Group 10 VIII

The classic catalyst consists of Co-Th02-MgO mixtures supported on Kieselguhr (see Ref. 269) group VIII metals, especially Ni, generally are active,... 

We consider next perhaps the bet understood catalyzed reaction the oxidation of CO over group VIII metal catalysts. The reaction is an important environmental one since it involves the conversion of CO to CO2 in automobile catalytic converters. The mechanism is straightforward ... 

These elements were unknown when Mendeleef constructed his periodic table, and are often said to constitute Group O . How ever, a more logical classification would be in Group VIII . 

In addition to the processes mentioned above, there are also ongoing efforts to synthesize formamide direcdy from carbon dioxide [124-38-9J, hydrogen [1333-74-0] and ammonia [7664-41-7] (29—32). Catalysts that have been proposed are Group VIII transition-metal coordination compounds. Under moderate reaction conditions, ie, 100—180°C, 1—10 MPa (10—100 bar), turnovers of up to 1000 mole formamide per mole catalyst have been achieved. However, since expensive noble metal catalysts are needed, further work is required prior to the technical realization of an industrial process for formamide synthesis based on carbon dioxide. 

Hydrogenation Catalysts. The key to catalytic hydrogenation is the catalyst, which promotes a reaction which otherwise would occur too slowly to be useful. Catalysts for the hydrogenation of nitro compounds and nitriles are generally based on one or more of the group VIII metals. The metals most commonly used are cobalt, nickel, palladium, platinum, rhodium, and mthenium, but others, including copper (16), iron (17), and tellurium... 

The oxidation reaction between butadiene and oxygen and water in the presence of CO2 or SO2 produces 1,4-butenediol. The catalysts consist of iron acetylacetonate and LiOH (99). The same reaction was also observed at 90°C with Group (VIII) transition metals such as Pd in the presence of I2 or iodides (100). The butenediol can then be hydrogenated to butanediol [110-63-4]. In the presence of copper compounds and at pH 2, hydrogenation leads to furan (101). 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

Cyclopentadiene itself has been used as a feedstock for carbon fiber manufacture (76). Cyclopentadiene is also a component of supported metallocene—alumoxane polymerization catalysts in the preparation of syndiotactic polyolefins (77), as a nickel or iron complex in the production of methanol and ethanol from synthesis gas (78), and as Group VIII metal complexes for the production of acetaldehyde from methanol and synthesis gas (79). 

The nine elements, Fe, Ru, Os Co, Rh, Ir Ni, Pd and Pt, together formed Group VIII of Mendeleev s periodic table. They will be treated here, like the other transition elements, in vertical triads, but because of the marked horizontal similarities it is not uncommon for Fe, Co and Ni to be distinguished from the other six elements (known collectively as the platinum metals) and the two sets of elements considered separately. 

Furan derivatives of group VIII elements 97KGS154. 

The reactions of the Group VIII di- and triborolyl or carboranes sandwiches are directed basically to their extension to multidecker derivatives. 

The formation of TMM complex from Group VIII transition metal such as Ir, Ru, and Os from precursors derived from (1) has been reported M.D. Jones, R. D.W. Kemmitt,/. Chem. Soc., Chem. Commun., 1985, 811-812. 

Catalysts. The methanation of CO and C02 is catalyzed by metals of Group VIII, by molybdenum (Group VI), and by silver (Group I). These catalysts were identified by Fischer, Tropsch, and Dilthey (18) who studied the methanation properties of various metals at temperatures up to 800°C. They found that methanation activity varied with the metal as follows ruthenium > iridium > rhodium > nickel > cobalt > osmium > platinum > iron > molybdenum > palladium > silver. 

Concerning consecutive reactions, a typical example is the hydrogenation of alkynes through alkenes to alkanes. Alkenes are more reactive alkynes, however, are much more strongly adsorbed, particularly on some group VIII noble metal catalysts. This situation is illustrated in Fig. 2 for a platinum catalyst, which was taken from the studies by Bond and Wells (45, 46) on hydrogenation of acetylene. The figure shows the decrease of... 

The results used for a subsequent comparison of catalytic activity of all group VIII metals are related by Mann and Lien to palladium studied at a temperature of 148°C. At this temperature the appearance of the hydride phase and of the poisoning effect due to it would require a hydrogen pressure of at least 1 atm. Although the respective direct experimental data are lacking, one can assume rather that the authors did not perform their experiments under such a high pressure (the sum of the partial pressures of both substrates would be equal to 2 atm). It can thus be assumed that their comparison of catalytic activities involves the a-phase of the Pd-H system instead of palladium itself, but not in the least the hydride. 

The Mechanism of Dehydration of Alcohols over Alumina Catalysts Herman Pines and Joost Manassen Complex Adsorption in Hydrogen Exchange on Group VIII Transition Metal Catalysts... 

Group VIII Fe Organic derivatives Methanol Terephthalic 49,182,... 

The dioxygen ligand in mononuclear group VIII transition metal complexes. J. S. Valentine, Chem. Rev., 1973, 73, 235-245 (101). 

High temperature coordination chemistry of group VIII. K. E. Johnson and J. R. Dickinson, Adv. Molten Salt Chem., 1973, 2, 83-198 (284). 

---