16-electron cationic species

The equation does not take into account such pertubation factors as steric effects, solvent effects, and ion-pair formation. These factors, however, may be neglected when experiments are carried out in the same solvent at the same temperature and concentration for an homogeneous set of substrates. So, for a given ambident nucleophile the rate ratio kj/kj will depend on A and B, which vary with (a) the attacked electrophilic center, (b) the solvent, and (c) the counterpart cationic species of the anion. The important point in this kind of study is to change only one parameter at a time. This simple rule has not always been followed, and little systematic work has been done in this field (12) stiH widely open after the discovery of the role played by single electron transfer mechanism in ambident reactivity (1689). 

Friedel-Crafts (Lewis) acids have been shown to be much more effective in the initiation of cationic polymerization when in the presence of a cocatalyst such as water, alkyl haUdes, and protic acids. Virtually all feedstocks used in the synthesis of hydrocarbon resins contain at least traces of water, which serves as a cocatalyst. The accepted mechanism for the activation of boron trifluoride in the presence of water is shown in equation 1 (10). Other Lewis acids are activated by similar mechanisms. In a more general sense, water may be replaced by any appropriate electron-donating species (eg, ether, alcohol, alkyl haUde) to generate a cationic intermediate and a Lewis acid complex counterion. 

In all the cluster compounds discussed above there are sufficient electrons to form 2-centre 2-electron bonds between each pair of adjacent atoms. Such is not the case, however, for the cationic bismuth species now to be discussed and these must be considered as electron deficient . The unparalleled ability of Bi/BiCb to form numerous low oxidation-state compounds in the presence of suitable complex anions has already been mentioned (p. 564) and the cationic species shown in Table 13.12 have been unequivocally identified. 

Figure 17.15 The structure of (a) the nonlinear p" cation in laAsFg and (b) the weaker cation-anion interactions along the chain (cf Fig. 17.13). For comparison, the dimensions of (c) the linear 22-electron cation L" and (d) the nonlinear 20-electron cation Te3 are given. The data for this latter species refer to the compound [K(crypt)]2Te3.en in K2Tc3 itself, where there are stronger cation-anion interactions, the dimensions are r = 280 pm and angle = 104.4°).

Naphthol 1 is initially protonated at a carbon center of high electron density (C-2 or C-4). The cationic species 3 thus formed is stabilized by resonance it can add a bisulfite anion at C-3. The addition product can tautomerize to give the more stable tetralone sulfonate 4 the tetralone carbonyl group is then attacked by a nucleophilic amine (e.g. ammonia). Subsequent dehydration leads to the cation... 

Similar arguments can be used to predict the relative stabilities of the cyclo-heptatrienyl cation, radical, and anion. Removal of a hydrogen from cyclohepta-triene can generate the six-77-electron cation, the seven-77-electron radical, 01 the eight-77-elec iron anion (Figure 15.6). All three species again have numerous resonance forms, but HiickeTs rule predicts that only the six-7r-electron cyclohep-tatrienyl cation should be aromatic. The seven-77-electron cycloheptatrienyl radical and the eight-77-electron anion are antiaromatic. 

The reactivity of neutral dienophiles is greatly increased by converting them to the corresponding cation radicals because these highly electron-deficient species can then react readily with dienes. 

A cation may associate with electron-donating species to form a complex. 

The all-silicon version of the cyclobutenyl radical, cyclotetrasilenyl radical 40, was recently reported by Sekiguchi et al. Its synthesis was accomplished by the one-electron reduction of the precursor cationic species, cyclotetrasilenylium ion 20 TPFPB with either t-Bu3SiNa or KCg in Et20 (Scheme 2.33). The four-membered Si4 ring of 40 is nearly planar with the Sil-Si2 and Si2-Si3 bonds... 

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