox cycles. In this respect, transition metal with quasi-permanent cationic state such as cobalt or with quasi permanent metallic state such as platinum exhibited the lowest activity. By contrast copper, rhodium, iridium and particularly palladium showed the highest activity though with varying selectivities. 

Comparison of this sequence with Fig. 33 shows clearly that the metals that are most active for olefin isomerization, rhodium (> 80°) and nickel, yield the least 1-butene in 1,3-butadiene hydrogenation the reverse is also true in that copper and iridium, being poor isomerization catalysts, give the most 1-butene. Platinum, ruthenium, and osmium occupy intermediate positions in the expected order. Furthermore, the activity of all metal catalysts for isomerization increases with increasing temperature and the yield of 1-butene from 1,3-butadiene decreases as the temperature is raised this agrees with expectation and helps to confirm the proposed mechanism. 

Solutions of acid copper sulfate (containing only chloride and carrier) were used as the copper electroplating bath. A piece of titanium mesh (diameter = 55 mm) coated with iridium oxide was used as an insoluble anode. The bath was pumped through the anode to the cathode under 1 l/min and controlled at 25 °C. The cathode rotating speed was maintained at 165 rpm. The copper electrodeposition tests were conducted under different electric field waveforms with an average cathodic current density of 25 to 32 ASF, which was controlled by the cell voltage. Samples were cross-sectioned with a focused ion beam scanning electron microscope (FIB-SEM) to inspect both the quality of the copper deposits in the trenches or via-holes. 

The UPS technique was briefly introduced in Section 4.3. It was extensively applied to ethene, ethyne and benzene chemisorbed at low temperatures (100-200 K) on single crystal surfaces of nickel, copper, palladium, iridium and platinum (Table 4.1), and, notwithstanding its constraint in observing all adsorbed species, it led to the conclusion that under these conditions the molecules were adsorbed without dissociation or rearrangement, i.e. in n or na states. This agrees with the conclusions reached by the other techniques discussed above. 

In chloride electrolyte systems, titanium anodes with iridium or ruthenium compound catalytic coatings are used to allow evolution of chlorine at the anodes. For these anodes, each short circuit from nodules and dendrites not only destroys the local active coating and its catalytic effect but also completely destroys any ability for that area to oxidize chloride to chlorine. Shorts thereby reduce the life of these anodes which is important since these anodes are relatively expensive compared to lead alloy anodes normally utilized in sulphate based systems. The use of such catalytic anodes is expanding with some sulphate electrolyte copper electrowinning plants now moving to a form of these titanium catalytic anodes a nickel plant has these anodes for mixed chloride/sulphate duty and there appears scope for further expansion into nickel sulphate electrowinning. 

For organometailic compounds, the situation becomes even more complicated because the presence of elements such as platinum, iron, and copper introduces more complex isotopic patterns. In a very general sense, for inorganic chemistry, as atomic number increases, the number of isotopes occurring naturally for any one element can increase considerably. An element of small atomic number, lithium, has only two natural isotopes, but tin has ten, xenon has nine, and mercury has seven isotopes. This general phenomenon should be approached with caution because, for example, yttrium of atomic mass 89 is monoisotopic, and iridium has just two natural isotopes at masses 191 and 193. Nevertheless, the occurrence and variation in patterns of multi-isotopic elements often make their mass spectrometric identification easy, as depicted for the cases of dimethylmercury and dimethylplatinum in Figure 47.4. 

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

Pyridazines form complexes with iodine, iodine monochloride, bromine, nickel(II) ethyl xanthate, iron carbonyls, iron carbonyl and triphenylphosphine, boron trihalides, silver salts, mercury(I) salts, iridium and ruthenium salts, chromium carbonyl and transition metals, and pentammine complexes of osmium(II) and osmium(III) (79ACS(A)125). Pyridazine N- oxide and its methyl and phenyl substituted derivatives form copper complexes (78TL1979). 

More than 200 ores are known to contain cobalt but only a few are of commercial value. The more important are arsenides and sulfides such as smaltite, C0AS2, cobaltite (or cobalt glance), CoAsS, and linnaeite, C03S4. These are invariably associated with nickel, and often also with copper and lead, and it is usually obtained as a byproduct or coproduct in the recovery of these metals. The world s major sources of cobalt are the African continent and Canada with smaller reserves in Australia and the former USSR. All the platinum metals are generally associated with each other and rhodium and iridium therefore occur wherever the other platinum metals are found. However, the relative proportions of the individual metals are by no means constant and the more important sources of rhodium are the nickel-copper-sulfide ores found in South Africa and in Sudbury, Canada, which contain about 0.1% Rh. Iridium is usually obtained from native osmiridium (Ir 50%) or iridiosmium (Ir 70%) found chiefiy in Alaska as well as South Africa. 

