Arenium ions stabilization

Substituents Relative Arenium Ion stability Relative n-Complex Stability Rate of Chlorination" Rate of Nitration ... 

How can we tell if 10 is present on the reaction path If it is present, there are two possibilities (1) The formation of 10 is rate determining (the conversion of 10 to 11 is much faster), or (2) the formation of 10 is rapid, and the conversion 10 to 11 is rate determining. One way to ascertain which species is formed in the rate determining step in a given reaction is to use the stability information given in Table 11.1. We measure the relative rates of reaction of a given electrophile with the series of compounds Usted in Table 11.1. If the relative rates resemble the arenium ion stabilities, we conclude that the arenium ion is formed in the slow step but if they resemble the stabilities of the Jt complexes, the latter are formed in the slow step. When such experiments are carried out, it is found in most cases that the relative rates are similar to the arenium ion and not to the n complex stabilities. For example,... 

Examples of arenium ion stabilization by resonance and inductive effects... 

The carbocation formed m this step is a cyclohexadienyl cation Other commonly used terms include arenium ion and a complex It is an allylic carbocation and is stabilized by electron delocalization which can be represented by resonance... 

To involve allylic resonance in stabilizing the arenium ion formed during attack at C 2 the benzenoid character of the other ring is sacrificed... 

TABLE 11.1 Relative Stabilities of Arenium Ions and ir Complexes and Relative Rates of Chlorination and Nitration ... 

An important contribution to silylium ion chemistry has been made by the group of Muller, who very recently published a series of papers describing the synthesis of intramolecularly stabilized silylium ions as well as silyl-substituted vinyl cations and arenium ions by the classical hydride transfer reactions with PhjC TPEPB in benzene. Thus, the transient 7-silanorbornadien-7-ylium ion 8 was stabilized and isolated in the form of its nitrile complex [8(N=C-CD3)]+ TPFPB (Scheme 2.15), whereas the free 8 was unstable and possibly rearranged at room temperature into the highly reactive [PhSi /tetraphenylnaphthalene] complex. ... 

The results indicate that the formation of long-lived trimethyl substituted silyl cations, in the presence of aromatic solvents, as claimed by Lambert et al.95 is not feasible under these conditions. Persistent silicenium ions require sterically more shielding substituents at silicon or hypercoordinative stabilization.96 98 13C and 29Si NMR chemical shifts were calculated for a series of disilylated arenium ions 85 using density functional theory (DFT). The calculations predict consistently the unsaturated carbon atoms to be too deshielded by 8-15 ppm. Applying an empirical correction, the deviation between experiment and theory was reduced to -0.4 to 9 ppm, and the 13C NMR chemical shift of the highly diagnostic cipso is reproduced by the calculations (Ad = -3.8 to 2.7 ppm).99... 

Silylium ions, which are not protected sterically or are not stabilized either electronically or by intramolecular interaction with a remote substituent do interact strongly with the solvent and/or the counteranion. The reaction of the transient silylium ion with solvents like ethers, nitriles and even aromatic hydrocarbons lead to oxonium, nitrilium and arenium ions with a tetrahedral environment for the silicon atom. These new cationic species can be clearly identified by their characteristic Si NMR chemical shifts. That is, the oxonium salt [Me3SiOEt2] TFPB is characterized by S Si = 66.9 in CD2CI2 solution at —70°C. " Similar chemical shifts are found for related silylated oxonium ions. Nitrilium ions formed by the reaction of intermediate trialkyl silylium ions with nitriles are identified by Si NMR chemical shifts S Si = 30—40 (see also Table VI for some examples). Trialkyl-substituted silylium ions generated in benzene solution yield silylated benzenium ions, which can be easily detected by a silicon NMR resonance at 8 Si = 90—100 (see Table VI). ... 

The intramolecular stabilization of germyl cation 34 by a remote aryl substituent was demonstrated by the NMR chemical shifts of the coordinated aryl ring. The chemical shift pattern found for the coordinated arene ring of 34 is characteristic for arenium ions and it closely resembles that found bissilylated arenium ions 78. 

Substituents already bonded to an aromatic ring influence both the rate of electrophilic substitution and the position of any further substitution. The effect of a particular substituent can be predicted by a consideration of the relative stability of the first-formed arenium cation, formation of which constitutes the rate-lintiting step. In general, substituents that are electron releasing activate the ring to further substitution - they help to stabilize the arenium ion. Substituents that are electron withdrawing destabilize the arenium ion, therefore, are deactivating and hinder further substitution. 

Stabilization of the arenium ion through electron-donating effects is typical of alkyl substituents. This is not strictly an inductive effect (see Section 4.3.3),... 

Energies for various possible arenium ions and regioisomeric benzylic cations were computed at the DFT B3LYP/6-31G(d) level or by AMI for comparison with the experimental results. These findings provided further evidence in support of the stability sequence 1-pyrenyl > 4-pyrenyl > 2-pyrenyl in a-pyrene-substituted carbocations as models for the intermediates arising from BaP-epoxide ring opening (Fig. 10). 

Wheland intermediates, a complexes, or arenium ions In the case of benzenoid systems they are cyclohexadienyl cations. It is easily seen that the great stability associated with an aromatic sextet is no longer present in 1, though the ion is stabilized by resonance of its own. The arenium ion is generally a highly reactive intermediate and must stabilize itself by a further reaction, although it has been isolated (see p. 504). 

TABLE 11.1 Relative stabilities of arenium ions and ir complexes and relative rates of chlorination and nitration... 

The orientation and reactivity effects of each group are explained on the basis of resonance and field effects on the stability of the intermediate arenium ion. To understand why we can use this approach, it is necessary to know that in these reactions the product is usually kinetically and not thermodynamically controlled (see p. 214). Some of the reactions are irreversible and the others are usually stopped well before equilibrium is reached. Therefore, which of the three possible intermediates is formed is dependent not on the thermodynamic stability of the products but on the activation energy necessary to form each of the three... 

---