Radicals by ESR spectroscopy

Morkovnik et al. (1989) found experimentally that the addition of an equimolar amount of 4-morpholino- or 4-dimethylaminoaniline to a suspension of nitrosyl perchlorate in 100 % acetic acid, dioxan, or acetonitrile yields a mixture of the diazonium perchlorate and the perchlorate salt of the amine radical cation, with liberation of gaseous nitric oxide. Analogous results in benzene, including evidence for radicals by ESR spectroscopy and by spin trapping experiments, were obtained by Reszka et al. (1990). 

In addition to the stabilization by suitable substituents and the absence of other termination reactions than recombination, it is the strength of the bond formed in the dimerization which is a necessary cofactor for the observation of free radicals by esr spectroscopy. The stability of nitroxides [4] or hydrazyls [5] (Forrester et al., 1968) derives not only from their merostabilized or captodative character but also from a weak N-N bond in the dimer. The same should be the case for captodative-substituted aminyls... 

The formation of the RZn(f-BuDAB) radicals is notable and it appeared that these radicals are examples of persistent organometallic radicals in equilibrium with their C—C coupled dimer. These dimers could be independently synthesized in high yield from the reaction of (f-BuDAB)K and the corresponding RZnCl compound. The rate constant of the equilibrium between the persistent radical and its C—C coupled dimer is sufficiently small to study the dimers by NMR spectroscopy and the radicals by ESR spectroscopy . The obtained ESR data are in agreement with a structure for the radical in which the zinc atom adopts a trigonal planar geometry. In this respect it should be noted that the in situ... 

II/III Structure of free radicals by ESR spectroscopy, including spin trapping (no direct organometallic content) 71... 

ESR studies 112,114-118a) are also consistent with the formation of free radicals upon photolysis of alkylcobalamin and coenzyme Bi2- For example, Lappert and co-workers 116) demonstrated that homolysis of the cobalt-alkyl bond occurs upon photolysis of coenzyme B12 and ethylcobalamin by trapping the S -deoxyadenosyl and ethyl radicals produced with (CH3)3CN0. They were able to detect the spin-trapped (CH3)3CN(0)R radicals by ESR spectroscopy. Homolysis of the cobalt-methyl bond was also shown to occur upon anaerobic photolysis of methylcobalamin 117). However, the presence of traces of oxygen in the methanol solvent was shown to affect signiflcantly the photochemistry of methylcobalamin 118). Indeed, under those conditions, the 5,S-dimethyl-1-pyrroline iV-oxide (DMPO) spin adducts of both the methyl and hydrogen radicals, 113 and 114, respectively, were detected by ESR spectro-... 

Chapter 7 is devoted to direct ESR measurements of propagating radicals by ESR spectroscopy under conditions similar to the conventional radical polymerization. Special cavities used for this purpose are described. Directly measured rate constants are compared with the values obtained by other methods. 

Direct quantification of propagahng radicals by ESR spectroscopy is known as one of the most promising techniques for the determination of the rate constants [103], An example... 

Rxn. with Co irradiation -> nature of radicals by ESR spectroscopy (693). Polarographic reduction, followed by rxn. with numerous inorganic, organic and organometalllc entities (963, 966-8). 

The diaziridine ring exhibits a surprising stability towards strong oxidizing agents. Diaziridines unsubstituted at both N atoms can be transformed into diazirines by dichromate in acidic solution or by chlorine (Section 5.08.4.3). Radical attack by decomposing peroxide converts (136) to the diaziridinyl radical (137), as evidenced by ESR spectroscopy (76TL4205). 

Of some relevance in this connection is a study216 on the structure of the anion radicals formed when diaryl sulphones react with n-butyllithium in hexane-HMPA solution under an argon atmosphere. Apparently, a dehydrogenative cyclization and a further one-electron reduction occurs to produce the anion radicals of substituted dibenzothiophene-S, S-dioxides. These anion radicals were studied by ESR spectroscopy. 

