Group 9 VIII rhodium

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... 

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. 

The dominant role of copper catalysts has been challenged by the introduction of powerful group VIII metal catalysts. From a systematic screening, palladium(II) and rhodium(II) derivatives, especially the respective carboxylates62)63)64-, have emerged as catalysts of choice. In addition, rhodium and ruthenium carbonyl clusters, Rh COJjg 65> and Ru3(CO)12 e6), seem to work well. Tables 3 and 4 present a comparison of the efficiency of different catalysts in cyclopropanation reactions with ethyl diazoacetate under standardized conditions. 

It is a matter of speculation as to whether or not the activity would pass through a significant maximum at a surface composition between 0 and 30% Rh. It is interesting to note in this connection that the magnetic susceptibility (156, 157) and the electronic specific heat coefficient (156) increase from low values at 60% Ag-Pd through pure palladium and reach a maximum at - 5% Rh-Pd, thereafter decreasing smoothly to pure rhodium. Activity maxima have also been reported for reduced mixed oxides and supported alloys of group VIII metal pairs. For example, in the... 

The mentioning of exotic hydroformylation catalysts in patents does not reflect their real importance, because it is frequently done for completeness ( metals of Group VIII ). Sometimes cooperative or synergistic effects are claimed when bimetallic catalysts are used. A recent example for man-ganese/rhodium is found in [ 10,11 ]. 

The reaction is catalyzed by a group VIII metal species, particularly that of rhodium or palladium. The initial metal species may be any variety of complexes (e.g., PdCl2 Pd acetate, etc.). A source of halide is necessary iodide is especially effective. The most convenient source is methyl iodide, since it is likely a reaction intermediate. In addition, an organic promoter must be included for catalytic activity. These promoters are generally tertiary phosphines or amines. Also, chromium complexes were found to have an important promotional effect. 

This preparation is an illustration of the hydroformylation of olefins (oxo synthesis). The reaction occurs in the presence of soluble catalytic complexes containing metals of Group VIII of the periodic system. Although the metal originally used by Roelen and still largely used in the industry for the production of aliphatic aldehydes and alcohols is cobalt, the most active and selective catalysts are rhodium-containing compounds. The catalytic activity of the other Group VIII metals is in... 

Alkenes. Most Group VIII metals, metal salts, and complexes may be used as catalyst in hydrosilylation of alkenes. Platinum and its derivatives show the highest activity. Rhodium, nickel, and palladium complexes, although less active, may exhibit unique selectivities. The addition is exothermic and it is usually performed without a solvent. Transition-metal complexes with chiral ligands may be employed in asymmetric hydrosilylation 406,422... 

All Group VIII metals, as well as Mn, Cr, and Cu, exhibit some activity in hydroformylation.6 11 Cobalt, the catalyst in the original discovery, is still used mainly in industry rhodium, introduced later, is one of the most active and studied catalysts. The metal catalysts may be applied as homogeneous soluble complexes, heteroge-nized metal complexes, or supported metals. 

Metal catalysed decomposition of diazocarbonyl compounds in the presence of alkenes provides a facile and powerful means of constructing electrophilic cyclopropanes. The cyclopropanation process can proceed intermolecularly or intramolecularly. Early work on the topic of intramolecular cyclopropanation (mainly using diazoketones as precursors) has been surveyed31. With the discovery of powerful group VIII metal catalysts, in particular the rhodium(II) derivatives, metal catalysed cyclopropanation of diazocarbonyls is currently the most fertile area in cyclopropyl chemistry. In this section, we will review the efficiency and versatility of the various catalysts employed in the cyclopropanation of diazocarbonyls. Cyclopropanations have been organized according to the types of diazocarbonyl precursors. Emphasis is placed on recent examples. 

There are also several situations where the metal can act as both a homolytic and heterolytic catalyst. For example, vanadium complexes catalyze the epoxidation of allylic alcohols by alkyl hydroperoxides stereoselectively,57 and they involve vanadium(V) alkyl peroxides as reactive intermediates. However, vanadium(V)-alkyl peroxide complexes such as (dipic)VO(OOR)L, having no available coordination site for the complexation of alkenes to occur, react homolyti-cally.46 On the other hand, Group VIII dioxygen complexes generally oxidize alkenes homolytically under forced conditions, while some rhodium-dioxygen complexes oxidize terminal alkenes to methyl ketones at room temperature. 

With the notable exception of rhodium, Group VIII metal-peroxo complexes are generally reluctant to react with simple alkenes by nonradical pathways. However, such an oxygen transfer has been shown to occur in the reaction of 180-labeled [(AsPh3)4Rh02]+C104" with terminal alkenes under 02-free, anhydrous conditions, producing lsO-labeled methyl ketone (equation 52).131... 

All Group VIII, IX and X transition metals show some catalytic activity for hydroformylation, although cobalt and rhodium are the most active, rhodium catalysts being 104 times more reactive. More recently, platinum catalysts containing the trichlorostannate ligand have been shown to be selective catalysts that effect hydroformylation under mild conditions.6... 

The hydrocarboxylation reaction of alkenes and alkynes is one which utilizes carbon monoxide to produce carboxylic acid derivatives. The source of hydrogen is a protic solvent (equation 35) dihydrogen is not usually added to the reaction. There are a number of variations to this reaction, since the solvent can be water, alcohols, amines, acids, etc. The catalysts can be Group VIII-X transition metals, but cobalt, rhodium, nickel, palladium and platinum have found the most use. 

Hydrosilylation of various carbonyl compounds, enones and related functional groups catalyzed by Group VIII transition metal complexes, especially phosphine-rhodium complexes, have been extensively studied1,3, and the reactions continue to serve as useful methods in organic syntheses. 

Extremely high regioselectivity has been observed for hydroformylation of fluoro-olefins RfCH=CH2, catalysed by group VIII transition metals. While a Co catalyst gives the normal product 345 on hydroformylation of 344, a Rh catalyst gives mostly the isomeric aldehyde 346470. In another study, hydroformylation of 1-hexene was catalysed by rhodium(I) with concomitant isomerization471. 

We place hydrogen as the first element in the first period, along with helium. When helium was discovered, Mendeleev put it in the second period. We put the triads of iron, cobalt, and nickel ruthenium, rhodium and palladium and osmium, iridium, and platinum in group VIIIB, in the middle of the table. Mendeleev put them in group VIII. We also have two long groups, the lanthanides and actinides, that were a headache for Mendeleev. 

In Group VIII, each position instead of being filled by a single element is occupied by a group of three elements. Thus there appear in triads iron, cobalt, and nickel ruthenium, rhodium, and palladium and osmium, iridium, and platinum. In this group there is no subdivision into families, but all the members are heavy metals. 

The production of C2 alcohols is higher on the metals left from the diagonal in Group VIII (Fe, Co, Ru) since these metals tend to accumulate CHX groups on the whole metallic surface. Rhodium is most suitable for producing ethanol its CO dissociation activity is weak and thus the CHX units are preferentially formed on the metal surface round the patches of the promoting oxide. 

Cobaltic sulphate, like the sulphates of rhodium and iridium, unites with the sulphates of the alkali metals to yield a series of well-defined, crystalline salts known as alums. These are isomorphous with those of iron, manganese, chromium, and aluminium, and form an interesting link between these metals and the central vertical column in Group VIII of the Periodic Table, of which column cobalt is the first member. 

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