Dimerization radical

Reactions with Parting of Radicals. The one-electron oxidation of cationic dyes yields a corresponding radical dication. The stabihty of the radicals depends on the molecular stmcture and concentration of the radical particles. They are susceptible to radical—radical dimerization at unsubstituted, even-membered methine carbon atoms (77) (Fig. 6). 

The fluorinated titanocycle related to (28) is not obtained from C H CMUCgF. Photolysis of CP2T1X2 always gives first scission of a Cp—Tibond. In a chlorinated solvent, the place vacated by Cp is assumed by Cl. In the absence of some donor, the radical dimerizes (298—299). 

EPR studies of S-N radicals were reviewed in 1990. Many radicals containing the S-N linkage are persistent for more than several hours in solution at room temperature. Perhaps the best known example is the nitrosodisulfonate dianion [0N(S03)] , named as Fremy s salt. In the solid state this radical dianion dimerizes through weak N 0 interactions, but it forms a paramagnetic blue-violet monomer in solution. Although most chalcogen-nitrogen radicals dimerize in the solid state, a few heterocyclic C-S-N systems can be isolated as monomers (Section 11.3). 

The selenium analogue [PhCNSeSeN] and cyano-functionalized diselenadiazolyl radicals adopt cofacial dimeric structures, e.g., 11.4 (E = Se), with unequal Se Se interactions of ca. 3.15 and 3.35 A. In the latter case the radical dimers are linked together by electrostatic CN Se contacts.Tellurium analogues of dithiadiazolyl radicals (or the corresponding cations) are unknown, but calculations predict that the radical dimers, e.g., 11.4 (E = Te), will be more strongly associated than the sulfur or selenium analogues. ... 

The reactions of binary cyclic S-N cations with the radical dimer... 

Majeti11 has studied the photochemistry of simple /I-ketosulfoxides, PhCOCH2SOCH3, and found cleavage of the sulfur-carbon bond, especially in polar solvents, and the Norrish Type II process to be the predominant pathways, leading to both 1,2-dibenzoylethane and methyl methanethiolsulfonate by radical dimerization, as well as acetophenone (equation 3). Nozaki and coworkers12 independently revealed similar results and reported in addition a pH-dependent distribution of products. Miyamoto and Nozaki13 have shown the incorporation of protic solvents into methyl styryl sulfoxide, by a polar addition mechanism. 

The effect has been most commonly encountered in the decomposition of symmetrical diacyl peroxides where it is easily recognized since the symmetrical radical dimer, for which Ag must be zero, is formed and shows net polarization. Clearly, studies of such systems are capable of providing valuable information on the dynamics of radicals and radical pairs in solution, the polarization process providing a time base for events (see Section V,B). 

A mixture of water/pyridine appears to be the solvent of choice to aid carbenium ion formation [246]. In the Hofer-Moest reaction the formation of alcohols is optimized by adding alkali bicarbonates, sulfates [39] or perchlorates. In methanol solution the presence of a small amount of sodium perchlorate shifts the decarboxylation totally to the carbenium ion pathway [31]. The structure of the carboxylate can also support non-Kolbe electrolysis. By comparing the products of the electrolysis of different carboxylates with the ionization potentials of the corresponding radicals one can draw the conclusion that alkyl radicals with gas phase ionization potentials smaller than 8 e V should be oxidized to carbenium ions [8 c] in the course of Kolbe electrolysis. This gives some indication in which cases preferential carbenium ion formation or radical dimerization is to be expected. Thus a-alkyl, cycloalkyl [, ... 

Recently, an interesting example of stereoselective radical dimerization was described which awaits explanation. It was found that radical 49 (X = p-Cl R = t-butyl) dimerizes diastereoselectively120) to the more stable D, L-diastereomer in contrast to other radicals 49 with smaller side chains R. It has not been clearly decided so far... 

Scheme 3.47. Head-to-head reductive radical dimerization.

The isolation of calycanthine (9) in 1888 by Eccles [28] and the subsequent proposition for its origins in the oxidative dimerization of tryptamine by Woodward [29] and Robinson [30] had prompted several key synthetic studies based on a biomimetic approach. Hendrickson was the first to experimentally verify the plausibility of forming the C3-C3 linked dimers through an oxidative radical dimerization strategy (Scheme 9.2a). He demonstrated that the sodium enolate of a tryptamine-derived oxindole could be oxidized with iodine to afford a mixture of three possible stereoisomers. The racemic product was isolated in 13 % yield, while the meso product was isolated in 8 % yield. Global reduction of the oxindole and carbamates afforded the first synthetic samples of chimonanthine (7) [9a],... 

