Ruthenium VIII

A number of oxepin derivatives with alkano bridges across the 3- and 6-positions and across the central C-C double bond have been oxidized with ruthenium(VIII) oxide. Usually, all of the double bonds of the heterocycle are cleaved and a macrocycle 5 is formed that contains two 1,2-diketone functions.142,199... 

Oxidation of diethyl 3,6-hexanooxepin-4,5-dicarboxylate with ruthenium(VIII) oxide, generated from ruthenium(III) chloride and sodium periodate in situ, gives the corresponding hexa-no-bridged furan 1 a with loss of two carbon atoms (see Houben-Weyl, Vol. E6a, p 77).200 201 One of the central methylene groups can be replaced by a carbonyl group to give lb.200... 

See Chromyl chloride Non-metal halides Oxygen (Gas) Phosphorus tribromide Ruthenium(VIII) oxide Phosphorus tribromide... 

Nitrosyl perchlorate Organic materials Perchloric acid Alcohols Permanganic acid Organic materials Peroxodisulfuric acid Organic liquids Potassium dioxide Ethanol Potassium perchlorate Ethanol Potassium permanganate Ethanol, etc. Ruthenium(VIII) oxide Organic materials Silver perchlorate Aromatic compounds Sodium peroxide Hydroxy compounds Uranium hexafluoride Aromatic hydrocarbons, etc. Uranyl perchlorate Ethanol See v-halomides Alcohols... 

See Ruthenium(VIII) oxide Ammonia See related metal oxides... 

Hall and Bischofberger177 found that, when 2,3 5,6-di-0-isopro-pylidene-D-gulono-1,4-lactone was oxidized with ruthenium(VIII) oxide and an excess of sodium periodate, it gave 2,3 5,6-di-0-isopro-pylidene-D-riho-4-hexulosono-l,4-[(R) or (S)]-lactol. Similar results were observed with 2,3 5,6-di-0-isopropylidene-D-mannono-1,4-lactone and 2,3 5,6-di-O-isopropylidene-D-allono-l,4-lactone. This oxidation presumably proceeds by way of lactone cleavage and oxidation of the free 4-hydroxyl group followed, on acidification by relac-tonization, and formation of the new lactol. 

Rhenium tetrachloride oxide, 4167 Ruthenium(VIII) oxide, 4862... 

Palladium(II) oxide, 4825 Palladium(IV) oxide, 4835 Perchloric acid, 3998 Periodic acid, 4425 Permanganic acid, 4434 Peroxodisulfuric acid, 4482 Peroxodisulfuryl difluoride, 4328 Peroxomonosulfuric acid, 4481 Peroxytrifluoroacetic acid, 0666 Platinum hexafluoride, 4371 Platinum(IV) oxide, 4836 Plutonium hexafluoride, 4372 Potassium bromate, 0255 Potassium chlorate, 4017 Potassium dichromate, 4248 Potassium iodate, 4619 Potassium nitrate, 4650 Potassium nitrite, 4649 Potassium perchlorate, 4018 Potassium periodate, 4620 Potassium permanganate, 4647 Rhenium hexafluoride, 4373 Rubidium fluoroxysulfate, 4309 Ruthenium(VIII) oxide, 4862 Selenium dioxide, 4838 Selenium dioxide, 4838 Silver permanganate, 0021 Sodium chlorate, 4039 Sodium chlorite, 4038 Sodium dichromate, 4250 Sodium iodate, 4624 Sodium nitrate, 4721 Sodium nitrite, 4720... 

No nitrido complexes of ruthenium(VIII) have been isolated. For osmium, the only well-established osmium(VIII) nitrido species is [0s(0)3(N)] , which has been well documented in CCC (1987). A number of heterometallic complexes formed by the interaction of [0s(0)3(N)] with a second metal center have been reported. In these complexes, the [0s(0)3(N)] ion acts as a... 

