Rhodium dioxide

Since conjugated dienes form stable rc-allyl complexes with [Co(CO)4]2, they undergo hydroformylation very slowly to give saturated monoaldehydes in low yields.8 Mixtures of mono- and dialdehydes are usually formed in rhodium-catalyzed hydroformylations.71 72 Saturated monoaldehydes were isolated, however, when 1,3-butadiene and 1,3-pentadiene were hydroformylated in the presence of rhodium dioxide.70... 

Rhodium Dioxide, Rh02, results in the anhydrous state on fusing a mixture of rhodium and potassium hydroxide and nitrate in a crucible heated to redness. The product is washed with water, then with hydrochloric acid, and finally dried at 100° C. in an inert gas such as carbon dioxide. It is a brown powder, insoluble in acids, in aqua regia, and even in boiling alkalies.3... 

Hydrated Rhodium Dioxide, Rh02.2H20 or Rh(OH)4, has been obtained in a variety of ways. 

Rh02[g] RHODIUM DIOXIDE (GAS) 1393 SbCI5[g] ANTIMONY PENTACHLORIDE (GAS) 1439... 

Miscellaneous. Ruthenium dioxide-based thick-film resistors have been used as secondary thermometers below I K (92). Ruthenium dioxide-coated anodes ate the most widely used anode for chlorine production (93). Ruthenium(IV) oxide and other compounds ate used in the electronics industry as resistor material in apphcations where thick-film technology is used to print electrical circuits (94) (see Electronic materials). Ruthenium electroplate has similar properties to those of rhodium, but is much less expensive. Electrolytes used for mthenium electroplating (95) include [Ru2Clg(OH2)2N] Na2[Ru(N02)4(N0)0H] [13859-66-0] and (NH 2P uds(NO)] [13820-58-1], Several photocatalytic cycles that generate... 

Direct production of select MDCHA isomer mixtures has been accompHshed usiag mthenium dioxide (30), mthenium oa alumiaa (31), alkah-moderated mthenium (32) and rhodium (33). Specific isomer mixtures are commercially available from an improved 5—7 MPa (700—1000 psi) medium pressure process tolerant of oligomer-containing MDA feeds (34). Dimethylenetri(cyclohexylamine) (8) [25131 -42-4] is a coproduct. 

In one patent (31), a filtered, heated mixture of air, methane, and ammonia ia a volume ratio of 5 1 1 was passed over a 90% platinum—10% rhodium gauze catalyst at 200 kPa (2 atm). The unreacted ammonia was absorbed from the off-gas ia a phosphate solution that was subsequently stripped and refined to 90% ammonia—10% water and recycled to the converter. The yield of hydrogen cyanide from ammonia was about 80%. On the basis of these data, the converter off-gas mol % composition can be estimated nitrogen, 49.9% water, 21.7% hydrogen, 13.5% hydrogen cyanide, 8.1% carbon monoxide, 3.7% carbon dioxide, 0.2% methane, 0.6% and ammonia, 2.3%. 

Z 1 Niobium 1 Nitrate 1 Osmium 73 a. I Perchlorate Phenols u a o Platinum o 0. 1 5 u 1 Rhodium 1 Rubidium Ruthenium Scandium 1 Selenium Silver I Sodium 1 Strontium 1 Sulphate Sulphides, organic Sulphur dioxide 1 Tantalum 1 Tellurium 1 Thallium Thorium e H 1 Titanium a u ab a 1- I Uranium 1 Vanadium 1 Yttrium 1 Zinc Zirconium... 

The transition-metal catalyzed decomposition of thiirene dioxides has been also investigated primarily via kinetic studies103. Zerovalent platinum and palladium complexes and monovalent iridium and rhodium complexes were found to affect this process, whereas divalent platinum and palladium had no effect. The kinetic data suggested the mechanism in equation 7. 

GP 8] [R 7] Ignition occurs at a rhodium catalyst at catalyst temperatures between 550 and 700 °C, depending on the process parameters [3]. Total oxidation to water and carbon dioxide is favored at low conversion (< 10%) prior to ignition. Once ignited, the methane conversion increases and hence the catalyst temperature increases abruptly. 

The photocatalyzed reduction of carbon dioxide at elevated pressure was also investigated. Porous glass beads were used to obtain efficient gas-liquid contact. With isopropanol as the solvent and 2-propyl formate as the reducing agent,the reaction products were carbon monoxide and hydrogen. The catalyst, chloro(tetraphenyl-porphinato)rhodium(III), was irradiated with visible light /21/. 

