Radical anion decay

The radical-anions of aliphatic nitrocompounds are detectable in aqueous solution as transient intermediates formed during continuous electrolysis in the cavity of the esr spectrometer [4], Decay of the species occurs by protonation and then further reactions. 2-Methyl-2-nitropropane has no acidic hydrogens so that it can be examined in aqueous alkaline solution where the radical-anion is not protonated. Over the pH range 9-11, this radical-anion decays by a first order process with k = 0.8 0.1 s at 26 C. Decay results from cleavage of the carbon-nitrogen bond to give a carbon centred radical and nitrite ion. Ultimately, the di-(ferr,-butyI)nitrone radical is formed in follow-up reactions [5],... 

A dramatic difference was observed in the behavior of porphyrin radical anions that contain phenyl v . pyridinium substituents at the meso positions. It was suggested that the radical anions decay either via protonation, to form a neutral radical, or disproportionation, to form a dianion, which then protonates very rapidly. The dianion can take-up a proton at a meso site to form a phlorin anion or take up two protons at a pyrrole ring to form a chlorin. 

When the radical cation and radical anion decay completely after laser pulse, the generated radical ion pair returns to the corresponding neutral ground state by the back electron-transfer process [60]. When the solvent is highly polar, the generated radical ions are solvated as free radical ions thus, the back electron transfer obeys second-order kinetics [Eq. (6)]. On the other hand, in the less-polar solvents, the radical ions are present as geminate ion pairs thus, the back electron transfer obeys first-order kinetics [Eq. (7)] ... 

The combination of electrochemical and EPR studies can provide valuable information about unstable S-N radical species. A classic early experiment involved the electrochemical reduction of S4N4 to the anion radical [S4N4] , which was characterized by a nine-line EPR spectrum. The decay of the radical anion was shown by a combination of EPR and... 

Morishima et al. [75, 76] have shown a remarkable effect of the polyelectrolyte surface potential on photoinduced ET in the laser photolysis of APh-x (8) and QPh-x (12) with viologens as electron acceptors. Decay profiles for the SPV (14) radical anion (SPV- ) generated by the photoinduced ET following a 347.1-nm laser excitation were monitored at 602 nm (Fig. 13) [75], For APh-9, the SPV- transient absorption persisted for several hundred microseconds after the laser pulse. The second-order rate constant (kb) for the back ET from SPV- to the oxidized Phen residue (Phen+) was estimated to be 8.7 x 107 M 1 s-1 for the APh-9-SPV system. For the monomer model system (AM(15)-SPV), on the other hand, kb was 2.8 x 109 M-1 s-1. This marked retardation of the back ET in the APh-9-SPV system is attributed to the electrostatic repulsion of SPV- by the electric field on the molecular surface of APh-9. The addition of NaCl decreases the electrostatic interaction. In fact, it increased the back ET rate. For example, at NaCl concentrations of 0.025 and 0.2 M, the value of kb increased to 2.5 x 108 and... 

Another intermediate of the photolysis of TiO was observed in experiments with platinized particles (in the absence of polyvinyl alcohol). The spectrum shown in Fig. 22 is prraent immediately after the laser flash. The signal decays as shown by the inset in the figure. The rate of decay is not influenced by oxygen but is increased by oxidizable compounds such as Br ions in the solution. The broad absorption band in Fig. 22 with a maximum at 430 nm was attributed to trapped positive holes. Chemically, a trapped hole is an 0 radical anion. In homogeneous aqueous solution, 0 ... 

The resnlts from the TR experiments presented in Fignres 3.19-3.21 above were used to determine single exponential rate constants of 5.1 X 10 s for the decay of the ketyl radical, 1.6 X 10 s for the formation of the flnoranil anion and 8.4 X 10" s for the decay of the flnoranil radical anion. These rate constants snggest that the flnoranil radical anion is forming from the ketyl radical. A reaction mechanism for the intermo-lecular abstraction reaction can be described as follows ... 

Reaction step 5 in Scheme 3.1 can be rnled ont becanse the flnoranil ketyl radical (FAH ) reaches a maximum concentration within 100 ns as the triplet state ( FA) decays by reaction step 2 while the fluoranil radical anion (FA ) takes more than 500 ns to reach a maximum concentration. This difference snggests that the flnoranil radical anion (FA ) is being produced from the fluoranil ketyl radical (FAH ). Reaction steps 1 and 2 are the most likely pathway for prodncing the flnoranil ketyl radical (FAH ) from the triplet state ( FA) and is consistent with the TR resnlts above and other experiments in the literatnre. The kinetic analysis of the TR experiments indicates the fluoranil radical anion (FA ) is being prodnced with a hrst order rate constant and not a second order rate constant. This can be nsed to rnle ont reaction step 4 and indicates that the flnoranil radical anion (FA ) is being prodnced by reaction step 3. Therefore, the reaction mechanism for the intermolecular hydrogen abstraction reaction of fluoranil with 2-propanol is likely to predominantly occur through reaction steps 1 to 3. 

The second-order decays of the uncharged neutral radicals are very similar to those of the radical anions so that, perhaps surprisingly, the negative charge does not hinder the radical-radical interaction. 