As seen before, the radical cation of dimethyl sulfoxide (CH3)2SO has been detected by ESR spectroscopy among other radicals when DMSO glasses at 77 K are submitted to y-irradiation28. It has also been reported in pulse radiolysis experiments30 (Table 6). Constant current electrochemical oxidation of bis(dialkylamino)sulfoxides (R2N)2SO gives rise to radical cations which have been detected by ESR spectroscopy33. 

Sulfinyl radicals studied by ESR spectroscopy have been generated photolytically either from the appropriate sulfoxide or from the corresponding chlorides, namely10,12"14,16... 

The photo-Kolbe reaction is the decarboxylation of carboxylic acids at tow voltage under irradiation at semiconductor anodes (TiO ), that are partially doped with metals, e.g. platinum [343, 344]. On semiconductor powders the dominant product is a hydrocarbon by substitution of the carboxylate group for hydrogen (Eq. 41), whereas on an n-TiOj single crystal in the oxidation of acetic acid the formation of ethane besides methane could be observed [345, 346]. Dependent on the kind of semiconductor, the adsorbed metal, and the pH of the solution the extent of alkyl coupling versus reduction to the hydrocarbon can be controlled to some extent [346]. The intermediacy of alkyl radicals has been demonstrated by ESR-spectroscopy [347], that of the alkyl anion by deuterium incorporation [344]. With vicinal diacids the mono- or bisdecarboxylation can be controlled by the light flux [348]. Adipic acid yielded butane [349] with levulinic acid the products of decarboxylation, methyl ethyl-... 

More recently, 84 may have been identified by ESR spectroscopy of solutions of Li2S ( >6) in DMF at 303 K. The lithium polysulfide was prepared from the elements in liquid ammonia. These polysulfide solutions also contain the trisulfide radical anion ( 2.0290) but at high sulfur contents a second radical at g=2.031 (Lorentzian lineshape) was formed which was assumed to be 84 generated by dissociation of octasulfide dianions see Eq. (32) [137],... 

The species S3 (absorbing at 420 nm) and S4 (absorbing at 530 nm) have been detected by reflection spectra in the condensate but the formation of S4 is unexplained [16]. S3 and SO2 have also been observed by Raman spectroscopy in such samples [15] (the expected S4 Raman line at 678 cm was probably obscured by the SS stretching mode of S2O at 673 cm but a shoulder at the high-frequency side of the S2O line indicates that some S4 may have been present). While the reddish colors turn yellow on warming at about -120 °C, the sulfur radicals could be observed by ESR spectroscopy up to 0 °C [10]. If the condensation of S2O gas is performed very slowly at -196 °C the condensate is almost colorless and turns red only if the temperature is allowed to increase slowly. Hence, it has been suspected that S2O is actually colorless like SO2. 

On condensation at low temperatures, on dissolution in inert solvents or on raising its partial pressure substantially above 1 mbar (100 Pa) S2O polymerizes with partial disproportionation. Since sulfur radicals have been detected in such condensates by ESR spectroscopy [10] it has been proposed that a radical-chain reaction takes place according to Scheme 5. 

The term persistent is typically applied to long-lived radicals7" which in a majority of cases can be characterized by ESR spectroscopy. " However, the lifetime of those radicals can vary rather broadly from several minutes to months, depending on the environment around the radical center. In this contribution, we will use the terminology of persistent radicals for those radical species with a relatively long lifetime however, those persistent radicals that can be isolated as individual room temperature stable compounds and in many cases characterized by X-ray crystallography will be specifically named as stable radicals (for the chemistry of stable radicals, see Section 2.2.4). 

Electrochemical methods have been used extensively to elucidate the mechanism of reduction of tetrazolium salts. In aprotic media, the first step is a reversible one-electron reduction to the radical 154 as confirmed by ESR spectroscopy.256,266 As shown in Scheme 26, this radical can then disproportionate to the tetrazolium salt and the formazan anion (166) or take up another electron to the formazan dianion (167). The formation of the dianion through a direct reduction or through the intermediate tetrazolyl anion (168) has also been proposed.272-28 1,294 In aqueous solutions, where protonation/deprotonation equilibria contribute to the complexity of the reduction process, the reduction potentials are pH dependent and a one-electron wave is seldom observed. 

