Osmium sulfur containing

Osmium (continued) carbide, 24 233 dianion, lA. Xil, 317-319 with phosphines and diphosphines, 30 191 protonation/deprotonation, 30 169 raft hexaosmium clusters, 30 180-182 reactions of condensation, 30 145 with hexafluoroacetone, 30 288 redox, 30 184-185 structural transformations, 30 203 sulfur-containing, synthesis of, 30 147 sulfur derivatives, 24 269, 300-310 synthesis... 

Chemical Properties. Compound 2 is readily decarbonylated upon exposure to UV irradiation.5 Irradiated solutions of 2 readily yield addition products of sulfur containing small molecules such as COS, CS2, and H2S. In the absence of reagents it will form the hexanuclear compound Os6(CO)17(/r4-S)2. It reacts with other metal complexes to form higher nuclearity osmium clusters and heteronuclear metal cluster compounds.5,11,12... 

Chiral thiols 59 were derived from 10-camphorsulfonic add by reduction of the sulfony] chloride with lithium aluminum hydride, yielding a 1 4 mixture of enrfo/exo-diastereomers, which can be separated by chromatography60. Containing a hydroxy and a thiol functionality, 59 can be used for the formation of sulfur-containing heterocycles such as oxathianes which can react with carbanions (Section D.l.3.4.4.) or form enolates (Section D. 1.5.3.4.2.1.) and can direct osmium tetroxide catalyzed dihydroxylations (Section D.4.4.). 

The reaction of an osmium carbene cluster containing the cyclic carbene ligand = C(CH=CH)2C(Ph)H which is side on bound to a nonacarbo-nyltriosmium unit with either elemental sulfur/NEt3 or cyclohexene sulfide also afforded a rf-thioketone complex.184... 

Figure 7 The effect of sulfur content of metallic liquid on the magnitude of the solid metal/liquid metal (SM/LM) partition coefficient. Note that copper and silver have an affinity for S-bearing liquid, whereas nickel, gallium, tungsten, osmium, and rhenium all prefer the solid metal. The connection to core formation is that the latter group of elements will have a lower metal/silicate partition coefficient if the metal is liquid and contains sulfur. Similar effects have been documented for carbon (Willis and Goldstein, 1982) (sources Chabot et al., 2003 Malvin et al., 1986 Jones and Drake, 1983 Liu and Reel, 2001 Fleet et al., 1999).

Accordingly, the dihydrate should be a tetrabasic acid if the acidity were due to the hydrogen of the hydroxyl, but this is contrary to experimental facts. Similarly, osmium and ruthenium oxides might be expected to show a greater tendency to form acids than sulfur trioxide since they contain more oxygen atoms with double linking to combine with the water. It is evident, therefore, that a knowledge of the co-ordination number as well as of the atomic valence is necessary in order to determine the basicity of an acid. 

A series of benzylidene and low-valent alkylidene complexes have also been prepared from sulfur ylides. Deprotonation of benzyl or alkyl diphenylsulfonium salts with a strong base, such as KN(SiMe3)2, KNPr j or LiNPr generates the corresponding sulfur ylide. Reaction of this ylide with low-valent ruthenium, osmium, rhodium, or iridium complexes containing a labile ligand leads to transfer of the carbene unit from sulfur to... 

PGM are quite acid-resistant. At room temperature they are not dissolved by concentrated hydrochloric, sulfuric, or hydrofluoric acid. According to [3], the decomposition rate amounts to less than 0.01 mg/cm -hr. Only strongly oxidizing agents such as hot nitric acid and aqua regia dissolve palladium, osmium, and platinum, whereas rhodium and iridium are only dissolved by oxygen-containing cyanide or hydroxide melts (Table 3). 

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