Of rhodium

Rhodium occurs native with other platinum metals in river sands of the Urals and in North and South America. It is also found with other platinum metals in the copper-nickel sulfide area of the Sudbury, Ontario region. Although the quantity occurring here is very small, the large tonnages of nickel processed make the recovery commercially feasible. The annual world production of rhodium is only 7 or 8 tons. 

R. S. Dickson, Homogeneous Catalysis with Compounds of Rhodium and Iridium, Reidel, Dordrecht, The Netherlands, 1985. 

Patents on the catbonylation of methyl chlotide [74-87-3] using carbon monoxide [630-08-0] in the presence of rhodium, palladium, and tidium complexes, iodo compounds, and phosphonium iodides or phosphine oxides have been obtained (26). In one example the reaction was conducted for 35... 

Other Methods. A variety of other methods have been studied, including phenol hydroxylation by N2O with HZSM-5 as catalyst (69), selective access to resorcinol from 5-methyloxohexanoate in the presence of Pd/C (70), cyclotrimerization of carbon monoxide and ethylene to form hydroquinone in the presence of rhodium catalysts (71), the electrochemical oxidation of benzene to hydroquinone and -benzoquinone (72), the air oxidation of phenol to catechol in the presence of a stoichiometric CuCl and Cu(0) catalyst (73), and the isomerization of dihydroxybenzenes on HZSM-5 catalysts (74). 

Ligand-Modified Rhodium Process. The triphenylphosphine-modified rhodium oxo process, termed the LP Oxo process, is the industry standard for the hydroformylation of ethylene and propylene as of this writing (ca 1995). It employs a triphenylphosphine [603-35-0] (TPP) (1) modified rhodium catalyst. The process operates at low (0.7—3 MPa (100—450 psi)) pressures and low (80—120°C) temperatures. Suitable sources of rhodium are the alkanoate, 2,4-pentanedionate, or nitrate. A low (60—80 kPa (8.7—11.6 psi)) CO partial pressure and high (10—12%) TPP concentration are critical to obtaining a high (eg, 10 1) normal-to-branched aldehyde ratio. The process, first commercialized in 1976 by Union Carbide Corporation in Ponce, Puerto Rico, has been ficensed worldwide by Union Carbide Corporation and Davy Process Technology. 

Mechanism ofLP Oxo Rea.ction. The LP Oxo reaction proceeds through a number of rhodium complex equilibria analogous to those ia the Heck-Breslow mechanism described for the ligand-free cobalt process (see Fig. 1). 

Ruthenium. Ruthenium, as a hydroformylation catalyst (14), has an activity signiftcandy lower than that of rhodium and even cobalt (22). Monomeric mthenium carbonyl triphenylphosphine species (23) yield only modest normal to branched regioselectivities under relatively forcing conditions. For example, after 22 hours at 120°C, 10 MPa (1450 psi) of carbon monoxide and hydrogen, biscarbonyltristriphenylphosphine mthenium [61647-76-5] ... 

High enantioselectivities and regioselectivities have been obtained using both mono- and 1,2-disubstituted prochinal olefins employing chiral phosphine phosphite (33,34) modified rhodium catalysts. For example, i7j -2-butene ia the presence of rhodium and (12) (33) gave (3)-2-meth5ibutanal ia an optical yield of 82% at a turnover number of 9.84. ... 

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. 

Extensive PGM deposits, similar geologically to the Bushveld Complex, exist on the Great Dyke in Zimbabwe. There has been extensive exploration in the 1990s, but as of this writing (1995) exploitation has been delayed. Should the operation proceed, it has been estimated that Zimbabwe could produce up to 4.7 tons of platinum, 3.4 tons of palladium, and 0.35 tons of rhodium annually. 

Numbers in parentheses represent the quantity of rhodium recovered from this industry. ... 

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... 

The most common oxidatiou states and corresponding electronic configurations of rhodium are +1 which is usually square planar although some five coordinate complexes are known, and +3 (t7 ) which is usually octahedral. Dimeric rhodium carboxylates are +2 (t/) complexes. Compounds iu oxidatiou states —1 to +6 (t5 ) exist. Significant iudustrial appHcatious iuclude rhodium-catalyzed carbouylatiou of methanol to acetic acid and acetic anhydride, and hydroformylation of propene to -butyraldehyde. Enantioselective catalytic reduction has also been demonstrated. 

