Ruthenium, chloro

Ruthenium Chloro Complexes. Fig, 26-F-l gives some common reactions of these chloro species. 

RuCisH22, Ruthenium, V-1.5-cycloocta-diene) Tt -l, 3,5-cyclooctatriene)-, 22 178 RuCitHgg, Ruthenium 0), bis Ti -ethylene) T -hexamethylbenzene)-, 21 76 RuCigHge, Ruthenium 0), -n -l,3-cycIohexa-diene) T -hexamethylbenzene)-, 21 77 RuClPgCgiHjj, Ruthenium ), chloro Ti -cyclo-pentadienyl)bis triphenylphosphine)-, 21 78... 

Ruthenium chloro-complexes have been separated by electrophoresis. ° RuCl3, prepared as a fission isotope from U, exchanged the ruthenium atom with the cobalt of Co "(acac)3 in the solid state. The yield of Ru (acac>3 was consistent with first-order kinetics for the exchange process. If the cobalt remained correlated with the ruthenium after exchange, then slow cooling to a lower temperature should decrease the yield of Ru (acac>3 this did not occur, and the yield of exchanged product may depend on the relative strengths of the Ru—O and Co—O bonds in the acetylacetone complexes. 

Binary Compounds. The mthenium fluorides are RuF [51621 -05-7] RuF [71500-16-8] tetrameric (RuF ) [14521 -18-7] (15), and RuF [13693-087-8]. The chlorides of mthenium are RUCI2 [13465-51-5] an insoluble RuCl [10049-08-8] which exists in an a- and p-form, mthenium trichloride ttihydrate [13815-94-6], RuCl3-3H2 0, and RuCl [13465-52-6]. Commercial RuCl3-3H2 0 has a variable composition, consisting of a mixture of chloro, 0x0, hydroxo, and often nitrosyl complexes. The overall mthenium oxidation state is closer to +4 than +3. It is a water-soluble source of mthenium, and is used widely as a starting material. Ruthenium forms bromides, RuBr2 [59201-36-4] and RuBr [14014-88-1], and an iodide, Rul [13896-65-6]. 

Chloro-2-(3-methyl-4H-1,2,4-triazol-4-yDbenzophenone (Oxidation of 7solution prepared by adding sodium periodate (2 g) to a stirred suspension of ruthenium dioxide (200 mg) in water (35 ml). The mixture became dark. Additional sodium periodate 18 g) was added during the next 15 minutes. The ice-bath was removed and the mixture was stirred for 45 minutes. Additional sodium periodate (4 g) was added and the mixture was stirred at ambient temperature for 18 hours and filtered. The solid was washed with acetone and the combined filtrate was concentrated in vacuo. The residue was suspended in water and extracted with methylene chloride. The extract was dried over anhydrous potassium carbonate and concentrated. The residue was chromatographed on silica... 

As described in U.S. Patent 3,025,292, the desired product may be made by hydrogenation of chlorothiazide. Three grams of 6-chloro-7-sulfamyl-1,2,4-benzothiadiazine-1,1-dioxide (chlorothiazide) is suspended in 100 ml of methanol. Then 1.0 gram of a 5% ruthenium on charcoal catalyst is added, and the mixture is reduced at room temperature and at an initial hydrogen pressure of 39 psig. The theoretical amount of hydrogen to form the 3,4-dihydro derivative is absorbed after a period of about 10 hours. 

These results were explained by the discovery that the chloro-ruthenium complexes are not the primary photoproducts under CO in 1.0 M CCl /octane solution. Instead Ru(CO>5 proved to be the initial product even after nearly complete photofragmentation of the starting material, and the chlorocarbonyl ruthenium products to be the result of a secondary, dark reaction between the Ru(C0)5 and CCI4 (3) ... 

The dichlororuthenium arene dimers are conveniently prepared by refluxing ethanolic ruthenium trichloride in the appropriate cyclohexadiene [19]. The di-chloro(pentamethylcyclopentadienyl) rhodium dimer is prepared by refluxing Dewar benzene and rhodium trichloride, whilst the dichloro(pentamethylcyclo-pentadienyl)iridium dimer is prepared by reaction of the cyclopentadiene with iridium trichloride [20]. Alternatively, the complexes can be purchased from most precious-metal suppliers. It should be noted that these ruthenium, rhodium and iridium arenes are all fine, dusty, solids and are potential respiratory sensitizers. Hence, the materials should be handled with great care, especially when weighing or charging operations are being carried out. Appropriate protective clothing and air extraction facilities should be used at all times. 

Ruthenium(m).—Group VII Donors. The consecutive stability constants Ky—Kj of chloro-complexes of Ru have been determined in aqueous and aqueous-alcoholic 1N-HC104. Other Russian workers have compared the... 

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