Ruthenium nitrosyls

Table 1.9 summarizes structural data for a number of ruthenium nitrosyl complexes, along with IR data [121, 122],... 

Table 1.9 Ruthenium nitrosyl complexes structural and IR data ...

Ruthenium, hydroxyoxobis[bis(2,2 -bipyridyl)]-chloride oxidation, 1,488 Ruthenium, iodotris(dimethyldithiocarbamato)-stereochemistry, 1, 82 Ruthenium, nitrosyl-complcxcs... 

For example, the substituted aniline Ar-NH2 (Ar = />-CH3OC6H4) reacts with the ruthenium nitrosyl complex Ru(bpy)2(Cl)(NO)2+ (bpy = 2,2 -bipyridine) to give a complex of the diazo ligand, namely Ru(bpy)2(Cl)(NNAr)2+ (57). Upon employing the 15N labeled nitrosyl complex Ru(bpy)2Cl(15NO)2+ this reaction resulted in the 15N coordinated product, Ru(bpy)2Cl(15NNAr)2+, demonstrating that the reaction occurs within the metal complex coordination sphere. When the reactions were conducted in non-protic solvents, these nucleophile-nitrosyl adducts could be isolated. 

Fig. 5.6 Structures of some typical ruthenium nitrosyl complexes.

NMR shift tensor components ruthenium nitrosyl complexes, 34 331,... 

Surprisingly, among the variable set of nucleophiles whose reactions had been studied with NP, the case of N2H4 was absent, in contrast with data available for some ruthenium-nitrosyl complexes (28). 

Figure 40 Variations in the relative quantities of different ruthenium nitrosyl complexes in nitric acid at 20 °C for 10-3 M total ruthenium10,300...

Works CF, Ford PC. Photoreactivity of the ruthenium nitrosyl complex, ru(salen)(cl)(no). solvent effects on the back reaction of NO with the Lewis acid Rum(salen)(Cl). J Am Chem Soc 2000 122 7592. 

An interesting synthesis of the cyclopentadienyl bisphosphine ruthenium nitrosyl complex 9 involves the thermal displacement of both phenyl groups from (i75-C5H5)Ru(NC))PIi2 (8) with a chelating diphosphine [Eq. (6)] (72). Infrared data indicate that the nitrosyl ligand is linear (3 e ... 

Since a far greater number of nitrosyl complexes have been isolated for ruthenium than for any other metal it might be expected that osmium should rival ruthenium in this respect. There seems no reason why this should not be so, and the present disparity in numbers of known osmium and ruthenium nitrosyls simply suggests that much less work has been carried out on the osmium systems. 

There are several recent and comprehensive reviews on metal nitrosyl complexes which give good coverage to the osmium complexes 198 a review on ruthenium nitrosyl complexes is particularly... 

Many ruthenium nitrosyl complexes are well characterized and appear to act as NO+ carriers. For example the bipyridyl complex [Ru(bipy)2(NO)Cl] + reacts with azide ion to give the aquo complex, nitrogen and nitrous oxide... 

Miller and Meyer, 1971). The gaseous products are the same as those derived from the reaction of nitrous acid with azide ion. The reaction is kinetically first order in each reactant, and it is likely that an intermediate complex is also formed in this case. Similarly a p-nitroso complex is formed from the same ruthenium nitrosyl and N-methylaniline, possibly by initial... 

Fig. 7. Plot of Mossbauer shifts for some ruthenium nitrosyl and related complexes , Ru A, Ru +, Ru O, Ru x, Ru anomalous complexes.

The behaviour of ruthenium presents a far more complicated problem because of the variety of ruthenium species which may be present in the solution, and the relatively slow kinetics of their interconversion. The ruthenium is present in dissolver solutions as complexes of the very stable Ru(NO) ion. The coordination chemistry of ruthenium nitrosyls has been reviewed in general and also in particular relation to fuel reprocessing.The species present in the solution may be represented by the general formula [Ru(N0)(N03)x(N02),(OH)2(H20)5 (x+v+r)] - In solutions of high nitrate and low nitrite concentration, species having y = z = 0 and x 4 predominate. At low nitrate concentrations hydroxy species with x = y = 0 and z 2 or x = z = l and j = 0 may also be found. The... 

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