The system is not limited to the use of synthesis gas as feed. Mixtures of carbon dioxide and hydrogen also give rise to the formation of polyhydric alcohols, and it is also claimed that the reaction mixture can consist of steam and carbon monoxide (62). This latter claim is consistent with the presence of C02 in the reaction mixture when CO/H2 is used as feed [infrared data (62)], and suggests that these ionic rhodium systems are also active catalysts for the water gas-shift reaction (vide infra). 

With reference to the homogeneous catalyst systems thus far reported for the synthesis of hydrocarbons/chemicals from carbon monoxide and hydrogen, only the anionic rhodium systems of Union Carbide show any appreciable shift activity. With neutral species of the type M3(CO)12 (M = Ru or Os), only small quantities of carbon dioxide are produced under the synthesis conditions (57). 

In addition to the polymeric rhodium catalysts previously discussed, monomeric rhodium systems prepared from [Rh(CO)2Cl]2 by addition of strong acid (HC1 or HBF4) and Nal in glacial acetic acid have also been shown to be active homogeneous shift catalysts (80). The active species is thought to be an anionic iodorhodium carbonyl species, dihydrogen being produced by the reduction of protons with concomitant oxidation of Rh(I) to Rh(III) [Eq. (18)], and carbon dioxide by nucleophilic attack of water on a Rh(III)-coordinated carbonyl [Eq. (19)]. 

For example, the reaction of nitronates (123) with a zinc copper pair in ethanol followed by treatment of the intermediate with aqueous ammonium chloride a to give an equilibrium mixture of ketoximes (124) and their cyclic esters 125. Heating of this mixture b affords pyocoles (126). Successive treatment of nitronates (123) with boron trifluoride etherate and water c affords 1,4-diketones (127). Catalytic hydrogenation of acyl nitronates (123) over platinum dioxide d or 5% rhodium on aluminum oxide e gives a-hydroxypyrrolidines (128) or pyrrolidines 129, respectively. Finally, smooth dehydration of a-hydroxypyrrolidines (128) into pyrrolines (130f) can be performed. 

Another study on the preparation of supported oxides illustrates how SIMS can be used to follow the decomposition of catalyst precursors during calcination. We discuss the formation of zirconium dioxide from zirconium ethoxide on a silica support [15], Zr02 is catalytically active for a number of reactions such as isosynthesis, methanol synthesis, and catalytic cracking, but is also of considerable interest as a barrier against diffusion of catalytically active metals such as rhodium or cobalt into alumina supports at elevated temperatures. 

D. Koch, W. Leitner, Rhodium-Catalyzed Hydroformylation in Supercritical Carbon Dioxide ,/ Am. Chem. Soc 1998,120,13398. 

Carbon monoxide oxidation is a relatively simple reaction, and generally its structurally insensitive nature makes it an ideal model of heterogeneous catalytic reactions. Each of the important mechanistic steps of this reaction, such as reactant adsorption and desorption, surface reaction, and desorption of products, has been studied extensively using modem surface-science techniques.17 The structure insensitivity of this reaction is illustrated in Figure 10.4. Here, carbon dioxide turnover frequencies over Rh(l 11) and Rh(100) surfaces are compared with supported Rh catalysts.3 As with CO hydrogenation on nickel, it is readily apparent that, not only does the choice of surface plane matters, but also the size of the active species.18-21 Studies of this system also indicated that, under the reaction conditions of Figure 10.4, the rhodium surface was covered with CO. This means that the reaction is limited by the desorption of carbon monoxide and the adsorption of oxygen. 

Supercritical fluids (e.g. supercritical carbon dioxide, scCCb) are regarded as benign alternatives to organic solvents and there are many examples of their use in chemical synthesis, but usually under homogeneous conditions without the need for other solvents. However, SCCO2 has been combined with ionic liquids for the hydroformylation of 1-octene [16]. Since ionic liquids have no vapour pressure and are essentially insoluble in SCCO2, the product can be extracted from the reaction using CO2 virtually uncontaminated by the rhodium catalyst. This process is not a true biphasic process, as the reaction is carried out in the ionic liquid and the supercritical phase is only added once reaction is complete. 

Another way of getting around the problem of the separation of the catalyst from the substrate is via use of a flow reactor [38], Supercritical carbon dioxide has been used successfully as a medium for the hydroformylation of 1-octene using an immobilized rhodium catalyst. The catalyst is covalently fixed to silica through the modifying ligand A-(3-trimethoxysilyl-n-propyl)-4,5-bis(diphenylphosphino)phenoxazine (Figure 8.13). Selectivity was found to be... 

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