Nitrosyl group

The bond length to nitrosyl groups is underestimated, the N-N bond in N2O3, for example, is 0.7 A too short. 

The NO ligand can be supplied by nitric oxide itself, but there are many other sources such as nitrite, nitrate or nitric acid, nitrosonium salts or N-methyl-7V-nitrosotoluene-p-sulphonamide (MNTS). The introduction of a nitrosyl group into a ruthenium complex is an ever-present possibility. 

Many of the nitrosyls studied are 5-coordinate, and analysis of crystallographic results indicates that, in general, in the trigonal bipyramid structures NO is found in the equatorial position in a linear geometry whereas in a square pyramidal structure, there is a bent M—N—O linkage in an apical position. A further point of interest is that in compounds like Ir(NO)Cl2(PPh3)2, the nitrosyl group bends in the more hindered (P—Ir—P) plane. 

Electrophilic reactivity and structure of the coordinated nitrosyl group. J. Masek, Inorg. Chim. Acta, Rev., 1969,3, 99-108 (36). 

The electrophilic addition of nitrosyl chloride with 3-methyl-l,2-butadiene at 0°C afforded 2-nitroso-3-chloro-3-methyl-l-butene, in which the nitrosyl group was connected to the central carbon atom [10]. 

A number of compounds containing nitroso or coordinated nitrosyl groups exhibit instability under appropriate conditions. Individually indexed compounds are Ammonium /V-nitrosophcnvlaminooxidc. 2399 A-(2-Chlorocthyl)-A-nitrosocarbamoyl azide, 1131 1 -Chloro-1 -nitrosocyclohexane, 2419 2-Chloro-1 -nitroso-2-phenylpropane, 3147... 

Cluster Compounds.—The green nitrosyl cluster Os3(CO)jo(NO)2 has been reported in 13% yield from the reaction of NO with Os3(CO) 2 benzene. Its i.r. spectrum suggests bridging nitrosyl groups, which was confirmed from an X-ray analysis of the Ru analogue. I.r. studies show that the structure (23)... 

Crystallographic data (.continued) for transition metal tetrafluorides, 27 98 for transition metal trifluorides, 27 92 Crystallographic disorder, nitrosyl groups, 34 304-305 Crystallography fuscoredoxin, 47 380 prismane protein, 47 232-233 Rieske and Rieske-type proteins, 47 92-109 Crystal radii, of various ions, 2 7 Crystals, 39 402 Crystal structure actinide metals, 31 36 copper-cobalt supetoxide dismutases, 45 ... 

The SNP molecule consists of a ferrous core surrounded by five cyanide groups and a nitrosyl group (Figure 8.2). SNP solutions can be inactivated by trace contaminants. Products of these reactions are toxic, and are often blue. 

The nitrosyl group and the nitro group also are able to accept an additional pair of binding electrons, and the bonds in complexes such as... 

Fig. 15.15 Complexes containing bent nitrosyl groups la, llrlPPhjJjlCOllNOJCI] anil (b) lRu(PPh3) (NOhC,r. Phenyl groups have been omitted for clarity, disiances are in picomeiers. [Structure (a) from Hodgson, D. J., Payne, N. C. McGinnety, J. A. Pearson, R. G. Ibers, J. A. J. Am. Chem. See. 1968, 90, 4486-4488. Structure

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