Ruthenium Blue

Ru02 can be made by high-temperature oxidation of ruthenium. It has the rutile structure (Ru—O 1.942 A and 1.984 A) and forms blue-black crystals [49b]. 

Recently Ru03 has been made as a brown solid by photolysis  

In matrices, Ru02 is bent (149°) while Ru03 is trigonal planar. 

Copper-coloured 0s02 also has the rutile structure it can be made from the metal and NO at 650°C. 

Os04 will add to C=C bonds but will only attack the most reactive aromatic bonds thus benzene is inert, but it will attack the 9,10 bond in phenanthrene and will convert anthracene to 1,2,3,4-tetrahydroxytetra-hydroanthracene. It can be used catalytically in the presence of oxidizing agents such as NaC103 or H2O2 [53], 

OSO4 is obtained on oxidation of any osmium compound or by direct synthesis at 300-800°C from the elements [50], Its solubility in CCI4 and volatility make it easy to purify it forms pale yellow crystals (m.p. 40.46°C, b.p. 131°C). Like RUO4 it forms tetrahedral molecules with Os-O 1.684-1.710 A, O—Os—O 106.7-110.7° in the solid state Os-O 1.711A in the gas phase [51], It is soluble in water as well as in CCI4 and is very toxic (TLV 2.5 ppm), affecting the eyes. (Its use as a biological stain involves its reaction with tissue.) 

It has long been known (Claus, 1846) that reduction (e.g. Zn, H2 with Pt catalyst) of some ruthenium salts gives a blue solution, which on treatment with HCl or oxidation turns green. Various claims have been made for 

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Reaction of the reduced ruthenium blue solution with thiols such as 2-aminobenzenethiol and 4-toluenethiol (LH) gives highly insoluble compounds of stoichiometry [Ru(L)2] which are prob-... 

Although there are a number of reports of the preparation of RuC12 in the early literature, it appears that this species has never been prepared in a pure state. In fact the reported method of preparation is similar to that established for /f-RuCl3 (see Section 45.9.6.I)2285 and incomplete chlorination with consequent contamination of RuC13 by ruthenium metal was probably responsible for the erroneous claims. However, residues with Ru Cl ratios of ca. 1 2 have been isolated from the reduced ruthenium blue solution (see below) a black solid with a Ru Br ratio of ca. 1 2 is obtained from the corresponding violet-blue Ru" bromide solution.2286,22 7 No RuX2 (X = F, I) are known. 

Finally, reaction of azobenzene with the methanolic ruthenium blue solution gives [ Ru(azb)Cl2 2 ()x-PhN=NPh)] which on treatment with PPh3 in MeOH produces [Ru(azb)Cl(PPh3)3].676... 

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