Aromatic anion radicals protonation

Returning to direction a in Scheme 1.10, it is interesting to compare pK values of protonated aromatic anion-radicals, pA, j(ArH2 ) and pK values of parent aromatics protonated in the absence of a preliminary electron transfer, p/f (ArH2). As seen from Table 1.3, if the anion-radicals accept a proton, they hold it much more firmly than the parental neutral molecules (ApK values are positive). 

Another common solvent that contains the oxygen atom easily available for coordination with metal cations is THE. The ability of anion-radicals to remove a proton from the position 2 of THE is sometimes a problem. Dimethyl ether is more stable as a solvent its oxygen atom is also exposed and can coordinate with a metal cation with no steric hindrance from the framing alkyl groups. An added advantage of dimethyl ether is that, because of its low boiling point (-22°C), it can be readily removed after reductive metallation and replaced by the desired solvent. The use of aromatic anion-radicals in dimethyl ether (instead of THE) is well documented (Cohen et al. 2001, references therein). 

The reversible one-electron transfer to form an anion radical (R ) is followed by an irreversible chemical protonation to form /f H, which is subsequently reduced itself (the reduction potential of the species / H, has been shown to be more positive3 than that of the parent, R) and then undergoes another irreversible protonation reaction. In a protic solvent, the reactions proceed rapidly to the final product, / H2. In a rigorously purified aprotic solvent, the intermediate anion radical R , has an appreciable lifetime and reacts only slowly, principally with adventitious impurities in the solvent. Thus, the stability of aromatic anion radicals can be taken as a measure of the protic character of a solvent. 

Aromatic anion radicals can protonate on the ring to yield cyclohexadienyl radicals. This process has been observed with the electron adduct of benzene [reaction (81)] (Michael and Hart, 1970)... 

Rates of protonation of aromatic anion radicals also have been estimated from polarographic measurements by observation of changes in the curve shape upon protonation ( ). These experiments were carried out in DMSO as solvent with various phenols as proton donors. This method, however, is applicable only within a limited range of protonation rates and is less reliable than the direct observation of the kinetic process. Furthermore, correlation of the protonation rates ( ) with calculated electron densities does not appear to be satisfactory. 

Kinetics of Formation and Protonation of Aromatic Anion Radicals ... 

The reactivities of aromatic compounds have been correlated with various physical parameters, such as ionization potentials, triplet energies, free valence, and energy levels of lowest unoccupied orbitals (10,11) < It was noted that simplified HMO calculations were sufficient to account for many experimental observations. However, the reactivities of aromatic anion radicals toward proton donors have not been successfully correlated with any physical parameter. Such a correlation may shed light on the mechanism and allow prediction of unknown rates. 

In the early work on aromatic anion radicals, Paul, Lipkin, and Weissman (1) correlated the reactivities of these radicals with electron affinities derived from their spectra. Bank and Bockrath ( ) compared the rates of protonation of naphthalene and anthracene anion radicals and concluded that the higher rate for naphthalene was in contradiction to their prediction from molecular orbital localization energy calculations. Fry and Schuettenberg (5) correlated the rates of protonation of various aromatic... 

The present study shows that the rate of protonation of an aromatic anion radical can be correlated with the energy level (LUMO) of the unpaired electron. This finding suggests, on the basis of Hammond s postulate (] ), that the transition state in the protonation process resembles the anion radical more than it resembles the product (neutral radical). 

In the presence of a proton source, the radical anion is protonated and further reduction occurs (the Birch reduction Part B, Section 5.5.1). In general, when no proton source is present, it is relatively difficult to add a second electron. Solutions of the radical anions of aromatic hydrocarbons can be maintained for relatively long periods in the absence of oxygen or protons. 

More recently it has become apparent that proton equilibria and hence pH can be equally important in aprotic and other non-aqueous solvents. For example, the addition of a proton donor, such as phenol or water, to dimethylformamide has a marked effect on the i-E curve for the reduction of a polynuclear aromatic hydrocarbon (Peover, 1967). In the absence of a proton donor the curve shows two one-electron reduction waves. The first electron addition is reversible and leads to the formation of the anion radical while the second wave is irreversible owing to rapid abstraction of protons from the solvent by the dicarbanion. 

Allyl (27, 60, 119-125) and benzyl (26, 27, 60, 121, 125-133) radicals have been studied intensively. Other theoretical studies have concerned pentadienyl (60,124), triphenylmethyl-type radicals (27), odd polyenes and odd a,w-diphenylpolyenes (60), radicals of the benzyl and phenalenyl types (60), cyclohexadienyl and a-hydronaphthyl (134), radical ions of nonalternant hydrocarbons (11, 135), radical anions derived from nitroso- and nitrobenzene, benzonitrile, and four polycyanobenzenes (10), anilino and phenoxyl radicals (130), tetramethyl-p-phenylenediamine radical cation (56), tetracyanoquinodi-methane radical anion (62), perfluoro-2,l,3-benzoselenadiazole radical anion (136), 0-protonated neutral aromatic ketyl radicals (137), benzene cation (138), benzene anion (139-141), paracyclophane radical anion (141), sulfur-containing conjugated radicals (142), nitrogen-containing violenes (143), and p-semi-quinones (17, 144, 145). Some representative results are presented in Figure 12. 

