Nitrosyl salts, reactions with

Nitrosyl fluoroborate Reactions with nitrosyl salts Diazonium salts from azomethines... 

Reaction with concentrated acids provides a preparative route to nitrosyl salts such as N0[HS04], N0[HSe04], N0[C104], and NO[Bp4], e.g. ... 

Nitrosyl complexes. The new cationic species [Os(NO)(CO)2(PPh3)2] has been isolated as its BPhJ salt from the reaction of CO and NaBPh4 with [Os(NO)(CO)(PPh3)2Cl]. The complex undergoes an interesting reversible reaction with methoxide ion ... 

For weakly basic amines, i.e. anilines with poly nitro groups, e.g. 2, 4,-dintro-6-bromoaniline, and also most heterocyclic amines, an alternative method must be adopted using nitrosylsulfuric acid. This diazotising medium can be made by dissolving sodium nitrite in concentrated sulfuric acid, but is also available preformed from chemical suppliers. The weakly basic amine is added gradually to the nitrosyl-sulfuric acid with cooling, and after reaction is complete the mixture is poured into ice and water to give a solution of the diazonium salt. 

Diazomethane (called Diazomethan in Ger), C cNiN mw 42.04, N 66.64% poisonous yel gas condensing to a yel liq, bp -24 to -23° and solidifying in pale-yel crysts, fr p -145° explodes violently when heated to a higher temp sol in eth more important methods of prepn are from nitrosomethylurea, nitroso-methylurethane, a mixt of chloroform fit hydrazine hydrate, or l-methyl-l-nitroso-3-nitro-guanidine by reaction with KOH from nitrosyl chloride methylamine by treatment of the Na salt of formaldehyde oxime with chloramine and by other methods... 

Butler, A.R., Glidewell, C. and Glidewell, S.M. (1992) Formation of the dinuclear iron-nitrosyl complex [Fe2(SMe)2(NO)4] by incorporation of SMe groups from methionine in reactions with iron(II) salts and nitrite. J. Chem. Soc. Chem. Commun., 141-142. 

Reaction with otefins. Nitrosyl tctrafluoroborate reacts with primary or secondary olefins in acetonitrile to give 2-methyl-N-hydroxyimidazolium salts (I) at - 15 to 0°. 

The NO + MF, (except NO -f WF,) reactions proceed spontaneously at 20°. The reactions were followed tensimetrically. Gaseous products were identified by infrared spectroscopy and the solid products were examined by. y-ray powder-photography. Both ReF, and OsF, formed NO+[MF,] (cub.) salts and neither salt could be induced to combine with more NO to yield the quadrivalent (NO),MF, compound. In their reactions with nitrosyl fluoride at 20°, however, the rhenium and osmium fluorides are clearly differentiated ReF, readily forms a thermally stable 2 1 adduct, which is isomorphous with (NOjjWFg, whereas the OsF, -i- ONF reaction is complex. The identification of small quantities of nitrogen oxide trifluoride, in the gaseous product of the reaction, indicate the existence of an... 

Reactions 14.68 and 14.69 showed the formation of salts containing the [NO] (nitrosyl) cation. Many salts are known and X-ray diffraction data confirm an N—O distance of 106 pm, i.e. less than in NO (115 pm). A molecular orbital treatment of the bonding (seeproblem 14.16 at the end of the chapter) is consistent with this observation. In going from NO to [NO] there is an increase in the NO vibrational frequency (1876 to Rs2300cm ), in keeping with an increase in bond strength. All nitrosyl salts are decomposed by water (equation 14.94). 

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