The cyclopentadienyl radical is well established by ESR spectroscopy while the fate of the Sn(I) radical is uncertain183). It should nevertheless be noted that no Sn(III) radical is formed, proving again the difference between cyclopentadienylstannylenes and other molecular tin(II) compounds. 

When several magnetically equivalent nuclei are present in a radical, some of the multiplet lines appear at exactly the same field position, i.e., are degenerate , resulting in variations in component intensity. Equivalent spin-1/2 nuclei such as 1H, 19F, or 31P result in multiplets with intensities given by binomial coefficients (1 1 for one nucleus, 1 2 1 for two, 1 3 3 1 for three, 1 4 6 4 1 for four, etc.). One of the first aromatic organic radical anions studied by ESR spectroscopy was the naphthalene anion radical,1 the spectrum of which is shown in Figure 2.2. The spectrum consists of 25 lines, a quintet of quintets as expected for hyperfine coupling to two sets of four equivalent protons. 

Monitored by ESR spectroscopy, the continuous radiolysis of furan derivatives in water leads, in effect, to the addition of the hydroxy group at the 2-position ring opening of the resultant radical is rapid.2Sla... 

Note that the identity of the radical pair in equation (52) is confirmed by the observation of both the TCNE anion radical and hydrogen atom (H ) by ESR spectroscopy in a frozen matrix.188... 

Several thiadiazole-fused organic radicals have been characterized by ESR spectroscopy, and significant spin delocalization can be seen from the hyperfine coupling constants (hfcc s) N (Table 5). 

Probably, the most convincing proof of free radical mechanism of peroxynitrite reactions is the formation of dityrosine [117,118]. It has been suggested [118] that the nitric dioxide radical is responsible for the formation of both 3-nitrotyrosine and dityrosine (Figure 21.1), however, hydroxyl radicals (which were identified in this system by ESR spectroscopy [119]) may also participate in this process. Pfeiffer et al. [118] proposed that dityrosine is predominantly formed at low fluxes of superoxide and nitric oxide, which corresponds to in vivo conditions, however, this observation was not confirmed by Sawa et al. [117],... 

Heterolytic mechanism is important in the absence of substrates and homolytic one occurs in the presence of oxidizable biomolecules. Bonini et al. [139] were able to identify C03 radical in the reaction of peroxynitrite with carbon dioxide by ESR spectroscopy. 

Various hydroxyl and amino derivatives of aromatic compounds are oxidized by peroxidases in the presence of hydrogen peroxide, yielding neutral or cation free radicals. Thus the phenacetin metabolites p-phenetidine (4-ethoxyaniline) and acetaminophen (TV-acetyl-p-aminophenol) were oxidized by LPO or HRP into the 4-ethoxyaniline cation radical and neutral V-acetyl-4-aminophenoxyl radical, respectively [198,199]. In both cases free radicals were detected by using fast-flow ESR spectroscopy. Catechols, Dopa methyl ester (dihydrox-yphenylalanine methyl ester), and 6-hydroxy-Dopa (trihydroxyphenylalanine) were oxidized by LPO mainly to o-semiquinone free radicals [200]. Another catechol derivative adrenaline (epinephrine) was oxidized into adrenochrome in the reaction catalyzed by HRP [201], This reaction can proceed in the absence of hydrogen peroxide and accompanied by oxygen consumption. It was proposed that the oxidation of adrenaline was mediated by superoxide. HRP and LPO catalyzed the oxidation of Trolox C (an analog of a-tocopherol) into phenoxyl radical [202]. The formation of phenoxyl radicals was monitored by ESR spectroscopy, and the rate constants for the reaction of Compounds II with Trolox C were determined (Table 22.1). 

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