Hydrogen peroxide converts morpholine into its 4-hydroxy derivative (50JA2280), but TV-alkyl morpholines yield 3-oxo compounds if ruthenium(VIII) oxide or sodium metaperiodate are used as oxidants (76S598). Chlorine at -70 °C oxidizes the thiomorpholine (116) to the dihydro-1,4-thiazine (117) (73JCS(Pl)l32l), but more vigorous conditions result in the formation of S-oxides. 

Ruthenium(III) hydroxide is formed by the action of alkali on a solution of ruthenium(III) chloride. It is easily oxidized by air to the tetravalent state, The dioxide, R11O2, forms when the metal is heated in air. Hydrous ruthenium(IV) oxide can be precipitated by adding alcohol to a less than 3-M NaOH solution of ruthenium(VIII) oxide, followed by boiling. Above 3-complete reduction is not obtained. The hydrous oxide that is soluble in concentrated HQ tends to occlude impurities. 

Anhydrous ruthenium(lll) chloride, RuCL, is made by direct chlorination of the metal at 700°C. Two aliotropic forms result. The trihydrate is made by evaporating an HQ solution of rulheinuiu(III) hydroxide to dryness or reducing ruthenium(VIII) oxide in a HQ solution. The tnhydrate, RuCk 3R>0, is the usual commercial form. Aqueous solutions of the tri-hydrate are a straw color in dilute solution and red-brown in concentrated solution. Ruthenium(lll) chloride in solution apparently forms a variety of aquo- and hydroxy complexes. The analogous bromide. RuBr3, is made by the same solution techniques as the chloride, using HBr instead of HQ. 

Ruthenium(IV) hydroxide, 4527 Ruthenium(IV) sulfide, 4889 Ruthenium, 4888 Ruthenium salts, 4890 Ruthenium(VIII) oxide, 4856... 

Palladium(II) oxide, 4819 Palladium(IV) oxide, 4829 Perchloric acid, 3992 Periodic acid, 4419 Permanganic acid, 4428 Peroxodisulfuric acid, 4476 Peroxodisulfuryl difluoride, 4322 Peroxomonosulfuric acid, 4475 Peroxytrifluoroacetic acid, 0662 Platinum hexafluoride, 4365 Platinum(IV) oxide, 4830 Plutonium hexafluoride, 4366 Potassium bromate, 0255 Potassium chlorate, 4011 Potassium dichromate, 4242 Potassium iodate, 4614 Potassium nitrate, 4645 Potassium nitrite, 4644 Potassium perchlorate, 4012 Potassium periodate, 4615 Potassium permanganate, 4642 Rhenium hexafluoride, 4367 Rubidium fluoroxysulfate, 4303 Ruthenium(VIII) oxide, 4856 Selenium dioxide, 4832 Selenium dioxide, 4832 Silver permanganate, 0021... 

A. K. Singh, A. Singh, M. Saxema, R. Gupta, and B. Singh, Kinetic studies of ruthenium(VIII) catalyzed oxidation of some hexoses by iV-bromoacetamide solution, Oxid. Commun., 15 (1992) 56-62. 

V. M. Parikh and J. K. N. Jones, Oxidation of sugars with ruthenium dioxide-sodium periodate a simple method for the preparation of substituted keto sugars, Can. J. Chem., 43 (1965) 3452-3453 compare R. H. Hall and K. Bischofberger, The preparation of aldonolactones and lactols by oxidation of aldoses with ruthenium(VIII) oxide, Carbohydr. Res., 65 (1978) 139-143. 

Fig. 17.29. The Ru04 cleavage of a phenyl ring is exemplified by the case of an altylated aromatic compound using the modified Lemieux-von Rudloff conditions (Figure 17.26). The reaction involves three key intermediates the cr-ketoalde-hyde A, the a-keto acid E, and the ruthenium(VIII) acid diester G. It is unclear how the reaction of E —> G proceeds. In the last step, G undergoes a fragmentation via a cyclic transition state and forms a substituted acetic acid I, Ru03 and carbon dioxide.

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