Osmium metal, oxidation

Chlorins, e.g. 14, form adducts with osmium(VIII) oxide, which can be hydrolyzed in aqueous sodium sulfide to bacteriochlorindiols, e g. 2, or isobacteriochlorindiols, e.g. 3. Thus, similar to diimide reductions of chlorins, metal-free tetraphenylchlorin 14 (M = 2H) is selectively oxidized to a corresponding bacteriochlorin 2 whereas the zinc chlorin gives an isobac-teriochlorin 3 on oxidation with osmium(VIII) oxide.40 With less symmetrical chlorins, very complex mixtures of constitutional isomers and stereoisomers are formed by /i-bishydroxyla-tion.17... 

In the case of the osmium(VIII) oxide oxidation of 5,10,15,20-tetraphenylchlorin,3b the metal-free macrocycle gives the bacteriochlorin 6, whereas the corresponding zinc derivative leads to an isobacteriochlorin. 

The most successful class of active ingredient for both oxidation and reduction is that of the noble metals silver, gold, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Platinum and palladium readily oxidize carbon monoxide, all the hydrocarbons except methane, and the partially oxygenated organic compounds such as aldehydes and alcohols. Under reducing conditions, platinum can convert NO to N2 and to NH3. Platinum and palladium are used in small quantities as promoters for less active base metal oxide catalysts. Platinum is also a candidate for simultaneous oxidation and reduction when the oxidant/re-ductant ratio is within 1% of stoichiometry. The other four elements of the platinum family are in short supply. Ruthenium produces the least NH3 concentration in NO reduction in comparison with other catalysts, but it forms volatile toxic oxides. 

Osmium(VIII) will also oxidize sulphoxides to sulphones146 although this is usually accomplished in alkaline media in contrast to other transition-metal oxidations described above. The reaction may also be carried out in the presence of potassium... 

The oxidative cleavage of C=C bond is a common type of reaction encountered in organic synthesis and has played a historical role in the structural elucidation of organic compounds. There are two main conventional methods to oxidatively cleave a C=C bond (1) via ozonol-ysis and (2) via oxidation with high-valent transition-metal oxidizing reagents. A more recent method developed is via the osmium oxide catalyzed periodate oxidative cleavage of alkenes. All these methods can occur under aqueous conditions. 

An interesting oxycarbonyl cluster has been isolated in the reaction of 0s04 with CO under pressure. This was an intermediate in the preparation of the Os3(CO)i2. The X-ray analysis has established this as a cubane structure, with an oxygen bridging the four faces of the osmium tetrahedron. The Os-Os distance is 3.20 A and implies no bonding between the osmium centers. This molecule is of obvious interest as a potential model in the studies of carbon monoxide interaction with metal oxides and also metal surfaces, when the formation of metal oxides occurs (200). 

Flowever, some associated materials might be perceived as toxic. For example, complexes of osmium find frequent use as electron mediators, because of their rich chemistry, stability, and redox activity. Osmium metal and most compounds are considered nontoxic, but the neat tetroxide of osmium is a strong oxidizer and is considered highly toxic in the U.S. and very toxic by the European Union. On the other hand, the aqueous solution, osmic acid, has been injected at 1% concentration in several European clinical trials, starting in the 1970s, for treatment of arthritis and hemophilia. - No toxic effects were observed. Thus, osmium toxicity might be a question not of in vivo chemistry, but of manufacture, where a concentrated form of the oxide might need to be handled. ... 

Osmium This metal had already been found by Haber to be an excellent ammonia catalyst. Its activity is further increased by alkali metal oxides, especially by potassium hydroxide. As the pure metal 2% ammonia, promoted, 4%. 

