Aryl radicals rate constants

The Z group both modifies the reactivity of the macromonomer transfer agent (1) towards radical addition and conveys stability to the intermediate radical (2). Z is most often an ester or an aryl group. Rate constants for radical addition to the macromonomer transfer agents are generally similar to that of the common monomers they resemble 10 -10 M s ) and transfer... 

Absolute rate constants for the attack of aryl radicals on a variety of substrates have been reported by Scaiano and Stewart (Ph ) 7 and Citterio at al. (/j-CIPh-).379,384 The reactions are extremely facile in comparison with additions of other carbon-centered radicals [e.g. jfc(S) = 1.1x10s M"1 s"1 at 25 °C].3,7 Relative reactivities are available for a wider range of monomers and other substrates (Tabic 3.b). Phenyl radicals do not show clear cut electrophilic or... 

The sum of all results is consistent with the formation of both the aryl cation and the aryl radical in the aqueous acid system without copper, and with the dominance of the aryl radical in the presence of copper. The product ratios are also qualitatively consistent with the hypothesis that the reactivity of aryl cations with nucleophiles is close to that of a diffusion-controlled process (see Sec. 8.3), and that aryl radicals have arylation rate constants that are about two orders of magnitude smaller than that for diffusion control (0.4-1.7 X 107 m-1s-1 Kryger et al., 1977 Scaiano and Stewart, 1983). Due to the relatively low yields of these dediazoniations in the pentyl nitrite/benzene systems, no conclusions should be drawn from the results. 

Table 3.3. Fragmentation Rate Constants and Standard Potentials for Aryl Chlorides Anion Radicals in DMF...

FIGURE 3.19. Correlation between the fragmentation rate constant (in s-1) and the standard potential and the fragmentation standard free energy (in V vs. SCE) (top) and activationdriving force relationship (free enthalpies in eV) (bottom) for aryl chloride anion radicals. Data from Table 33. Adapted from Figure 3 of reference 30, with permission from the American Chemical Society. 

Fig. 11 Forward electron transfer (90) rate constant, k, versus the standard potential, F /q, of a series of aromatic anion radicals for rapidly cleaved aryl halide anion radicals (DMF, 20°C). kjy is the bimolecular diffusion limit. (Adapted from Andrieux et al., 1979.)...

Several methods have been employed to extract the rate constant of the addition of nucleophiles to the aryl radicals from the kinetics of Sr I reactions. Relative reactivities of two nucleophiles towards the same aryl radical have been obtained from the ratio of the two substitution products after preparative-scale reaction of the substrate with a mixture of the two nucleophiles under photochemical or solvated-electron induction (Galli and Bunnett, 1981). 

A quick and non-destructive method for measuring relative reactivities of two nucleophiles towards the same aryl radical derives from repetitive cyclic voltammetry of a solution containing the substrate and the two nucleophiles (Amatore et ai, 1985b). The ratio of the peak heights corresponding to the two substitution products provides straightforwardly the ratio of the two rate constants. 

Table 1 Rate constants (m s ) for the reaction of nucleophiles with aryl radicals...

Rate constants and Arrhenius parameters for the reaction of Et3Si radicals with various carbonyl compounds are available. Some data are collected in Table 5.2 [49]. The ease of addition of EtsSi radicals was found to decrease in the order 1,4-benzoquinone > cyclic diaryl ketones, benzaldehyde, benzil, perfluoro propionic anhydride > benzophenone alkyl aryl ketone, alkyl aldehyde > oxalate > benzoate, trifluoroacetate, anhydride > cyclic dialkyl ketone > acyclic dialkyl ketone > formate > acetate [49,50]. This order of reactivity was rationalized in terms of bond energy differences, stabilization of the radical formed, polar effects, and steric factors. Thus, a phenyl or acyl group adjacent to the carbonyl will stabilize the radical adduct whereas a perfluoroalkyl or acyloxy group next to the carbonyl moiety will enhance the contribution given by the canonical structure with a charge separation to the transition state (Equation 5.24). 

The radical-cation is relatively stable when the 1-aryl group has a para-substituent and can be characterised by uv-spectroscopy [34], When this para-substituent is not present, two radical-cations dimerise by carbon-carbon bond formation at this position, followed by loss of two protons. The rate constant for this dimerization step can be deduced from the variation of the rotating disc elec-... 