FIGURE 14.7 Transient absorption spectra observed following pulse radiolysis of CAN and formate in argon-saturated aqueous 2% TX-100 (pH = 7.1). Inset Kinetic traces of CANH at 570 nm and CAN " at 720 nm, showing the decay of the radical anion and concomitant formation of the neutral radical. 

The electrochemical reduction of cycloheptatriene (CHT) in liquid ammonia takes place at about —2.5 V vs SCE and forms the radical anion of CHT. The radical anion is stable in ammonia on the voltammetric time scale but decays slowly by disproportionation and coupling reaction pathways to give respectively 1,3- and 1,4-cycloheptadienes (total yield 34-39%) and C14H18 (in yields of 55-58%) isomers which incorporate the bitropyl carbon skeleta20. 

During the decay of (A) no increase in dNP formation was noted, and dNP formation was found to be complete in shorter periods than 20 (xs. Thus (A) is no intermediate, but has instead been identified, by comparison with ESR-results, as the radical anion of dNA. 

Unfortunately, transient (B) absorbs almost exactly at the same wavelength as the final product dNP (Amax 400—410 nm). It is very likely a precursor of the radical anion, and it is considered to be an aromate-nucleopliile complex, which may decay to dNA, dNP or the radical anion (transient A). The latter ultimately may lead to photoreduction products, the major portion of it, however, returns to starting material. 

At pH < 7 the nitroxyl radicals do not undergo an observable heterolysis (khs 10 s ), but decay by bimolecular reactions. However, in basic solution an OH -catalyzed heterolysis takes place to yield the radical anion of the nitrobenzene and an oxidized pyrimidine. In the case of the nitroxyls substituted at N(l) by H (i.e. those derived from the free bases), the OH catalysis involves deprotonation at N(l) which is adjacent to the reaction site [= C(6)] (cf. Eq. 15) [26] ... 

Hydroxyl radicals were generated radiolytically in NaO-saturated aqueous solutions of thiourea and tetramethylthiourea. Conductometric detection showed that HO and a dimeric radical cation were produced. The dimeric radical cation is formed by addition of a primary radical to a molecule of thiourea. In basic solution, the dimeric radical cation decays rapidly to a dimeric radical anion, which is formed via neutralization of the cation and subsequent deprotonation of the neutral dimeric radical (Scheme 16). This was not observed in tetramethylurea. These dimeric radical cations of thiourea and tetramethylurea are strong oxidants and readily oxidize the superoxide radical, phenolate ion, and azide ion. 

In order to measure the absorption spectra, the radical anions were generated electrochemically in the optical path of a spectrophotometer. The absorption spectrum of 3,5-dinitroanisole radical anion (Figure 11, curve c) is very similar to that of the 550-570 nm species produced photochemically. So we believe this species to be the radical anion formed by electron transfer from the nucleophile to the excited 3,5-dinitroanisole and decaying by interaction with its surroundings including the nucleophile radical cation. The behaviour described seems to be rather general for aromatic nitro-compounds since it is observed with a series of these compounds with various nucleophilic reagents. 

During the decay of the 412 nm species an absorption at 512-550 nm builds up. An isosbestic point is observed at ca. 535 nm (Figure 12). The optical density of the solution continues to increase until about 1"5 ns after the exciting pulse and then remains constant (at 512-550 nm) up to the maximum time of measurement (10 /is). We think this last absorption to be due to the radical anion of 3,5-dinitroanisole (Figure 11, curve b) formed from the 412 nm species. 

The decay of a radical-anion can be followed directly by generating the intermediate within the cavity of an esr spectrometer through application of a controlled potential pulse to the cathode of a thin electrochemical cell [46]. Loss of the radical-anion is then followed by decay of the esr signal. Decay is second order in radical-ion concentration for dimethyl fumarate (k = 160 M s ) and for cin-namonitrile (k = 2.1 x 10 M s ) in dimethylformamide with tetrabutylammonium counter ion. Similar values for these rate constants have been obtained using purely electrochemical techniques [47]. 

Rate constants in excess of 10 M s are determined by pulse-radiolysis methods [4, 5]. High-energy irradiation of a solution containing the substrate and an excess of the aromatic species, generates the aromatic radical-anion. The decay of this by electron transfer to the substrate is followed using uv-spectroscopy and affords a rate constant for the second-order process. Slow rates of electron transfer are determined by adding the substrate to a solution of the aromatic radical-anion and following the reaction by conventional methods. 

Decay of arene hydrocarbon radical-anions formed during preparative scale electrochemical reduction in the presence of general acids involves protonation as... 

An early electrochemical study of corannulene revealed the presence of two well-defined polarographic waves with half-wave potentials of-1.88 and -2.36 V (r-butylammonium perchlorate in acetonitrile). The first wave represented a reversible, one-electron reduction leading to radical anion formation (emerald green solution) further characterized by UV-VIS and ESR. The second wave was reported to be associated with the formation of a bright red species which is not paramagnetic, but it is not believed to be the dianion, but rather some decay product of it. Treatment of THF solutions of 8 with sodium and potassium metals also led to the formation of the same species. ... 

Waygood, S. J., and W. J. McElroy, Spectroscopy and Decay Kinetics of the Sulfite Radical Anion in Aqueous Solution, J. Chem. Soc. Faraday Trans., 88, 1525-1530 (1992). 

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