Anion-radicals definition

Besides the numerous examples of anionic/anionic processes, anionic/pericydic domino reactions have become increasingly important and present the second largest group of anionically induced sequences. In contrast, there are only a few examples of anionic/radical, anionic/transition metal-mediated, as well as anionic/re-ductive or anionic/oxidative domino reactions. Anionic/photochemically induced and anionic/enzyme-mediated domino sequences have not been found in the literature during the past few decades. It should be noted that, as a consequence of our definition, anionic/cationic domino processes are not listed, as already stated for cationic/anionic domino processes. Thus, these reactions would require an oxidative and reductive step, respectively, which would be discussed under oxidative or reductive processes. 

Analysis of the transition state in terms of energy is certainly a key aspect of the S 2-ET problem. Entropy considerations may, however, bring about additional information, possibly helping us to conceive better the transition between the two mechanisms. It was observed in this connection that, whereas the entropy of activation of both the anthracene anion radical and of the ETIOPFe(O) porphyrin (pp. 99, 100) (which have about the same standard potential) is close to zero in their reaction with s- and t-butyl bromides a definitely negative value, ca. — 20 eu is obtained for the reaction of the porphyrin with n-butyl bromide (Lexa et al., 1988). The same was found for the reaction of two other iron porphyrins, TPPFe(o) and OEP-Fe(i). These activation entropies were estimated from (153), where Z is... 

Let us compare anion-radicals with dianions, which are definitely stronger bases. For example, the cyclooctatetraene dianion (CgHg ) accepts protons even from solvents such as dimethylsulfoxide (DMSO) and V,V-dimethylformamide. The latter is traditionally qualified as an aprotic solvent. In this solvent, the cyclooctatetraene dianion undergoes protonation resulting in the formation of cyclooctatrienes (Allendoerfer and Rieger 1965) + 2H+ CgHjo. It is seen that... 

By comparing these constants with the equilibrium constants of anion-radical reactions (entries 7-10 in Table 2.1), one can conclude that in case of dianions, the equilibrium is definitely shifted to the right. The equilibrium constants of ca. 0.35 are increased almost twofold, up to approximately 0.7, but remain less than unity. This means that even with the formation of dianions, the possibility of isotopic enrichment still remains qnite feasible, although the process becomes less favorable than that in the case of nitrobenzene. 

As mentioned earlier, much attention was being given to the formation of ion-radical conductors in the appropriate crystalline form. Meanwhile, Ziolkovskiy et al. (2004) reported data on high conductivity at 77-300 K of the methyl-TCNQ anion-radical salts with A-alkylpyridinium cations that keep their conductivity after crystallization from the melted forms. The melting temperatures of the salts described are rather low and the melting proceeds without salt destruction. This feature opens a possibility to create definite, much essential constructive elements directly from the liquid phase. Importantly, these salts also possess affinity to metals due to the metal-nitrogen coordina-tive ability. The authors notice that such ion-radical salts are promising for use in electronics and microelectronics. 

In the most general sense, any anion radical produced by reduction with a metal, or by electrolytic reduction in the presence of a metallic counterion could be considered an organometallic anion radical. Any review based on such a definition would be monumental. To achieve a manageable volume of material, with a content suitable to the context of this series, we have limited this chapter to anion radicals produced from organometallic compounds. Anion radicals for which the metal is present solely as the reducing agent or counterion have, for the most part, been excluded. 

The definition also includes species in which a common radical function such as a ketyl, nitro anion-radical, or semiquinone is conjugated with a heteroaromatic system, e.g., 6-9. Certain major radical series are, however,... 

Other reactions of aromatic hydrocarbon anion radicals and amine cation radicals lead to exciplex emission, particularly in nonpolar solvents [15], Luminescence from exciplexes is most definitively observed in systems for which the redox reaction is energetically unable to yield a localized excited state. The free energy of exciplex formation, jE exc, is associated with solvation and geometry optimization in the encounter complex of and A+. 

Perhaps the most interesting reaction of all of the possible anion radical pericyclic reactions, a Diels-Alder cycloaddition, has not been definitively exemplified, but one potential example of such a reaction has been proposed [127],... 

T]he mechanism still remains to be clarified since there is almost no definite information on the mechanism by which an alkyl or aryl group is transferred to the initially formed anion radicals. 

The effect of substituents on electron-transfer rate constants has also been reported [201], and a summary of these studies have been given in several reviews [2, 7, 10]. The previously open-to-question assignment of the Fe(II) reduction product as an Fe(I) species or an Fe (11) porphyrin n -anion radical [202] now seems definitive in many cases [203, 204], but the exact site of electron transfer wiU vary as a function of the solution conditions as well as the porphyrin macrocycle. 

With respect to our definition of photoassisted reactions also catalyzed photolyses are covered by this category. It was shown very recently [42] that the quantum yield of the well known photo decomposition of ferrioxalate is increased in the presence of copper(II) ions. Here, copper(II) in the ground state acts as a catalyst. Mechanistically, it is assumed that copper(II) accelerates the decomposition of the coordinated oxalate anion radical in the intermediate iron(II) complex. Copper(I) formed thereby is reoxidized in a thermal reaction by another ferrioxalate ion. In the absence of copper(II) the intramolecular back electron-transfer within the intermediate iron(II) complex is responsible for quantum yields lower than the theoretical limit. 

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