Some homolytic fragmentation reactions are driven by formation of small, stable molecules. Alkyl acyloxyl radicals (RCOp decarboxylate rapidly (fe > 1 x 10 s ) to give alkyl radicals, and even aryl acyloxyl radicals (ArCOp decarboxylate to aryl radicals with rate constants in the 10 s range." Azo radicals produced in the homolysis of azo initiators eliminate nitrogen rapidly. Elimination of carbon monoxide from acyl radicals occurs but is slow enough (fe 10" -10 such that the acyl radical can be trapped in a bimolecular process,... 

Aryl radical additions to anions are generally very fast, with many reactions occurring at or near the diffusion limit. For example, competition studies involving mixtures of nucleophiles competing for the phenyl radical showed that the relative reactivities were within a factor of 10, suggesting encounter control,and absolute rate constants for additions of cyanophenyl and 1-naphthyl radicals to thiophenox-ide, diethyl phosphite anion, and the enolate of acetone are within an order of magnitude of the diffusional rate constant. ... 

The formation of RSSR from RS and RS species is particularly relevant in the present context because it is the reverse of the electro-induced radical anion cleavage (equation 76). Actually, the formation of RSSR from reaction (79) is as well studied as the reaction between aryl carbon radicals and anionic nucleophiles, the fundamental step of the SrnI. Equilibrium constants in the range 10 -10 M for reaction (79) were determined for a number of alkyl-type systems in water, although the corresponding values for aryl-type systems are smaller. The rate constants... 

The electrochemical analysis allowed the determination of kinetic constants for this reaction46. Thus, in the presence of bromobenzene, the rate constant for the oxidative addition was found to be equal to about 70 M 1 s 1. The a-arylnickel complexes are unstable, except those obtained from o-tolyl or mesityl bromide as starting substrates. In these particular cases, the arylnickel complexes can be prepared by electrolysis from an ArBr/NiBr2(bpy) equimolar ratio. However, the exhaustive electrolysis of an aromatic iodide in the presence of ZnBr2, in DMF and at —1.4 V/SCE, leads to the corresponding arylzinc compound but the yield remains low (<20%). Indeed, the aryl iodide is mainly converted to ArH according to, very likely, a radical process (Scheme 11). 

In aprotic solvents, the radical anion, RX , for aryl halides has been detected as intermediate. In cyclic voltammetry of aryl halides, though an irreversible two-electron reduction occurs at low scan rate, a reversible one-electron reduction occurs at high scan rate. Thus, it is possible to get the values of the standard potential ( °) for the RX/RX couple and the rate constant (k) for RX -> R (therefore, the lifetime of RX ). In Fig. 8.18, the relation between ° and log k for aryl bromides in DMF is linear with a slope of 0.5 [5If], It is apparent that the lifetime of RX , obtained by 1/k, increases with the positive shift of E0. In contrast, the existence of RX for alkyl monohalides has never been confirmed. With these compounds, it is difficult to say whether the two processes, i.e. electron transfer and bond cleavage, are step-wise or concerted (RX+e -> R +X ). According to Sa-veant [5le], the smaller the bond dissociation energy, the larger the tendency for the concerted mechanism to prevail over the step-wise mechanism. 

Photolysis of aryl or pyridyl oxime esters in pyridine provides a-phenylpyridines as the major products together with bipyridyls (84TL3887). Rate constants for the addition of phenyl radical to protonated and non-protonated 4-substituted pyridines have been determined by studing the competition between phenyl radical addition and chlorine abstraction from carbon. The 4-arylpyridines were the major products, and no 3-substituted pyridines were observed. Among the solvents studied (MeCN, DMF, DMSO, and HMPA), MeCN gave the highest yields and selectivity (910PP438). 

Rate constants for quenching of 1-7 by methanol and acetic acid in hexane solution from fluorescence quenching and quantum yield data are 10 M l-s-l-. Limiting quantum yields for adduct formation are 0.1. The observation of reactions of protic solvent with 1-7 but not 1-t may reflect the longer lifetime and/or enhanced reactivity of the cyclic molecule. While photo-induced nucleophilic addition is a common reaction of aryl olefins, it is normally observed to occur only under conditions of electron-transfer sensitization (139). Under these conditions, it is the aryl olefin cation radical which undergoes nucleophilic attack. The reaction of 1-7 with protic solvents appears to be the only reported example of nucleophilic trapping of an aryl olefin it,it singlet state (140). 

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