The intermediately formed alkyl radical could be either further oxidized in presence of IPT and water molecules yielding corresponding alcohols or recombine with other radical (dimerization reaction) ... 

Rate Constants, Equilibrium Constants, Enthalpies, and Entropies of Aroxyl Radicals Dimerization in Hexane at T = 293 K... 

The color of the quinonoid compounds that may be obtained by disproportionation can be sufficiently like that of the radicals to cause confusion if visual observation or broad-band spectrophotometry is used.11 For example, Preckel and Selwood, using paramagnetism as a measure of the amount of radical, reported that solutions of triphenyl-methyl derivatives more or less rapidly lost their paramagnetism. The decomposed solutions were still highly colored, but the color was no longer dependent on the temperature as it is in the case of a radical-dimer equilibrium mixture. What is more striking, and an even more subtle and dirtier trick on the part of nature, is the fact that Preckel and Selwood s non-paramagnetic solutions were still rapidly bleached by exposure to the air. It is clear that radical-like reactivity is not a safe criterion for the presence of radicals. It is also clear that the ebullioscopic method is particularly unsatisfactory in view of the excellent chance for decomposition. 

Besides the mirror and addition reactions already discussed, gas phase radicals dimerize, disproportionate, transfer hydrogen, and polymerize olefins. Similar reactions in the liquid phase are an indication (but not proof) of free radical intermediates. 

For example, in the ferrous ion-initiated radical decomposition of some hydroperoxides, Kharasch suggests that the reaction is /9-cleavage rather than rearrangement since ketones but no rearranged radical dimers are formed. 

The concentration of copper(II) has a pronounced effect on the course of the reaction. In the presence of very low copper(II) concentrations, oxidation of allyl radical 69 is slow and major amounts of allyl radical dimer are formed. In the presence of very high concentrations of copper(II), radical 68 is oxidized rapidly before addition to diene can take place. An optimum yield of product 71 can therefore only be achieved at certain copper(II) concentrations. The metal-ion-promoted addition of chloramines to butadiene appears to follow the same mechanism93. 

It is interesting to note that among initiators studied, a benzyl ketal type initiator (2,2-dimethoxy-2-phenyl acetophenone) is more active than other initiators of acetophenone type. 2,2-Dimethoxy-2-phenyl acetophenone is more active than BME, probably due to the presence of the extra methoxy group on the -carbon, which gives a more active phenyldimethoxy methyl radical (and it further cleaves to give an even more active methyl radical) than the phenylmethoxy methyl radical from BME (4). It is known that the phenylmethoxy methyl radical dimerizes easily and thus loses some of its role as a radical in a... 

The redox characteristics, using linear sweep and cyclic voltammetry, of a series of (Z)-6-arylidene-2-phenyl-2,3-dihydrothiazolo[2,3-r][l,2,4]triazol-5(6//)-ones 155 (Figure 24) have been investigated in different dry solvents (acetonitrile, 1,2-dichloroethane, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO)) at platinum and gold electrodes. It was concluded that these compounds lose one electron forming the radical cation, which loses a proton to form the radical. The radical dimerizes to yield the bis-compound which is still electroactive and undergoes further oxidation in one irreversible two-electron process to form the diradical dication on the newly formed C-C bond <2001MI3>. 

The simplest electrodimerization mechanism occurs when the species formed as the result of a first electron transfer reaction reacts with itself to form a dimer (Scheme 2.7). This mechanism is usually termed radical-radical dimerization (RRD) because the most extensive studies where it occurs have dealt with the dimerization of anion and cation radicals formed upon a first electron transfer step as opposed to the case of radical-substrate dimerizations, which will be discussed subsequently. It is a bimolecular version of the EC mechanism. The bimolecular character of the follow-up reaction leads to nonlinear algebra and thus complicates slightly the analysis and numerical computation of the system. The main features of the cyclic voltammetric responses remain qualitatively similar, however. Unlike the EC case, however, the dimensionless parameter,... 

In ion-radical dimerizations, reactivity is thus governed by the interplay among three factors bond formation, Coulombic repulsion, and solvation. The latter factor is essential to counteract Coulombic repulsion, rendering exergonic a reaction that would otherwise have been thermodynamically unfavorable. 

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