Oxygen rhodium

The reaction of bis-phenylpropargyl ether (321) with tris(triphenylphosphine)rhodium chloride in benzene or toluene led to the formation of the unusual organometallic compound (322), which can be viewed as a derivative of an oxygen-rhodium pentalene system. Reaction of the rhodium complex (322) with sulfur leads to the corresponding 4,6-diphenyl-l,3-dihydro[3,4-c]furan (323). The selenium and tellurium analogs (324) and (325) were made in a similar manner (Scheme 111) (76LA1448). 

Rhodium and the Halogens —Hcxa-ohlor-rhoditos—Ponla-clilor-rhodilcs - -Rhodium and Oxygen—Rhodium and Sulphur—Tho Alums—Rhodium and Nitrogen—Rhodium, Phosphorus, and Arscaio—Rhodium and Carbon -Rhodi-oyanides. 

Oxidation has been observed by Patin and coworkers [166] in water as solvent during the preparation of a precatalyst by reaction of RhClj with TPPTS (Scheme 2.49). Under mild conditions and the strict exclusion of oxygen, rhodium(lll) was reduced to rhodium(I). The latter is trapped by TPPTS. As oxygen acceptor serves the excess of TPPTS, the phosphine is converted into the corresponding phosphine oxide (TPPTSO). Noteworthy, by this approach for the preparation of the rhodium(l) precatalyst, a part of the ligand is sacrificed. 

Rhodium is the whitest metal in the platinum group metals and it does not lose its luster under any atmospheres at ordinary temperatures. When rhodium is heated, the protective coating of rhodium oxide forms at 700°C. Further, at llOO C the oxide is dissociated to rhodium and oxygen. Rhodium dissolves in hot sulfuric acid or in aqua regia. Rhodium reacts with a halogen at high temperatures to afford a trihalide [1-6]. Rhodium has a high reflexibility and is used as a reflex mirror. The alloy with rhodium is used in thermocouples, crucibles, catalysts, electrical contact points, heat-resistant materials, corrosion resistant materials, etc. 

CO, and methanol react in the first step in the presence of cobalt carbonyl catalyst and pyridine [110-86-1] to produce methyl pentenoates. A similar second step, but at lower pressure and higher temperature with rhodium catalyst, produces dimethyl adipate [627-93-0]. This is then hydrolyzed to give adipic acid and methanol (135), which is recovered for recycle. Many variations to this basic process exist. Examples are ARCO s palladium/copper-catalyzed oxycarbonylation process (136—138), and Monsanto s palladium and quinone [106-51-4] process, which uses oxygen to reoxidize the by-product... 

Black nickel oxide is used as an oxygen donor in three-way catalysts containing rhodium, platinum, and palladium (143). Three-way catalysts, used in automobiles, oxidize hydrocarbons and CO, and reduce NO The donor quaUty, ie, the abiUty to provide oxygen for the oxidation, results from the capabihty of nickel oxide to chemisorb oxygen (see Exhaust control, automotive). 

Rhodium complexes with oxygen ligands, not nearly as numerous as those with amine and phosphine complexes, do, however, exist. A variety of compounds are known, iucluding [Rh(ox)3] [18307-26-1], [Rh(acac)3] [14284-92-5], the hexaaqua ion [Rh(OH2)3] [16920-31 -3], and Schiff base complexes. Soluble rhodium sulfate, Rh2(804 )3-a H2 0, exists iu a yellow form [15274-75-6], which probably coutaius [Rh(H20)3], and a red form [15274-78-9], which contains coordinated sulfate (125). The stmcture of the soluble nitrate [Rh(N03)3 2H20 [10139-58-9] is also complex (126). Another... 

The avermectins also possess a number of aUyflc positions that are susceptible to oxidative modification. In particular the 8a-methylene group, which is both aUyflc and alpha to an ether oxygen, is susceptible to radical oxidation. The primary product is the 8a-hydroperoxide, which has been isolated occasionally as an impurity of an avermectin B reaction (such as the catalytic hydrogenation of avermectin B with Wilkinson s rhodium chloride-triphenylphosphine catalyst to obtain ivermectin). An 8a-hydroxy derivative can also be detected occasionally as a metaboUte (42) or as an impurity arising presumably by air oxidation. An 8a-oxo-derivative can be obtained by oxidizing 5-0-protected avermectins with pyridinium dichromate (43). This also can arise by treating the 8a-hydroperoxide with base. 

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. 

The use of a catalyst such as cadmium oxide increases the yield of dibasic acids to about 51% of theoretical. The composition of the mixed acids is about 75% C-11 and 25% C-12 dibasic acids (73). Reaction of undecylenic acid with carbon monoxide using a triphenylphosphine—rhodium complex as catalyst gives 11-formylundecanoic acid, which, upon reaction with oxygen in the presence of Co(II) salts, gives 1,12-dodecanedioic acid in 70% yield (74). 

G. Fisher and co-workers, "Mechanism of the Nitric Oxide—Carbon Monoxide—Oxygen Reaction Over a Single Crystal Rhodium Catalyst," in M. 

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. 

The most important use of ammonia is in the production of nitric acid (HNO3). Ammonia burns in oxygen, releasing hydrogen to form water and free nitrogen. With the catalysts platinum and rhodium, ammonia is oxidized and reacted with water to form nitric acid. Nitric acid treated... 

Probably the most significant control technology breakthrough came m 1977, when Volvo released a computer-controlled, fuel-mjected vehicle equipped with a three-way catalyst. The new catalytic converters employed platinum, palladium, and rhodium to simultaneously reduce NO and oxidize CO and HC emissions under carefully controlled oxygen conditions. The new Bosch fuel injection system on the vehicle provided the precise air/fuel control necessary for the new catalyst to perform effectively. The combined fuel control and three-way catalyst system served as the foundation for emissions control on the next generation of vehicles. 

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