Nitrosyl ion

Sulfonic acids containing nitrogen have long been implicated as essential intermediates in the synthesis of H2SO4 by the lead-chamber process (p. 708) and, as shown by F. Seel and his group, the crucial stage is the oxidation of sulfite ions by the nitrosyl ion NO+ ... 

This statement does not mean, however, that the mechanism of diazotization was completely elucidated with that breakthrough. More recently it was possible to test the hypothesis that, in the reaction between the nitrosyl ion and an aromatic amine, a radical cation and the nitric oxide radical (NO ) are first formed by a one-electron transfer from the amine to NO+. Stability considerations imply that such a primary step is feasible, because NO is a stable radical and an aromatic amine will form a radical cation relatively easily, especially if electron-donating substituents are present. As discussed briefly in Section 2.6, Morkovnik et al. (1988) found that the radical cations of 4-dimethylamino- and 4-7V-morpholinoaniline form the corresponding diazonium ions with the nitric oxide radical (Scheme 2-39). 

The rate is no longer second-order with respect to nitrous acid, but first-order. Therefore, N203 cannot be the nitrosating reagent. The marked acid catalysis, as seen in the term h0, indicates that the new nitrosating agent is some species whose equilibrium concentration increases rapidly with increasing acidity. As shown in Scheme 3-8, this may be the nitrosoacidium ion (H20 —NO), but could also be the nitrosyl ion (NO+). 

The UV absorption spectra of sodium nitrite in aqueous solutions of sulfuric and perchloric acids were recorded by Seel and Winkler (1960) and by Bayliss et al. (1963). The absorption band at 250 nm is due either to the nitrosoacidium ion or to the nitrosyl ion. From the absorbancy of this band the equilibrium concentrations of HNO2 and NO or H20 —NO were calculated over the acid concentration ranges 0-100% H2S04 (by weight) and 0-72% HC104 (by weight). For both solvent systems the concentrations determined for the two (or three) equilibrium species correlate with the acidity function HR. This acidity function is defined for protonation-dehydration processes, and it is usually measured using triarylcarbinol indicators in the equilibrium shown in Scheme 3-15 (see Deno et al., 1955 Cox and Yates, 1983). 

Species 3.6 is therefore indeed a complex which, in classical terms, may be called a nitrosyl ion solvated with one molecule of water. The complex is calculated to be more stable than its fragments by 75 kJ mol-1. It is likely, as the authors say, that this calculated value is a little smaller than the true value. 

The low stability of the complex 3.6 is consistent with the hard and soft acids and bases principle of Pearson (1963, 1968 Parr and Pearson, 1983 theoretical aspects Pearson, 1989 Chatteraj et al., 1991 monograph Ho, 1977). According to that principle hard acids will tend to complex with hard bases and soft acids with soft bases. Water is a hard base, whereas the nitrosyl ion is classified by Pearson as a borderline acid with a tendency to be soft. 

In summary, it is now more likely that the solvated nitrosyl ion, not the nitroso-acidium ion, is the nitrosating agent in diazotizations. 

Region C corresponds to acidity levels at which the nitrous acid equilibrium of Scheme 3-8 is almost completely on the side of the nitrosyl ion, and that of the amine on the side of the anilinium ion. 

Aminopyridines, aminopyridine oxides, and 3-aminoquinoline are obviously diazotized by analogous mechanisms. Kalatzis (1967 b) studied the diazotization of 4-aminopyridine over a very large range of acid concentrations (0.0025-5.0 m HC104). This compound is comparable to 2-aminothiazole in its acid-base properties the heterocyclic nitrogen is easily protonated at pH 10, whereas the amino group is a very weak base (pKa = -6.5). Therefore, the kinetics indicate that the (mono-protonated) 4-aminopyridinium ion reacts with the nitrosyl ion. The... 

Neither the 2- nor 4-aminopyridine-l-oxides nor their substitution products can be protonated at the heterocyclic nitrogen. The findings regarding the diazotization kinetics of these compounds indicate that, under the reaction conditions studied by Kalatzis and Mastrokalos (1977), two simultaneous mechanisms take place. In the first of these, nitrosyl ions attack the free amine, whereas in the second they attack the protonated amine. 

The C-nitrosation of aromatic compounds is characterized by similar reaction conditions and mechanisms to those discussed earlier in this section. The reaction is normally carried out in a strongly acidic solution, and in most cases it is the nitrosyl ion which attacks the aromatic ring in the manner of an electrophilic aromatic substitution, i. e., via a a-complex as steady-state intermediate (see review by Williams, 1988, p. 58). We mention C-nitrosation here because it may interfere with diazotization of strongly basic aromatic amines if the reaction is carried out in concentrated sulfuric acid. Little information on such unwanted C-nitrosations of aromatic amines has been published (Blangey, 1938 see Sec. 2.2). 

It is appropriate to add here some comments on diazotization in anhydrous carboxylic acids. They may be relevant for the diazotization of heteroaromatic amines carried out in acetic acid/propionic acid mixtures (Sec. 2.2). Extensive studies by Casado et al. (1983, 1984) showed that in nitrosation of secondary amines the nitrosyl ion, nitrosyl acetate, and dinitrogen trioxide are formed, and all three may act as nitrosating agents. The results do not, however, account for the considerable improvement that is claimed in the patent literature (Weaver and Shuttleworth, 1982) to result from the addition of carboxylic acids in the diazotization of heteroaromatic amines. 

