Free radicals paramagnetism

Ph3C, R3C (free radicals) Paramagnetic species of varying stability... 

The term spin (unpaired electron) is commonly used to refer to any species, e.g., free radical, paramagnetic ion, which gives an ESR spectrum. 

For a sample to be EPR/ESR active, it must have one or more unpaired electrons. Stable free radicals, paramagnetic metal ions, and irradiated materials are some examples of such materials. The amount of sample required depends on the type of spectrometer (what band is used) and on the type of experiment—CW, pulsed, and double-resonance experiments like electron nuclear double resonance (ENDOR) (discussed in the following)—but in general, liquid and solid samples can be measured. Volumes of sample required range from 20 pL to 1 mL at concentrations of 10 nM to 20 mM for most experiments. 

In certain solid-phase materials, free radicals - paramagnetic species containing unpaired electrons - form upon irradiation. The concentration of these free radicals can be related to absorbed dose by electron paramagnetic resonance (EPR) analysis, sometimes referred to as... 

Smaller B, Remko J R and Avery E C 1968 Electron paramagnetic resonance studies of transient free radicals produced by pulse radiolysis J. Chem. Rhys. 48 5174-81... 

Magnetic susceptibiUty measurements indicate that the organic part of the coal is diamagnetic, having traces of paramagnetic behavior resulting from free radicals or unpaired electrons (6). 

The reactivity of NO towards atoms, free radicals, and other paramagnetic species has been much studied, and the chemiluminescent reactions with atomic N and O are important in assaying atomic N (p. 414). NO reacts rapidly with molecular O2 to give brown NO2, and this gas is the normal product of reactions which produce NO if these are carried out in air. The oxidation is unusual in following third-order reaction kinetics and, indeed, is the classic... 

Studies on the formation and reactivity of P-centered radicals continue to be a versatile source of mechanistic information and reactions of interest in synthetic chemistry. Various new persistent or stable P-centered radicals have been described and could find applications as paramagnetic probes. The possibility of influencing the properties of organic free radicals bearing an appropriately located phosphorus group should find interesting applications. 

Hyperfine coupling constants provide a direct experimental measure of the distribution of unpaired spin density in paramagnetic molecules and can serve as a critical benchmark for electronic wave functions [1,2], Conversely, given an accurate theoretical model, one can obtain considerable information on the equilibrium stmcture of a free radical from the computed hyperfine coupling constants and from their dependenee on temperature. In this scenario, proper account of vibrational modulation effects is not less important than the use of a high quality electronic wave function. 

Connor, H.D., Gao, W., Nukina, S., Lemasters, J.J., Mason, R.P. and Thurman, KG. (1992). Evidence that free radicals are involved in graft failure following orthotopic liver transplantation in the rat an electron paramagnetic resonance spin trapping study. Transplantation 54, 199-204. 

Up to date, several experimental techniques have been developed which are capable of detecting some of these particles under ordinary thermodynamic conditions. One can use these methods to keep track of transformations of the particles. For instance, it is relevant to mention here the method of electron paramagnetic resonance (EPR) with sensitivity of about 10 particles per cm [IJ. However, the above sensitivity is not sufficient to study physical and chemical processes developing in gaseous and liquid media (especially at the interface with solids). Moreover, this approach is not suitable if one is faced with detection of particles possessing the highest chemical activity, namely, free radicals and atoms. As for the detection of excited molecular or atom particles... 

Recently McConnell has introduced the technique of labelling proteins lipid membranes, and DNA, with a stable organic free radical, the nitro-xide radical, see reference (24). A measurement of the line shapes of the ESR signal of this label has revealed the rotational times of the molecules to which it is bound. If paramagnetic analogues of the anti-tumour compounds are found then their progress within a cell will be readily followed using ESR. Complexes of all the metals of Table 1 with odd numbers of electrons (d1, d3, d5 and d1) are potentially useful. Thus... 

Group VIA (Cr, Mo, W). y-Radiolysis studies have been carried out for the simple hexacarbonyls (31,32) and for certain carbonyl iodides (33) and cyclopentadienyl carbonyl iodides (34). In the case of the hexacarbonyls (31,32), two free-radical products have been detected and characterized for Cr(C0)6, weak unidentified EPR signals have been observed for Mo(C0)6, but irradiated W(C0)6 apparently contains no detectable paramagnetic centres. 

J. Kroh, B.C. Green, and J.W.J. Spinks, Electron paramagnetic resonance (EPR) studies on the production of free radicals in hydrogen peroxide at liquid nitrogen temperature. J. Am. Chem. Soc. 83, 2201-2202 (1961). 

Early attempts to fathom organic reactions were based on their classification into ionic (heterolytic) or free-radical (homolytic) types.1 These were later subclassified in terms of either electrophilic or nucleophilic reactivity of both ionic and paramagnetic intermediates - but none of these classifications carries with it any quantitative mechanistic information. Alternatively, organic reactions have been described in terms of acids and bases in the restricted Bronsted sense, or more generally in terms of Lewis acids and bases to generate cations and anions. However, organic cations are subject to one-electron reduction (and anions to oxidation) to produce radicals, i.e.,... 

On the other hand, the presence of a short-lived free radical was confirmed first from an elegant experiment in 1929 by Paneth and Hofeditz [44], although the existence of paramagnetic species was pointed out in the middle of the 19th century by Faraday [45]. When tetramethyllead was thermolyzed, a methyl radical was postulated to be formed as the reaction intermediate (Eq. 2)... 

The initial product of the inhibition step is not known in this case and may be a molecular complex.8 The direct reaction of the ethane with the peroxy radical is an example of a covalent compound giving a reaction resembling that of a related free radical. The molecular weight determination by Gomberg was therefore a necessary part of the proof that he was dealing with radicals and not merely an unusually reactive hydrocarbon. The presence of free radicals has since been confirmed by measurements of the paramagnetic susceptibility and the paramagnetic resonance absorption.9-10 The latter evidence also rules out an alter-... 

The primary measure of the amount of free radical must depend on those properties unambiguously due to the unpaired electron. In the past the most common method has been the measurement of the paramagnetic susceptibility, now subject to difficulties of quantitative interpretation. The method of paramagnetic resonance absorption is... 

When one of the aromatic groups of the triarylmethyl free radical is replaced by an alkyl group, a decrease in stability due to a loss of resonance stabilization is to be expected. The paramagnetism and reactions associated with these less stable radicals will therefore appear only when the ethane is heated well above room temperature, the dissociation being endothermic. The rate of formation, but not the equilibrium constant, is experimentally accessible for these radicals since the radical once formed is subject to rearrangement, cleavage, and disproportionation reactions ... 

The decomposition of aliphatic peroxides produces oxygen radicals too unstable for paramagnetic measurement. These radicals initiate the polymerization of olefins and give the complex mixtures of decomposition products associated with radical mechanisms. On the other hand, aliphatic peroxides are also capable of polar decomposition reactions, a subject to be taken up in Chapter VIII. The characteristic reactions of the less stable oxygen free radicals are /3-cleavage to form... 

Metal ketyls are ion-radicals analogous to semiquinone ion radicals and may be considered either oxygen or carbon free radicals. They are readily prepared by treating aromatic ketones with alkali metals in dry ether, benzene, or liquid ammonia under an inert atmosphere.124 125 Benzophenone potassium has been shown to be paramagnetic in the solid state.126... 

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