Ca.ta.lysis, The readily accessible +1 and +3 oxidation states of rhodium make it a useful catalyst. There are several reviews of the catalytic properties of rhodium available (130—132). Rhodium-catalyzed methanol carbonylation (Monsanto process) accounted for 81% of worldwide acetic acid by 1988 (133). The Monsanto acetic acid process is carried out at 175°0 and 1.5 MPa (200 psi). Rhodium is introduced as RhCl3 but is likely reduced in a water... 

Wilkinson Hyd.rogena.tion, One of the best understood catalytic cycles is that for olefin hydrogenation in the presence of phosphine complexes of rhodium, the Wilkinson hydrogenation (14,15). The reactions of a number of olefins, eg, cyclohexene and styrene, are rapid, taking place even at room temperature and atmospheric pressure but the reaction of ethylene is extremely slow. Complexes of a number of transition metals in addition to rhodium are active for the reaction. 

In addition to platinum and related metals, the principal active component ia the multiflmctioaal systems is cerium oxide. Each catalytic coaverter coataias 50—100 g of finely divided ceria dispersed within the washcoat. Elucidatioa of the detailed behavior of cerium is difficult and compHcated by the presence of other additives, eg, lanthanum oxide, that perform related functions. Ceria acts as a stabilizer for the high surface area alumina, as a promoter of the water gas shift reaction, as an oxygen storage component, and as an enhancer of the NO reduction capability of rhodium. 

Olefins can be aminomethylated with carbon monoxide [630-08-0] (CO) and amines in the presence of rhodium-based catalysts. Eor example, pipera2ine reacts with cyclohexene [110-83-8] to form W,Af-di-(l-cyclohexylmethyl)-pipera2ine [79952-94-6] (55). 

Rhodium. Rhodium is the most commonly plated platinum-group metal. In addition to its decorative uses, rhodium has useful properties for engineering appHcations. It has good corrosion resistance, stable electtical contact resistance, wear resistance, heat resistance, and good reflectivity. The use of rhodium for engineering purposes is covered by an ASTM specification (128). Typical formulas are shown in Table 15. The metal content is obtained from prepared solutions available from proptietary plating supply companies. Replenishment is requited because anodes are not soluble. Rhodium for decorative use may be 0.05—0.13 p.m thick for industtial use, it maybe 0.50—5.0 p.m thick. 

A.STM B634, Std. Spec. forEkctrodeposited Coatings of Rhodium for Engineering Use, American Society for Testing and Materials, Philadelphia, Pa., 1993. 

The replacement of rhodium from a wide range of rhodacycles to form condensed furans, thiophenes, selenophenes, tellurophenes and pyrroles has been widely explored and a range of examples is shown in Scheme 97. The rhodacycles are readily generated from the appropriate dialkyne and tris(triphenylphosphine)rhodium chloride. Replacement of the rhodium by sulfur, selenium or tellurium is effected by direct treatment with the element, replacement by oxygen using m-chloroperbenzoic acid and by nitrogen using nitrosobenzene. 

In another fluxional process involving ruthenium instead of rhodium, it has been shown that the rate-controlling step is the complex dissociation and that the ligand exchanges between the two annular nitrogen atoms by an intermolecular process. 

The reaction of thiocarbonyl compounds with diazoalkanes (alkyl, aryl substituted) frequently gives good to excellent yields of thiiranes. The mechanism may involve addition of a carbene across the thiocarbonyl group, especially in the presence of rhodium(II) acetate... 

When 6-diazopenicillanates are irradiated in the presence of sulfur nucleophiles, predominantly 6/3-substitution products are obtained (77JOC2224). When BFs-EtiO is used to catalyze the reaction with nucleophiles, however, the products are primarily the 6a-isomers (78TL995). The use of rhodium or copper catalysis led primarily to ring-opened thiazepine products, presumably by way of the intermediate (56 Scheme 39) (80CC798). 

Scheme 2.12. Enantioselective Reduction of 2-Acetamidoacrylic Acids by Chiral Phosphine Complexes of Rhodium...

A solution of rhodium trichloride trihydrate (2 g) in hot ethanol (70 ml) is added to a solution of freshly recrystallized triphenylphosphine (12 g) in hot... 

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. 

In 1996, consumption in the western world was 14.2 tonnes of rhodium and 3.8 tonnes of iridium. Unquestionably the main uses of rhodium (over 90%) are now catalytic, e.g. for the control of exhaust emissions in the car (automobile) industry and, in the form of phosphine complexes, in hydrogenation and hydroformylation reactions where it is frequently more efficient than the more commonly used cobalt catalysts. Iridium is used in the coating of anodes in chloralkali plant and as a catalyst in the production of acetic acid. It also finds small-scale applications in specialist hard alloys. 

---