A-radical cation

Thus two electrons exit the reaction zone, leaving a positively charged species (M ) called an ion (in this case, a molecular ion). Strictly, M" is a radical-cation. This electron/molecule interaction (or collision) was once called electron impact (also El), although no impact actually occurs. 

Fig. 6. One-electron oxidation and dimerization where (21a) is a dye, (21b) a radical cation, and (21c) a dimer.

Fig. 9. Initiation of epoxy cure. Irradiation of a triaryl sulfonium salt produces a radical cation that reacts with an organic substrate RH to produce a cation capable of releasing a proton. The proton initiates ring-opening polymerization. X = BF , PFg, AsFg, and SgFg. ...

Cobalt trifluoride fluorination corresponds to the electron-transfer mechanism via a radical cation. RF groups attached to the ring enhance the stability of intermediate dienes and monoenes. Perfluoroalkyl pyridines, pyrazines, and pyrimidines were successfully fluorinated but pyridazines eliminated nitrogen. The lack of certain dienes was attributed to the difference in stability of FC=C and RFC=C and steric effects [81JCS(P1)2059]. 

Two pathways for the reaction of sulfate radical anion with monomers have been described (Scheme 3.81).252 These are (A) direct addition to the double bond or (B) electron transfer to generate a radical cation. The radical cation may also be formed by an addition-elimination sequence. It has been postulated that the radical cation can propagate by either cationic or a radical mechanism (both mechanisms may occur simultaneously). However, in aqueous media the cation is likely to hydrate rapidly to give a hydroxyelhyl chain end. 

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 anodic polymerization of aniline can occur by a radical cation coupling mechanism analogous to that shown in Scheme 1, with coupling occurring between the N of one molecule and the para-position of another (Structure 4)21,22 However, a variety of other mechanisms have also been proposed,21 and it is likely that their relative rates depend upon the conditions (solvent, potential, pH, etc.) employed. The links between monomers are therefore not exclusively between the N and para-position (head-to-tail coupling). Head-head (-N=N-) and tail-tail (para-para) coupling occur more often as the pH is increased.71... 

Photo-induced Diels Alder reaction occurs either by direct photo activation of a diene or dienophile or by irradiation of a photosensitizer (Rose Bengal, Methylene Blue, hematoporphyrin, tetraphenylporphyrin) that interacts with diene or dienophile. These processes produce an electronically excited reagent (energy transfer) or a radical cation (electron transfer) or a radical (hydrogen abstraction) that is subsequently trapped by the other reagent. 

Substituted phenylacetic acids form Kolbe dimers when the phenyl substituents are hydrogen or are electron attracting (Table 2, Nos. 20-23) they yield methyl ethers (non-Kolbe products), when the substituents are electron donating (see also chap. 8). Benzoic acid does not decarboxylate to diphenyl. Here the aromatic nucleus is rather oxidized to a radical cation, that undergoes aromatic substitution with the solvent [145]. 

We postulated a reaction mechanism with participation of an aromatic radical cation which was formed by one electron transfer from an aromatic hydrocarbon to copper(II) chloride. Activated alumina has electron-acceptor properties, and formation of a radical cation of an aromatic hydrocarbon adsorbed on alumina has been observed by ESR (ref. 13). Therefore, it seemed to us that alumina as a support facilitates the generation of the radical cation of the aromatic hydrocarbon. 

The iodine reaction is possibly a one-electron oxidation with the initial formation of a radical cation ... 

Even the photoelectron spectroscopy of closed-shell molecules is valuable for the physical chemistry of radicals because a difference between the nth and the first adiabatic ionization potentials determines the excitation energy in a radical cation for a transition from the ground doublet state to the (n — 1) excited doublet state. 

This suggests a fast pre-equilibrium involving electron transfer followed by slow oxidation of a radical-cation, viz. 

H2SO4 = 0.09 M, fi = 2.0 M). Arrhenius parameters are A 10 ° I.mole . sec and E 28.5 kcal.mole . Successive alkylation of the olefinic bond increases the rate of reaction. One unusual feature is the lack of any acidity dependence. This implies that Co(H20)g is the active oxidant and that a radical cation is formed initially the lack of any retardation by added Co(II) means that the initial step is irreversible, viz. 

This is in accordance with the primary kinetic isotope effect for Mn(III) sulphate With Co(III) electron abstraction may occur to give a radical-cation which suffers further oxidation. The alternative explanation of the lack of an isotope effect is that formation of the Co(III)-ketone complex is rate-determining this lacks, however, other kinetic support . ... 

Swain and Hedberg have shown that the tertiary alcohol is not an intermediate, for the dehydration process is slower than the rate of formation of dye. Instead it is proposed that the tertiary hydrogen is removed to give a radical-cation which is further oxidised to the carbonium ion. The oxidation involves two steps one fast and one very much slower. This parallels the Ce(IV) oxidation of iodide ion and is therefore probably a function of the oxidant. 

Oxidation — Oxidizing radicals with high redox potential can remove one electron from the carotenoid molecule to yield a radical cation CAR - e- CAR+ (e.g. CAR H- R CAR + R). 

The localization of the HOMO is also important for another reason. Since it describes the distribution of a hole in a radical cation, it relates to the hindrance that a positive charge will encounter as it propagates along the chain. There is indeed experimental evidence (9) that the hole states of the polysilane chain are localized and that they move by a hopping mechanism. 

---