Nitro complexes, osmium

Al-Nitrosodiethanolamine, 2 449, 450 Nitroso dyes, 9 263-264 Nitro soluble dyes, 7 373t Nitroso soluble dyes, 7 373t Nitrosomonas, use in recirculating aquaculture biofiltration, 3 196 P-Nitrostyrenes, preparation by nitration of styrenes, 16 581 Nitrosyl chloride, 20 634 Nitrosyl complexes, osmium, 19 642 Nitrosyl perchlorate, 18 279 Nitrosyl tetrafluoroborate, 4 144t n-Nitrotoluene, 17 263... 

Nitrato and nitro complexes There are very few of these for osmium, and no unsubstituted ones. 

Reactions of the ruthenium and osmium nitro complexes, [M(N02)(C0)2(PPh3)2l, with triphenylphosphine generate the nitrosyl complexes, [M(NO)2(PPh3)2l/ triphenylphosphine oxide, and C0.153... 

No sulfoxide complexes of osmium have been reported. Unsymmetri-cal dialkyl sulfoxides have been utilized in extraction studies, and methyl-4,8-dimethylnonyl sulfoxide has found application in the extraction of iron (266). Extraction of ruthenium from hydrochloric acid solutions by sulfoxides has been studied (470) and comparisons of sul-fones, sulfoxides, and thioethers as extractants for nitrosoruthenium species reported (441, 443). Similar studies on the extraction of nitro-soosmium species have been reported (442). 

Nitric acid converts osmium to volatde osmium tetroxide but forms a nitro-syl complex with ruthenium that remains in the solution. After removal of trace osmium, the solution is treated with ammonium chloride. This precipitates ruthenium as crystals of ammonium chlororuthenate, NH4RUCI6. The precipitate is washed, dried, and ignited to form ruthenium black. This is reduced with hydrogen at 1,000°C to form very pure ruthenium powder. 

Sulfoxide groups direct the dihydroxylation of a remote double bond in an acyclic system perhaps by prior complexation of the sulfoxide oxygen with osmium tetroxide (eqs 16 and 17). Chiral sulfoximine-directed diastereoselective osmylation of cy-cloalkenes has been used for the synthesis of optically pure di-hydroxycycloalkanones (eq 18). Nitro groups also direct the osmylation of certain cycloalkenes, resulting in dihydroxylation from the more hindered side of the ring. In contrast, without the nitro group the dihydroxylation proceeds from the less hindered side (eq 19). ... 

A -alkyl derivatives of tubercidin and of 9-(6-deoxy-6-nitro-j8-D-glucopyrano-syl)adenine have been reported. Guanosine reacted with tetrakis(hydroxy-methyl)phosphonium chloride to give the JV -substituted phosphine (499). The preparation and properties of osmium-ligand complexes of nucleosides are mentioned in Chapter 18. ... 

Sulfonated films of polystyrene crosslinked with divinylbenzene are capable of ion exchange with Ru(bpy)32+ or Ru(NH3)62+. They offer a marked stability in acetonitrile and water. Tris(2,2 -bipyridine)osmium(III/II) complexes can also be used as electron transfer centers . Poly nitro-styrene) has also been proposed as a catalyst for the reduction of organic dihalides . 

---