The most stable carbonyls of rhodium and iridium are respectively red and yellow solids of the form [M4(CO)i2] which are obtained by heating MCI3 with copper metal under about 200 atm of CO. The black cobalt analogue is more simply obtained by heating [Co2(CO)g] in an inert atmosphere... 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

The behaviour of iridium is closely analogous to that of rhodium its corrosion diagram is very similar and it is, with rhodium, one of the least corrodible of metals. It is unattacked by alkalis, acids or oxidising agents in aqueous solution, although a fused mixture of caustic potash and potassium nitrate will attack it. The metal has an excellent resistance to fused lead oxide, silicates, molten copper and iron at temperatures up to 1 500°C. Additions of iridium to platinum considerably raise the corrosion resistance of the latter to a very wide range of reagents. 

Thermocouples of platinum with an alloy of platinum and 10 per cent, of rhodium or iridium are used at higher temperatures, and of copper and constantan at lower temperatures. 

The acetylacetonates are stable in air and readily soluble in organic solvents. From this standpoint, they have the advantage over the alkyls and other alkoxides, which, with the exception of the iron alkoxides, are not as easily soluble. They can be readily synthesized in the laboratory. Many are used extensively as catalysts and are readily available. They are also used in CVD in the deposition of metals such as iridium, scandium and rhenium and of compounds, such as the yttrium-barium-copper oxide complexes, used as superconductors. 1 1 PI Commercially available acetyl-acetonates are shown in Table 4.2. 

Because of- the similarity in the backscattering properties of platinum and iridium, we were not able to distinguish between neighboring platinum and iridium atoms in the analysis of the EXAFS associated with either component of platinum-iridium alloys or clusters. In this respect, the situation is very different from that for systems like ruthenium-copper, osmium-copper, or rhodium-copper. Therefore, we concentrated on the determination of interatomic distances. To obtain accurate values of interatomic distances, it is necessary to have precise information on phase shifts. For the platinum-iridium system, there is no problem in this regard, since the phase shifts of platinum and iridium are not very different. Hence the uncertainty in the phase shift of a platinum-iridium atom pair is very small. 

There appears to be concentration of rhodium in the surface of the iridium-rhodium clusters, on the basis that the total number of nearest neighbor atoms about rhodium atoms was found to be smaller than the nunber about iridium atoms in both catalysts investigated. This conclusion agrees with that of other workers (35) based on different types of measurements. The results on the average compositions of the first coordination shells of atoms about iridium and rhodium atoms in either catalyst Indicate that rhodium atoms are also incorporated extensively in the interiors of the clusters. In this respect the iridium-rhodium system differs markedly from a system such as ruthenium-copper (8), in which the copper appears to be present exclusively at the surface. 

IH of alkynylamines has been performed with a variety of catalytic systems based on palladium [274-281], cobalt, rhodium, iridium, ruthenium, platinum, copper, silver, zinc, cadmium, mercury [279-281], nickel [279-282], gold [279-281, 283], and molybdenum [284] derivatives. 

This volume is concerned with fundamental developments in the coordination chemistry of the elements of Groups 9-12 since 1982. The individual chapters cover the coordination chemistry of cobalt, iridium, nickel, palladium, platinum, copper, silver and gold, zinc and cadmium, and mercury. Unfortunately, because of factors beyond the Editors control, the manuscript for the proposed chapter on rhodium was not available in time for publication. 

Violence of reaction depends on concentration of acid and scale and proportion of reactants. The following observations were made with additions to 2-3 drops of ca. 90% acid. Nickel powder, becomes violent mercury, colloidal silver and thallium powder readily cause explosions zinc powder causes a violent explosion immediately. Iron powder is ineffective alone, but a trace of manganese dioxide promotes deflagration. Barium peroxide, copper(I) oxide, impure chromium trioxide, iridium dioxide, lead dioxide, manganese dioxide and vanadium pentoxide all cause violent decomposition, sometimes accelerating to explosion. Lead(II) oxide, lead(II),(IV) oxide and sodium peroxide all cause an immediate violent explosion. 

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