Palladium monoxide

Palladium catalysts, 10 42 14 49 16 250 Palladium-catalyzed carbonylation, 13 656 Palladium chloride/copper chloride, supported catalyst, 5 329 Palladium compounds, 19 650-654 synthesis of, 19 652 uses for, 19 653-654 Palladium films, 19 654 Palladium membranes, 15 813 Palladium monoxide, 19 651 Palladium oxide, 19 601... 

Synonyms palladium (11) oxide palladium monoxide palladous oxide... 

Palladium, like rhodium, but unlike platinum, dissolves in fused potassium hydrogen sulphate, yielding palladous sulphate. Fusion with sodium peroxide converts it into palladium monoxide. Heated with sulphur combination takes place with incandescence. 

Dried at 100° C. palladium black contains 072 per cent, of water, and hence, assuming the oxygen exists as palladium monoxide, the composition of the black is as follows 7 ... 

EINECS 215-218-3 Palladium monoxide Palladium oxide Palladium oxide (PdO). Reduction and hydrogenation catalyst in organic synthesis. Black powder d = 8.3 insoluble in H2O. 

Part I Specialty Chemical Monographs Palladium monoxide. See Palladium oxide Palladium nitrate (ous)... 

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... 

With a palladium chloride catalyst, butenediol is carbonylated by carbon monoxide, giving 3-hexenedioic acid [4436-74-2] C HgO (94). 

With palladium chloride catalyst, carbon monoxide, and an alcohol the labile hydroxyl is alkylated during carbonylation (199). 

Under high pressures and temperatures, iodine reacts with oxygen to form iodine pentoxide [12029-98-0] (44). The reaction of iodine with carbon monoxide under acidic conditions is catalyzed by palladium salts (45). Phosphorous vapor and iodine react to form phosphoms trHodide [13455-01 -17, PI (46). 

Other processes described in the Hterature for the production of malonates but which have not gained industrial importance are the reaction of ketene [463-51-4] with carbon monoxide in the presence of alkyl nitrite and a palladium salt as a catalyst (35) and the reaction of dichioromethane [75-09-2] with carbon monoxide in the presence of an alcohol, dicobalt octacarbonyl, and an imida2ole (36). 

The reaction of methyl propionate and formaldehyde in the gas phase proceeds with reasonable selectivity to MMA and MAA (ca 90%), but with conversions of only 30%. A variety of catalysts such as V—Sb on siUca-alumina (109), P—Zr, Al, boron oxide (110), and supported Fe—P (111) have been used. Methjial (dimethoxymethane) or methanol itself may be used in place of formaldehyde and often result in improved yields. Methyl propionate may be prepared in excellent yield by the reaction of ethylene and carbon monoxide in methanol over a mthenium acetylacetonate catalyst or by utilizing a palladium—phosphine ligand catalyst (112,113). 

PGM catalyst technology can also be appHed to the control of emissions from stationary internal combustion engines and gas turbines. Catalysts have been designed to treat carbon monoxide, unbumed hydrocarbons, and nitrogen oxides in the exhaust, which arise as a result of incomplete combustion. To reduce or prevent the formation of NO in the first place, catalytic combustion technology based on platinum or palladium has been developed, which is particularly suitable for appHcation in gas turbines. Environmental legislation enacted in many parts of the world has promoted, and is expected to continue to promote, the use of PGMs in these appHcations. 

Organometallic Compounds. Mononuclear carbon monoxide complexes of palladium are relatively uncommon because of palladium s high labihty, tendency to be reduced, and competing migratory insertion reactions in the presence of a Pd—C bond (201). A variety of multinuclear compounds... 

It has been discovered that styrene forms a linear alternating copolymer with carbon monoxide using palladium II—phenanthroline complexes. The polymers are syndiotactic and have a crystalline melting point - 280° C (59). Shell Oil Company is commercializing carbon monoxide a-olefin plastics based on this technology (60). 

Oxidation. Carbon monoxide can be oxidized without a catalyst or at a controlled rate with a catalyst (eq. 4) (26). Carbon monoxide oxidation proceeds explosively if the gases are mixed stoichiometticaHy and then ignited. Surface burning will continue at temperatures above 1173 K, but the reaction is slow below 923 K without a catalyst. HopcaUte, a mixture of manganese and copper oxides, catalyzes carbon monoxide oxidation at room temperature it was used in gas masks during World War I to destroy low levels of carbon monoxide. Catalysts prepared from platinum and palladium are particularly effective for carbon monoxide oxidation at 323 K and at space velocities of 50 to 10, 000 h . Such catalysts are used in catalytic converters on automobiles (27) (see Exhaust CONTHOL, automotive). 

Oxidative Garbonylation. Carbon monoxide is rapidly oxidized to carbon dioxide however, under proper conditions, carbon monoxide and oxygen react with organic molecules to form carboxyUc acids or esters. With olefins, unsaturated carboxyUc acids are produced, whereas alcohols yield esters of carbonic or oxalic acid. The formation of acryUc and methacrylic acid is carried out in the Hquid phase at 10 MPa (100 atm) and 110°C using palladium chloride or rhenium chloride catalysts (eq. 19) (64,65). 

Dimethyl carbonate [616-38-6] and dimethyl oxalate [553-90-2] are both obtained from carbon monoxide, oxygen, and methanol at 363 K and 10 MPa (100 atm) or less. The choice of catalyst is critical cuprous chloride (66) gives the carbonate (eq. 20) a palladium chloride—copper chloride mixture (67,68) gives the oxalate, (eq. 21). Anhydrous conditions should be maintained by removing product water to minimize the formation of by-product carbon dioxide. 

Aromatic Aldehydes. Carbon monoxide reacts with aromatic hydrocarbons or aryl haHdes to yield aromatic aldehydes (see Aldehydes). The reaction of equation 24 proceeds with yields of 89% when carried out at 273 K and 0.4 MPa (4 atm) using a boron trifluoride—hydrogen fluoride catalyst (72), whereas conversion of aryl haHdes to aldehydes in 84% yield by reaction with CO + H2 requires conditions of 423 K and 7 MPa (70 atm) with a homogeneous palladium catalyst (73) and also produces HCl. 

CO Oxidation Catalyzed by Palladium. One of the best understood catalytic reactions occurring on a metal surface is the oxidation of carbon monoxide on palladium ... 

With hydrogen sulfide at 500—600°C, monochlorotoluenes form the corresponding thiophenol derivatives (30). In the presence of palladium catalysts and carbon monoxide, monochlorotoluenes undergo carbonylation at 150—300°C and 0.1—20 MPa (1—200 atm) to give carboxyHc acids (31). Oxidative coupling of -chlorotoluene to form 4,4 -dimethylbiphenyl can be achieved in the presence of an organonickel catalyst, generated in situ, and zinc in dipolar aprotic solvents such as dimethyl acetamide (32,33). An example is shown in equation 4. 

The oxidative carbonylation of styrene with carbon monoxide, oxygen, and an aUphatic alcohol in the presence of a palladium salt, a copper salt, and sodium propionate also provides the requisite cinnamate. 

Vinyl chloride reacts at 270°C at >6.9 MPa (68 atm) with ethanol and carbon monoxide in the presence of a cobalt and palladium catalyst to give ethyl acrylate in 17% yield. 

Four-membered heterocycles can be formed by the addition of isocyanides to 1,3-dipoles (80AG(E)45) and by the reaction of carbon monoxide with -haloamines, with the aid of palladium catalysis (Scheme 10) (79CC699). 

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