When several magnetically equivalent nuclei are present in a radical, some of the multiplet lines appear at exactly the same field position, i.e., are degenerate , resulting in variations in component intensity. Equivalent spin-1/2 nuclei such as 1H, 19F, or 31P result in multiplets with intensities given by binomial coefficients (1 1 for one nucleus, 1 2 1 for two, 1 3 3 1 for three, 1 4 6 4 1 for four, etc.). One of the first aromatic organic radical anions studied by ESR spectroscopy was the naphthalene anion radical,1 the spectrum of which is shown in Figure 2.2. The spectrum consists of 25 lines, a quintet of quintets as expected for hyperfine coupling to two sets of four equivalent protons. 

For aromatic hydrocarbon radical anions, this approach works pretty well. Figure 2.7 shows a correlation plot of observed hyperfine splitting versus the spin density calculated from Hiickel MO theory. It also correctly predicts the negative sign of aH for protons attached to n systems. 

The reduction of organic halides in the presence of aromatic hydrocarbons, the subject of detailed kinetic studies, provide rate constants for the homogeneous ET [147-150] and the follow-up reaction [151]. The theoretical basis for this kind of experiment ( homogeneous redox catalysis ) was laid by Saveant s group in a series of papers during the years 1978-80 [152-157]. Homogeneous ET also plays an important role in the protonation of anion radicals [158]. 

Controlled one-electron reductions transform l,2,3,4-tetraphenyl-l,3-cyclopentadiene or 1,2,3, 4,5-pentaphenyl-l,3-cyclopentadiene into mixtures of the dihydrogenated products and the corresponding cyclopentadienyl anions (Famia et al. 1999). The anion-radicals initially formed are protonated by the substrates themselves. The latter are thermodynamically very strong acids because of their strong tendency to aromatization. As with the cyclopentadiene anion-radicals, they need two protons to give more or less stable cyclopentadienes. The following equations represent the initial one-electron electrode reduction of l,2,3,4,5-pentaphenyl-l,3-cyclopentadiene (CjHAtj) and explains the ratio and the nature of the products obtained at the expense of the further reactions in the electrolytic pool ... 

Differences in Values between Protonated Aromatic Compounds and Protonated Forms of the Anion-Radicals... 

Addition of 0- to double bonds and to aromatic systems was found to be quite slow. Simic et al. (1973) found that O- reacts with unsaturated aliphatic alcohols, especially by H-atom abstraction. As compared to O, HO reacts more rapidly (by two to three times) with the same compounds. In the case of 1,4-benzoquinone, the reaction with O consists of the hydrogen double abstraction and leads to the 2,3-dehydrobenzoquinone anion-radical (Davico et al. 1999, references therein). Christensen et al. (1973) found that 0- reacts with toluene in aqueous solution to form benzyl radical through an H-atom transfer process from the methyl group. Generally, the O anion-radical is a very strong H-atom abstractor, which can withdraw a proton even from organic dianions (Vieira et al. 1997). 

In case of benzene, the potassium salt of its anion-radical can be separated as a precipitate after benzene reduction by potassium in the presence of low concentrations of 18-crown-6-ether. For benzene, the heavy-form content is greatest in the solution, not in the precipitate. It is in the solution where most of the nonreduced neutral molecules remain. Since the neutral molecules are inert toward protons, the anion-radicals combine with the protons to give dihydro derivatives (products of the Birch reaction). Therefore, it is possible to conduct the separation chemically. The easiest way is to protonate a mixture after the electron transfer, than to separate the aromatic compounds from the respective dihydroaromatics (cyclohexadiene, dihydronaphthalene, etc.) (Chang and Coombe 1971, Stevenson and Alegria 1976 Stevenson et al. 1986a, 1986c, 1988). 

The final stage of the reaction in Scheme 3.65 involves protonation, yielding the derivative of 1,4-dihydronaphthalene. The oxidation may produce a 4-substituted binaphthyl, which is not contaminated with the isomeric products. It is worth noting here that the described ion-radical method of introduction of the alkyl group into the aromatic nucleus has an advantage over the radical or heteroly tic alkylation. In these cases, the neutral substrate may produce a composite mixture of isomeric products. The binaphthyl anion-radical reaction proceeds regioselectively and nonstereospecifically. 