Scheme 5-14 may be called a two-dimensional system of reactions, in contrast to Scheme 5-1 which consists of a one-dimensional sequence of two acid-base equilibria. In Scheme 5-14 the (Z/E) configurational isomerism is added to the acid-base reactions as a second dimension . The real situation, however, is yet more complex, as the TV-nitrosoamines may be involved as constitutional isomers of the diazohydroxide. In order not to make Scheme 5-14 too complex the nitrosoamines are not included, but are shown instead in Scheme 5-15. The latter also includes the addition reactions of the (Z)- and ( )-diazoates (5.4 and 5.5) to the diazonium ion to form the (Z,Z)-, (Z,E)- and (2 2i)-diazoanhydrides (5.6, 5.7 and 5.8) as well as proto-de-nitrosation reactions (steps 10, 11 and 12). This pathway corresponds to the reverse reaction of diazotization, as amine and nitrosating reagent (nitrosyl ion) are formed in this reaction sequence.

The kinetics and mechanism of formation of 2,3-naphthotriazole (6.49) were studied by Oh and Williams (1989). In aqueous solutions of 0.2-1.0 m HC104 the dependence of the reaction on acidity indicated simultaneous involvement of the protonated and unprotonated substrates (6.47 and 6.48 respectively). The unproton-ated form of 2,3-diaminonaphthalen (6.48) reacts with the nitrosyl ion (NO+) on encounter (rate constant k ). The 2-NH3 substituent reduces the reactivity of 6.47 by a factor of about 800 (ki/k2). The rate-limiting formation of the diazonium ion (Scheme 6-33) is followed by a rapid cyclization (Scheme 6-34). 

Very feebly basic amines cannot usually be diazotised in dilute acid media and in these instances the reaction has to be carried out in a concentrated acid, normally sulphuric acid. The usual technique is first to dissolve dry sodium nitrite in the concentrated acid, when reaction occurs in two stages (Scheme 4-8), resulting in the formation of nitrosylsulphuric acid (4.5). The nitrosyl ion - nitrous acid equilibrium has been evaluated spectroscopically. In 96% sulphuric acid the 15N-n.m.r. signal is characteristic of the free nitrosyl ion [4]. Reaction (2) of Scheme 4.8 is slow at room temperature and it is desirable to heat the mixture to 70 °C in order to attain equilibrium within a reasonable time. After cooling, the amine is added gradually and after a short time the reaction mixture is poured onto ice, giving an aqueous solution of the diazonium salt [20]. 

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. 

More than thirty years ago Seel and Winkler74 as well as Bayliss and coworkers75 investigated the UV absorption spectra of sodium nitrite in aqueous solutions of sulfuric and perchloric acids (equation 18, for H2SO4). The absorption band found at 250 nm is due either to the nitrosoacidium ion or to the nitrosyl ion. From the absorbency of... 

A speculative proposal was made thirty years ago by Schmid and Krenmayr77, namely that a nitrosyl ion solvated, but not covalently bonded, by a water molecule may be involved in these systems. This hypothesis was investigated theoretically in 1984 by Nguyen and Hegarty78 who carried out ab initio SCF calculations of structure and properties employing the minimal STO-3G basis set, a split-valence basis set plus polarization functions. Optimized geometries of six planar and two nonplanar forms were studied for the nitrosoacidium ion. The lowest minimum of molecular electrostatic potential... 

In the preceding section we concentrated on the rate-limiting steps of diazotizations in aqueous sulfuric and perchloric acid. The results were the identification of dinitrogen trioxide and (solvated) nitrosyl ions as electrophilic reagents, aniline and anilinium ion as nucleophilic reagents and an interpretation of the influence of acidity. 

Miiller-Dethlefs, K. Sander, M. Schlag, E.W. Two-Color PI Resonance Spectroscopy of Nitric Oxide Complete Separation of Rotational Levels of Nitrosyl Ion at the Ionization Threshold. Chem. Phys. Lett. 1984, 772,291-294. 

The nitric oxide molecule, NO. has a bond length of 115 pm and a bond order of 24. Ionization to the nitrosyl ion. NO, removes an antibonding if electron and results in a bond order of three (isoelectronk with N2) and a shortening of the bond length to 106 pm. In contrast, addition of an electron (to a if orbital) causes a decrease in bond order and an increase in bond length. 

The fact that the formation of the nitrosyl ion results from the removal of an ontUwnding electron makes the ionization energy (IE) for the reaction... 

In the oxidation state method, the ligand is viewed as a coordinated nitrosyl ion. NO+, when linear and a coordinated NO" when bent it is a two-electron donor in both forms. 

Molecular nitrogen. Ni- is isoelectronic with both carbon monoxide and the nitrosyl ion but, despite the numerous complexes of CO and NO, for many years it proved to be impossible to form complexes of dinitrogen This difference in behavior was usually ascribed to the lack of polarity of N2 and a resultant inability to behave as a 7T acceptor.49... 

Titov believes that phenols are formed from hydrocarbons under the influence of the nitrosyl ion, NO+ A nitroso compound forms first, which then undergoes a rearrangement ... 

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