Nitrosyl salts

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

Furthermore, Weiss and coworkers66 developed also a method of diazotizing aminocyclopropenium salts with nitrosyl salts in the presence of two equivalents of trimethylchlorosilane to trap the water produced. In a modification of this method the authors showed that the use of the terf-butylated amine was an advantage, as the risk of oxidation of the alkylated amino group by the nitrosyl ion is less than in the case of the primary amine. This method would also appear to be suitable for the diazotization of other sensitive amines. 

W. Manchot argued that since the absorption spectrum of the blue acid does not resemble the absorption spectra of the ferrous and cupric nitrosyl salts, it is not constituted as F. Raschig supposed, t F. Raschig replied ... 

There are many nitrosyl salts, including (N0)HS04, (N0)C104, (NO)BF4, (NO)FeCl4, (NO)AsFe, (NO)PtF6, (NO)PtCl6, and (NO)N3. 

As the nitrosyl ion, NO, is similar in size and shape to the dioxygenyl ion, a resemblance of the dioxygenyl hexafluoroplatinate(v) diffraction patterns to those of nitrosyl hexafluoro-osmate(v), -ruthenate(v), and -antimonate(v) is expected. Moreover, since the first ionisation energy of the nitric oxide molecule is 62 kcal. mole lower than that of oxygen, nitrosyl salts are not uncommon. From the unit-cell sizes and molar... 

Although the magnetic susceptibility of dioxy-genyl hexafluoroplatinate(v) has been measured over the temperature range 77—298°k and has been shown to be consistent with the combination of a pciramagnetic (nitric oxide-like) Oj+ and a paramagnetic [PtF,] species, the susceptibility of neither of these ions has been separately determined hitherto. On the basis of its anticipated structural similarity to 0,+[PtF,] the nitrosyl salt, NO+[PtF,] , appeared to be the most suitable for this purpose. 

Pozsgay, V., Jennings, H. J. Azide synthesis with stable nitrosyl salts. Tetrahedron Lett. 1987, 28, 5091-5092. 

Liquid dinitrogen tetraoxide, N2O4, undergoes the selfionization shown in equation 8.13. In this medium, nitrosyl salts such as [N0][C104] behave as acids, and metal nitrates (e.g. NaN03) behave as bases. 

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). 

Method b employs acyl chloride, but the quantitative removal of AgCl is very difficult. Method c does not suffer this disadvantage, because the gaseous NOCl can easily be removed from the reaction medium however, the starting material, i.e. the nitrosyl salt, may itself initiate the polymerization (e.g. polymerization of THF)131). Thus, this method cannot be used for the in situ formation of acyl cations, which is a frequent practice. 

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

Nitrosyl fluoride reacted with phenyltetrafluorophosphorane in FREON 113 )(b.p. 46,6°) or, preferably, FREON 12 medium (b.p. -30°) between -80 to 0 to give a light orange, solid 1 1 adduct [ ] [1] is stable below 0 , but undergoes a sudden irreversible decomposition at ca, 10 with formation of undefined, purple products. NOF thus cannot be recovered directly from the adduct. The result of an NMR study of [I] was not conclusive, due to its sensitivity both towards moisture and heat. Indirect evidence for the formulation of [I] as a nitrosyl salt, NO CgHgPF was obtained from some of its reactions. 

In general the fluoro-bridged [(PcMF)Iv] complexes (M = Al, Ga, Cr) show lower thermal stability, with regard to the loss of iodine, compared to ((PcSiO)Ivln [PcMF] (M = Al, Ga) can also be oxidized with nitrosyl salts, for instance with NO BF4 to give ((PcMF)(BF4)v] . The conductivities are 0.3 S/cm [1431. 

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