Oxidation rhenium

Although all of the above elements catalyze hydrogenation, only platinum, palladium, rhodium, ruthenium and nickel are currently used. In addition some other elements and compounds were found useful for catalytic hydrogenation copper (to a very limited extent), oxides of copper and zinc combined with chromium oxide, rhenium heptoxide, heptasulfide and heptaselen-ide, and sulfides of cobalt, molybdenum and tungsten. 

With the same excess of catalysts hydrogenations of the esters over Raney nickel could be carried out at temperatures as low as 25-125° at 350atm with comparable results (80% yields). However, benzene rings were saturated under these conditions [55]. In addition to nickel and copper, zinc and chromium oxides, rhenium obtained by reduction of rhenium heptoxide also catalyzes hydrogenation of esters to alcohols at 150-250° and 167-340 atm in 35-100% yields [42]. 

The reaction of the ketyl radical anion with the oxidized rhenium complex is the energy-releasing electron transfer step. This reaction cannot be carried out separately. While ketyl radical anions are stable species, the oxidized complex is not stable and must be generated as short-lived intermediat. ... 

FIGURE 11 The amount of oxidized rhenium remaining as a function of temperature calculated from the data in Figure 10. 

Since then, new developments related to the chemistry of organic compounds have followed. Davis [12] has constructed a magnetic sector mass spectrometer with a direct air sample inlet system and thermionic rhenium emitter. He demonstrated that many organic compounds in normal laboratory air were efficiently ionized on an oxidized rhenium surface. Along with these results, it was suggested that the SI phenomenon could be exploited in gas chromatography (GC) and mass spectrometry (MS). 

Technetium is a silvery-gray metal that tarnishes slowly in moist air. The common oxidation states of technetium are +7, +5, and +4. Under oxidizing conditions technetium (Vll) will exist as the pertechnetate ion, TcOr-. The chemistry of technetium is said to be similar to that of rhenium. Technetium dissolves in nitric acid, aqua regia, and cone, sulfuric acid, but is not soluble in hydrochloric acid of any strength. The element is a remarkable corrosion inhibitor for steel. The metal is an excellent superconductor at IIK and below. 

Alloys suitable for castings that ate to be bonded to porcelain must have expansion coefficients matching those of porcelain as well as soHdus temperatures above that at which the ceramic is fired. These ate composed of gold and palladium and small quantities of other constituents silver, calcium, iron, indium, tin, iridium, rhenium, and rhodium. The readily oxidi2able components increase the bond strength with the porcelain by chemical interaction of the oxidi2ed species with the oxide system of the enamel (see Dental materials). 

Propylene oxide is also produced in Hquid-phase homogeneous oxidation reactions using various molybdenum-containing catalysts (209,210), cuprous oxide (211), rhenium compounds (212), or an organomonovalent gold(I) complex (213). Whereas gas-phase oxidation of propylene on silver catalysts results primarily in propylene oxide, water, and carbon dioxide as products, the Hquid-phase oxidation of propylene results in an array of oxidation products, such as propylene oxide, acrolein, propylene glycol, acetone, acetaldehyde, and others. 

Polymers containing 8-hydroxyquinoline appear to be selective adsorbents for tungsten in alkaline brines (95). In the presence of tartrate and citrate, quinaldic acid [93-10-7] allows the separation of zinc from gallium and indium (96). Either of these compounds can selectively separate lead and zinc from oxide ores as complexes (97). It is also possible to separate by extraction micro quantities of rhenium(VII), using quinoline in basic solution (98). The... 

The oxidation potentials for rhenium in aqueous acidic solution are summarized in the following diagram (6). 

Rhenium exhibits a greater resistance than tungsten to the water cycle effect, in which lamps and electron tubes become blackened by deposition of metal. This phenomenon involves catalysis by small quantities of water that react with the metal in a hot filament to produce a volatile metal oxide and hydrogen. The oxide condenses on the surface of the bulb and is reduced back to the metal by hydrogen. 

A particularly significant part of rhenium chemistry involves cluster compounds in which there is metal—metal bonding. This chemistry centers largely around the +3 oxidation state. 

Rhenium oxides have been studied as catalyst materials in oxidation reactions of sulfur dioxide to sulfur trioxide, sulfite to sulfate, and nitrite to nitrate. There has been no commercial development in this area. These compounds have also been used as catalysts for reductions, but appear not to have exceptional properties. Rhenium sulfide catalysts have been used for hydrogenations of organic compounds, including benzene and styrene, and for dehydrogenation of alcohols to give aldehydes (qv) and ketones (qv). The significant property of these catalyst systems is that they are not poisoned by sulfur compounds. 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Compounds of the formulas Re(CR]), ReO(CH3)4, Li2[Re2(CH3)g] [60975-25-9], Re02(CH3)3 [56090-011-8], and Re03CH3 [70197-13-6] have been prepared. The first two compounds were obtained from reaction of rhenium hahdes or oxyhahdes and methyllithium the last three were formed from the species by oxidation or reduction reactions. The use of these hydride and alkyl complexes as catalysts is under investigation. 

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