Organic radical processes

Torrents A, BG Anderson, S Bilboulian, WE Johnson, CJ Hapeman (1997) Atrazine photolysis mechanistic investigations of direct and nitrate-mediated hydroxyl radical processes and the influence of dissolved organic carbon from the Chesapeake Bay. Environ Sci Technol 31 1476-1482. 

Although the work discussed thus far has covered primarily neutral organic radicals, there are many types of cation and anion radicals that are stabilized on the surface. Some of these ion radicals are formed through photochemical processes however, many others are spontaneously generated on a surface. The type of radical ion that is formed depends on the oxidizing or reducing character of particular sites on the surface, as well as on the ionization potential and the electronegativity of the adsorbed molecule. 

Of more intrinsic interest are processes involving two electrons, since these constitute the great bulk of organic reductive processes, especially in protonic solvents. The reason for this is that the first electron transfer will generate an unstable radical species, whereas the second can regenerate a stable closed-shell product. One example that we have already encountered is C02 reduction but a case that has been well studied is that of quinone reduction as ... 

For many years, investigations on the electronic structure of organic radical cations in general, and of polyenes in particular, were dominated by PE spectroscopy which represented by far the most copious source of data on this subject. Consequently, attention was focussed mainly on those excited states of radical ions which can be formed by direct photoionization. However, promotion of electrons into virtual MOs of radical cations is also possible, but as the corresponding excited states cannot be attained by a one-photon process from the neutral molecule they do not manifest themselves in PE spectra. On the other hand, they can be reached by electronic excitation of the radical cations, provided that the corresponding transitions are allowed by electric-dipole selection rules. As will be shown in Section III.C, the description of such states requires an extension of the simple models used in Section n, but before going into this, we would like to discuss them in a qualitative way and give a brief account of experimental techniques used to study them. 

Electrochemistry, organic, structure and mechanism in, 12, 1 Electrode processes, physical parameters for the control of, 10, 155 Electron donor-acceptor complexes, electron transfer in the thermal and photochemical activation of, in organic and organometallic reactions. 29, 185 Electron spin resonance, identification of organic free radicals, 1, 284 Electron spin resonance, studies of short-lived organic radicals, 5, 23 Electron storage and transfer in organic redox systems with multiple electrophores, 28, 1 Electron transfer, 35, 117... 

Small amounts of organic radicals are formed continually in the skin during photolysis (in a process with rate constant k( )). The radicals are consumed immediately by natural substances in the skin, termed antioxidants (in a different process with rate constant k(2)). Vitamin C (L-(+)-ascorbic acid, IV) is one of the best naturally occurring antioxidants. Red wine and tea also contain efficient antioxidants. 

The reaction of benzene with Cu(II) and Fe(III)-exchanged hectorites at elevated temperatures produced a variety of organic radical products, depending on the concentration of water in the reaction medium and the reaction time (90). The formation of free radicals was accompanied by a reduction in oxidation state of the metals, a process that had a zero-order dependence on the metal ion concentration. Under anhydrous conditions the free radicals appeared to populate sites in the interlayer region, the activation energies under these conditions being lower than in the hydrated samples. 

The intrinsic instability of organocopper] 11) compounds is most probably associated with the redox properties of copper. Decomposition of organocopper] 11) compounds can occur by two different routes (i) formation of an organocopper]I) compound and an organic radical R" that can undergo further reactions, which formally represents a one-electron reduction process, and (ii) direct formation of R-R and Cu]0), which is formally a two-electron reduction process (reductive elimination cf Eqns. 1 and 2 in Scheme 1.3). 

The hydrogen abstraction from the Si—H moiety of silanes is fundamentally important not only because it is the method of choice for studying spectroscopically the silyl radicals but also because it is associated with the reduction of organic molecules, process stabilizers and organic modification of silicon surfaces. 

Besides solvation, a solvent can also participate in entrainment of ion-radical transformations. The reaction between tertiary aliphatic nitro compounds and the sodium derivative of nitromethane, NaCH2N02, is an example (Kornblum and Erickson 1981). To prepare NaCHjNOj, nitromethane is treated with sodium hydride. Then a tertiary aliphatic nitro compound is introduced into the solution formed. Several organic solvents were probed and CHjSOjCHj (DMSO) turned out to be the most effective. Kornblum and Erickson (1981) attributed this result to the formation of small amounts of NaCH2SOCH3 (sodium dimsyl) that was produced from DMSO as a result of its reaction with sodium hydride. Sodium dimsyl acts as a powerful one-electron reducer that induces the following chain anion-radical process ... 

NaClO, or else in the two-phase system but with a quaternary ammonium (viz. AUquat) ion as a phase-transfer catalyst, overoxidation to the corresponding carboxylic acid is obtained (entry 4). Therefore, by proper choice of the experimental conditions, a synthetically useful distinction in products formation can be made for the oxidation of primary alcohols, even though we are far from a satisfactory understanding of the reason behind this different behaviour. In fact TEMPO, as a well-known inhibitor of free-radical processes is allegedly responsible for the lack of overoxidation of an aldehyde to carboxylic acid (entry 3) this notwithstanding, TEMPO is also present under those conditions where the overoxidation does occur (eutry 4). Moreover, a commou teuet is that the formation of the hydrated form of an aldehyde (in water solution) prevents further oxidation to the carboxylic acid however, both entries 3 and 4 refer to water-organic solutions, and their... 

Already in 1982, it was suggested that the intermediate chromium(V) state is involved in the carcinogenic process.9 Reactive Cr(V) and Cr(IV) intermediates may be harmful in many ways acting as tyrosine phosphatase inhibitors, or by forming organic radicals upon reaction with cellular reductants, which in turn can react with O2 and lead to reactive oxygen species.10 Reaction of chromium(VI) with... 

Fet us start this section with real-time measurements of the crystallization process of highly ordered thin films of the molecular organic radical / -NPNN grown from the vapour phase on glass substrates (Caro et al, 2000). These films exhibit 2D... 

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