The anion-radicals from aromatic nitro compounds preserve the second-order axis of symmetry. The analysis of superfine structure of the ESR spectrum of the nitrobenzene anion-radical reveals equivalency of the ortho and meta protons (Ludwig et al. 1964, Levy and Myers 1965). With the anion-radical of nitrosobenzene, the situation is quite different. This was evidenced from the ESR data (Levy and Myers 1965, Geels et al. 1965). Following electron transfer, the bent nitroso group fixes in the plane of the benzene ring to a certain extent. This produces five different types of protons, since both meta and ortho protons become nonequivalent. The nonequivalence of the ortho and meta protons has also been established for the anion-radicals of acetophenone (Dehl and Fraenkel 1963) and 5-methylthiobenzoate (Debacher et al. 1982 Scheme 6.17). 

It was realized that the mechanism of Birch reduction involves protonation of the anion-radical formed by the addition of one electron to the reacting aromatic compound. This is followed by rapid addition of a second electron and protonation of the forming carbanion to yield nonconjugated alicyclic products. Protonation of the anion-radical by added alcohol is the rate-limiting stage. Recent calculations show that the ortho and meta positions in anisole are most enhanced in density by electron introduction. The para position is not appreciably affected (Zimmerman and Alabugin 2001 Scheme 7.9). 

While donor substituents assist in ortho and meta protonation, acceptor substituents direct protonation of the primary anion-radicals to the ipso and para positions. It should be emphasized that water treatment of the naphthalene anion-radical in THF leads to 1,4-dihydronaphthalene. Notably, the same treatment of this anion-radical, but o-bound to rhodium, leads to strikingly different results. In the rhodium-naphthalene compound, an unpaired electron is localized in the naphthalene, but no protonation of the naphthalene part takes places on addition of water. Only evolution of hydrogen was observed (Freeh et al. 2006). Being a-bound to rhodium, naphthalene acts as an electron reservoir. The naphthalene anion-radical part reacts with a proton according to the electron-transfer scheme similar to the anion-radicals of aromatic nitro compounds (see Scheme 1.14). 

In 1969, Elschenbroich and Cais reported the ESR spectra of several ferrocenyl anion radicals, including benzoyl, p-tolyl, p-carbomethoxy-benzoyl, p-nitrophenyl, p-cyanophenyl, and nitroferrocene, prepared by electrolytic reduction in either acetonitrile or DMF (5S). In general, the ferrocenyl group destabilizes the anion radicals compared to a phenyl substituent. When both groups are present, delocalization of the unpaired electron into the phenyl substituent is more extensive, and the ESR spectra resemble, for the most part, anion radicals of substituted aromatics. There is small spin density in the ferrocenyl moiety, which appears as small hyperfine couplings for the cyclopentadienyl protons ortho to the point of substitution (38). 

The cation radical can undergo deprotonation to yield an allyl radical or nucleophilic attack by the solvent to produce a methoxyalkyl radical. Coupling of these radicals with the aromatic radical anion produces acyclic adducts. As an alternative, the anion radical can be protonated, ultimately giving reduction product. Thus, the degree of charge separation within the excited state complex dramatically influences the observable chemistry. 

Another example concerning the reduction of carbonyl compounds also relates to the salt effect theme. Shaefer and Peters (1980), Simon Peters (1981,1982,1983,1984), Rudzki et al. (1985), and Goodman and Peters (1986) described photoreductions of aromatic ketones by amines. In this case, the addition of excess NaC104 results in considerable retardation, even prevention, of final product formation. The two fundamental steps in this photoreduction consist of rapid electron transfer from the amine to the photoactivated ketone (in its triplet state), followed by the slow transfer of proton from the amine cation radical to the carbonyl anion radical ... 

It was realized that the mechanism of the Birch reduction involves protonation of the anion radical formed by addition of one electron to the reacting aromatic compound. This... 

The anion radicals from aromatic nitro compounds preserve the second-order axis of symmetry. The analysis of the superfine structure of the ESR spectrum of the nitrobenzene anion radical reveals equivalency of the ortho and me la protons (Ludwig et al. 1964 Levy Myers 1965). 

The protonation of anion radicals and dianions derived from aromatic hydrocarbons has been studied in some detail by Hoijtink and co-workers 113-11 s). it was shown that apart from the reactions given above (Eqs. (42)—(46)) other disproportionation equilibria also play an important role. These are different for different anion radicals, making the whole picture very complex. Kinetic studies on the disproportionation of the nitrobenzene anion radical and some of its derivati-ves 116,u 7) jlave s 10wn that in aqueous solution at a pH > 11.5, reaction (41) is of great importance, whereas the protonated radical ion and the radical ion are the kinetically active species in the pH interval between 3.2 and 11.5. 

The polarographic behavior of aromatic carbonyl compounds at the dropping mercury electrode in aqueous SSE s is rather complex 130 In acid medium two one-electron waves are observed, corresponding to reduction of the protonated ketone (protonation makes the reduction easier, shifting the first wave towards less cathodic potentials with decreasing pH) and the protonated anion radical, respectively ... 

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