To separate osmium from ruthenium, the aqueous solution is acidified with nitric acid. While nitric acid oxidizes osmate ion to volatile osmium tetroxide, Os04, it converts ruthenium to a nitric oxide complex. Osmium tetroxide is removed from the solution by distillation in air and collected in an aqueous solution of caustic soda containing ethanol. Osmium tetroxide solution is heated with ammonium chloride, upon which osmium precipitates out as a complex chloride, 0s02(NH3)4Cl2. The precipitate is filtered, washed and decomposed by ignition with hydrogen to yield osmium metal. 

Osmium tetroxide is obtained as an intermediate during recovery of osmium metal from osmiridium or other noble metal minerals (See Osmium). In general, oxidation of an aqueous solution of an osmium salt or complex, such as sodium osmate with nitric acid, yields the volatile tetroxide which may be distilled out from the solution. In the laboratory, the compound can be prepared by oxidation of the osmium tetrachloride, OsCh, or other halide solutions with sodium hypochlorite followed by distdlation. 

The direct aminolysis of metal oxides with primary amines is a useful synthetic route for imido compounds of rhenium and osmium (equation 41). 

Osmium carbonyls on MgO and on y-ALO, among other oxides, are catalysts (or catalyst precursors) for alkene isomerization and hydrogenation (Li et al., 1984). The activity depends on the metal oxide used as a support. The ligands present on the metal during catalysis have not yet been elucidated. 

Reaction between DNA/RNA and Mn04 or 0s04 , where the formal metal oxidation states are Mn + and Os +, results in base-specific modification of thymidine/uridine residues. These anionic metal species can oxidize the pyrimidine C5-C6 double bond, which results in formation of m-5,6-dihydroxy-5,6-dihydro-pyrimidine. This reaction is followed by opening of the pyrimidine ring and its subsequent removal from the polynucleotide chain. Permanganate can also oxidize and remove guanine residues (but not adenine) while osmium tetroxide acts much more specifically on pyrimidine residues with the following kinetic preferences (relative rates shown in parenthesis) T (45) U(4.5) > dU(2.8) >... 

Large metal clusters have been supported on many metal oxides. For example, the carbido-cluster anion [OsioC(CO)24] has been adsorbed directly onto MgO. This cluster anion can also be prepared in situ on MgO by the Reductive Carbonylation of adsorbed H2OSCI6. The adsorbed osmium cluster anion appears to be ionically bound to the surface. 

Preparation of Osmium Oxide Pentafluoride.—Osmium oxide pentafluoride was made in several ways, (a) Osmium metal was heated in a stream of oxygen and fluorine (1 2 v/v). The reaction was carried out in a quartz tube with the osmium in a nickel boat, and was initiated by the heat from a small flame. Once started, the reaction sustained itself. The product, which was caught in traps at —183°, was a mixture of an emerald green solid and a pale yellow, more volatile, solid. The difference in volatility of the components of the mixture permitted their separation by trap to trap sublimation under reduced pressure, from a trap held at —16° to receivers cooled with liquid nitrogen. The emerald green solid was retained in the —16° trap. The more volatile, yellow, component proved, from its infrared spectrum, to be osmium hexafluoride. The emerald green solid, m. p. 59-2°, established by infrared spectroscopy, to be free of OsFj, amounted to —50% of the product. 

It was assumed that OsO,F, would be colourless and diamagnetic and phjrsically similar to OsOF, and OsF,. The infrared spectra of osmium oxide pentafluoride samples taken from a variety of preparations were identical with one another. The entire product from one oxyfluorination of osmium metal was subjected to infrared examination. The bulk of the sample in a Monel trap, was isolated from the gas cell by a Hoke valve. After each vapour sample had been scanned it was discarded and a new sample of vapour admitted. This was repeated exhaustively. All the spectra were interpretable in terms of OsF OsOF OsO and traces of HF, CF, SiF and CO,. Two independent magnetic measurements on samples of OsOF one from an oxjrfluorination of the metal and the other from the fluorination of the dioxide gave magnetic susceptibility values equal within the usual experimental uncertainty. Furthermore the magnitude of the susceptibility was consistent with pure OsOF,. 

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