Ruthenium oxide fluorides

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]. 

Oxidation states IV to VIII inclusive are represented in the fluorine chemistry of osmium, as compared with III to VI for ruthenium and II and III for iron. Thus the fluorides of the iron-ruthenium-osmium triad well exemplify the greater tendency of second and third row elements to higher oxidation states with rc-donor ligands. 

The diols (97) from asymmetric dil droxylation are easily converted to cyclic sii e esters (98) and thence to cyclic sulfate esters (99).This two-step process, reaction of the diol (97) with thionyl chloride followed by ruthenium tetroxide catalyzed oxidation, can be done in one pot if desired and transforms the relatively unreactive diol into an epoxide mimic, ue. the 1,2-cyclic sulfate (99), which is an excellent electrophile. A survey of reactions shows that cyclic sulfates can be opened by hydride, azide, fluoride, thiocyanide, carboxylate and nitrate ions. Benzylmagnesium chloride and thie anion of dimethyl malonate can also be used to open the cyclic sulfates. Opening by a nucleophile leads to formation of an intermediate 3-sidfate aiuon (100) which is easily hydrolyzed to a -hydroxy compound (101). Conditions for cat ytic acid hydrolysis have been developed that allow for selective removal of the sulfate ester in the presence of other acid sensitive groups such as acetals, ketals and silyl ethers. 

Weinstock, Malm, and Weaver have shown that platinum hexafluoride is thermally unstable and dissociates to a lower fluoride and fluorine. In view of this capacity of the hexapositivc platinum to oxidise combined fluorine to the elemental furm. it is not surprising that it is also capable of oxidising the oxygen molecule. A similar oxidation by ruthenium and rhodium hexafluorides is to be looked for. 

The departure from the 1 1 reaction stoichiometry in the xenon-rhodium hexafluoride system is less than for the platinum system. This is surprising in view of the greater instability and chemical reactivity of the rhodium fluoride. Ruthenium hexafluoride, which is less reactive than rhodium hexafluoride, has been reported [7] to react non-stoichiometrically with xenon. Perhaps the use of small quantities of rhodium fluoride favored the 1 1 addition. There is as yet no evidence for the oxidation state of rhodium in the adduct, although the formulation Xe -1- [RhFe] would, as in the corresponding platinum case, appear to be energetically more favorable than Xe +[RhF6] . 

The room temperature oxidation of gold, ruthenium, osmium, iridium, platinum, or palladium with fluorine in anhydrous hydrogen fluoride... 

G. Lucier, S. H. Elder, L. Chacon and N. Bartlett, The Room Temperature Oxidation of Gold, Ruthenium, Osmium, Iridium, Platinum, or Palladium with Fluorine in Anhydrous Hydrogen Fluoride, European J. Solid State Inorg. Chem. 33 (1996) 809-820. 

O2CI2N2RUC12H8, Ruthenium(II), dicarbo-nyldichloro(2,2 -bipyridine)-, 25 108 02CrF2, Chromium fluoride oxide, 24 67 O2F2U, Uranium(VI), difluorodioxo-,... 

Use of modified gold electrodes is not the only approach to achieve cytochrome c electrochemistry. Indeed, a number of studies have been reported on a variety of electrode surfaces. In 1977, Yeh and Kuwana illustrated (23) well-behaved voltammetric response of cytochrome c at a tin-doped indium oxide electrode the electrode reaction was found to be diffusion-controlled up to a scan rate of 500 mV sec Metal oxide electrodes were further studied (24, 25) independently in Hawkridge and Hill s groups. The electrochemical response of cytochrome c at tin-doped indium oxide and fluoride-doped tin oxide was very sensitive to the pretreatment procedures of the electrode surface. At thin-film ruthenium dioxide electrodes, variation of the faradaic current with pH correlating with the acid-base protonation of the electrode surface was observed. 

BENSULFOID (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry materia forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysis, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium iodate, potassium peroxoferrate, rubidium acetylide, ruthenium tetraoxide, sodium, sodium chlorite, sodium peroxide, tin, uranium, zinc, zinc(II) nitrate, hexahydrate. Forms heat-, friction-, impact-, and shock-sensitive explosive or pyrophoric mixtures with ammonia, ammonium nitrate, barium bromate, bromates, calcium carbide, charcoal, hydrocarbons, iodates, iodine pentafluoride, iodine penloxide, iron, lead chromate, mercurous oxide, mercury nitrate, mercury oxide, nitryl fluoride, nitrogen dioxide, inorganic perchlorates, potassium bromate, potassium nitride, potassium perchlorate, silver nitrate, sodium hydride, sulfur dichloride. Incompatible with barium carbide, calcium, calcium carbide, calcium phosphide, chromates, chromic acid, chromic... 

---